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Polymer Testing 36 (2014) 6268

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material behaviour

Crystallization behavior and nucleation analysis of isotactic


polypropylene with a multiamide nucleating agent
Ting Xu a, Yaming Wang a, *, Yanmei Xu a, Wei Cao a, Chuntai Liu a,
Changyu Shen a, b
a

National Engineering Research Center for Advanced Polymer Processing Technology, Key Laboratory of Advanced Materials Processing &
Mold, Ministry of Education, Zhengzhou University, 97 Wenhua Road, Zhengzhou 450002, China
b
Department of Engineering Mechanics, Dalian University of Technology, Dalian 116024, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 14 February 2014
Accepted 20 March 2014

The effect of one of the 1,3,5-benzenetrisamide derivatives, N,N,N-tricyclohexyl-1,3,5benzenetricarboxylamide (dened here as TMC), on the crystallization behavior of isotactic
polypropylene (iPP) was investigated by differential scanning calorimetry. TMC shows
excellent nucleating effect on iPP. The nucleation efciency of the blends reaches 30% even
at a very low loading of 0.05 wt% TMC. For 0.1 wt% TMC, the crystallization half-time of the
blend decreases from 39.41 to 3.97 min at 136  C, compared with pure iPP. The isothermal
crystallization data were further analyzed by the Avrami model. The values of the Avrami
exponent of the blends are comparable to that of pure iPP, indicating that the presence of
TMC does not change the crystallization mechanism of the matrix. The presence of TMC
increases signicantly the nuclei density of iPP but has no discernible effect on its crystalline structure, evidenced by polarized optical microscopy and wide angle X-ray
diffraction measurements.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Isotactic polypropylene
Multiamide
Crystallization kinetics
Nucleation
Morphology

1. Introduction
Incorporation of nucleating agents with isotactic polypropylene (iPP) is an effective method to improve properties of iPP related to crystallization and morphology [16].
Most common are heterogeneous nucleating agents based
on inorganic particles (e.g., talc [7] and clay [8]) or organic
salts (e.g., zinc phenylphosphonate (PPZn) [9] and sodium
benzoate [10]). However, these nucleating agents are
intrinsically insoluble in the polymer matrix and, hence,
have to be nely dispersed during melt processing [710].
Recently, organic nucleating agents, which are soluble in
the polymer melt and crystallize into small supramolecular
objects prior to the polymer crystallization, have gained
* Corresponding author. Tel.: 86 37163887567;
37163887570.
E-mail address: wangyaming@zzu.edu.cn (Y. Wang).
http://dx.doi.org/10.1016/j.polymertesting.2014.03.015
0142-9418/ 2014 Elsevier Ltd. All rights reserved.

fax:

86

growing interest. Dibenzylidene sorbitol derivatives are


typical examples for this class of additive, which were
particularly developed for the nucleation and clarication
of iPP [1113]. Despite its commercial use, sugar-based
nucleating agents exhibit severe drawbacks, such as low
chemical and thermal resistance. The latter is also limiting
their use as additives for high melting semicrystalline
polymers.
1,3,5-Benzenetrisamide derivatives represent an alternative class of nucleating agents avoiding the mentioned
drawbacks and showing remarkable nucleation effects in
iPP [14], poly(lactic acid) (PLA) [1517], poly(vinylidene
uoride) (PVDF) [18] and poly(butylene terephthalate)
(PBT) [19]. Depending on their chemical structure, concentration and temperature, 1,3,5-benzenetrisamide derivatives are soluble in the iPP melt, and a selected few are
able to efciently nucleate and clarify iPP. N,N,N-tricyclohexyl-1,3,5-benzenetricarboxylamide (trade name:

T. Xu et al. / Polymer Testing 36 (2014) 6268

63

TMC-328, abbreviated as TMC in this article) is one of these


derivatives. The optical properties, mechanical properties,
thermal stability, and electret properties of iPP nucleated
with TMC has been studied [14,20]. However, to the best of
our knowledge, the crystallization behavior and nucleation
ability of TMC-nucleated iPP have not been investigated in
detail.
In this paper, the crystallization behavior, morphology
and crystal structure of iPP nucleated by TMC were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray
diffraction (WAXD). The isothermal crystallization kinetics
was analyzed based on the Avrami model [21,22], While the
nucleation efciency (NE) was analyzed based on a method
proposed by Fillon et al. [23].
2. Experimental section
2.1. Materials
The iPP used in this study was F401, a commercial
product of Lanzhou Petroleum Chemical (China) with a
tacticity of 97%. The number- and weight-average molecular weights of this resin were 160 and 530 kg/mol,
respectively [24]. The multiamide compound (TMC-328),
i.e., N,N,N-tricyclohexyl-1,3,5-benzenetricarboxylamide,
was kindly supplied by Shanxi Provincial Institute of the
Chemical Industry, China. Its chemical structure is shown in
Fig. 1.
2.2. Sample preparation
Pure iPP and iPP/TMC blends were prepared by direct
mixing in a Haake mixing chamber at 180  C 20 rpm for
8 min. The iPP and the nucleating agent were used without
further treatment. The weight fractions of TMC in iPP
blends were 0, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8 and 1 wt%, and
these blends were dened as pure iPP, TMC0.05, TMC0.1,
TMC0.2, TMC0.3, TMC0.5, TMC0.8 and TMC1.

O
HN

Fig. 2. DSC curves of (a) nonisothermal crystallization and (b) subsequent


melting for iPP/TMC samples with different TMC contents.

2.3. DSC measurements


A DSC 2920 (TA Instruments) was used to study the
crystallization behavior of pure iPP and iPP/TMC blends.
Calibration for the temperature and energy scale was carried out using a pure indium standard. The weight of
sample was about 7 mg. Each sample was used only once
and all the runs were carried out in a nitrogen atmosphere.
For nonisothermal crystallization, the samples were heated
to 200  C at 20  C/min and held for 5 min to erase the
thermal history. Then, the melt was cooled to crystallize at

HN

O
HN
O

Fig. 1. Chemical structure of TMC-328.

Table 1
Characteristic data of nonisothermal crystallization and subsequent
melting processes for pure iPP and iPP/TMC blends.
Sample

Tp ( C)

Tm ( C)

DHc (J/g)

Xc (%)

Pure iPP
TMC0.05
TMC0.1
TMC0.2
TMC0.3
TMC0.5
TMC0.8
TMC1

120.7
128.1
128.7
129.3
130.7
132.3
133.4
133.8

164.1
165.7
166.1
166.1
166.3
166.2
164.4
165.1

114.5
118.6
117.1
114.7
117.6
116.0
114.1
118.0

54.8
56.7
56.0
54.9
56.3
55.5
54.6
56.5

64

T. Xu et al. / Polymer Testing 36 (2014) 6268

60

2.4. POM measurements


The spherulitic morphologies of the samples were
investigated on an Olympus BX61 polarizing microscope,
equipped with a digital camera system and a Linkam THMS
600 hot stage. A thin lm of each sample was sandwiched
between two glass slides. After melting at 200  C for 5 min,
it was quickly cooled to the selected isothermal crystallization temperature (140  C) and then the crystallization
process was recorded.

NE (%)

40

20

2.5. WAXD measurements

0
0.0

0.2

0.4
0.6
0.8
TMC content (wt %)

The wide angle X-ray diffraction (WAXD) patterns of


iPP/TMC blends were recorded on a Bruker NanoStar system. Monochromatized CuKa (l 1.54 
A) radiation was
used. The sample-to-detector distance was 108 mm.

1.0

Fig. 3. Variation of NE with TMC content.

3. Results and discussion


2  C/min and reheated to 200  C at 10  C/min to observe the
melting behavior. For isothermal crystallization, the samples were heated to 200  C at 20  C/min and held for 5 min
to eliminate prior thermal history, the melt was then
cooled rapidly to the designated crystallization temperature (Tc) and, nally, the DSC traces were recorded during
the isothermal process.

3.1. Nonisothermal crystallization


The effects of the TMC on the nonisothermal crystallization of iPP were rst investigated by DSC. Fig. 2 presents
the DSC curves recorded during the cooling and subsequent
heating processes for iPP/TMC samples with different TMC

0.02 W/g

0.1 W/g

50

100
t (min)

150

200

Exothermic

134 C
o
136 C
o
138 C
o
140 C
o
142 C

10

20

30

t (min)

40

20

30
t (min)

40

50

0.1 W/g

0.1 W/g

10

50

60

Exothermic

134 C
o
136 C
o
138 C
o
140 C
o
142 C

Exothermic

Exothermic

132 C
o
134 C
o
136 C
o
138 C
o
142 C

136 C
o
138 C
o
140 C
o
142 C
o
144 C

10

20

30

40

t (min)

Fig. 4. DSC exotherms of isothermal crystallization for (a) pure iPP, (b) TMC0.05, (c) TMC0.1, and (d) TMC0.5 at indicated Tcs.

T. Xu et al. / Polymer Testing 36 (2014) 6268

contents. The thermal properties such as the crystallization


peak temperature (Tp), the melting temperature (Tm), the
heat evolved during crystallization (DHc) and the absolute
degree of crystallinity (Xc) can be obtained from DSC
analysis, and the results are summarized in Table 1. Xc was
evaluated by comparing DHc with the heat of fusion of a
0
0
perfect crystal (DHm
), taken as DHm
209 J/g [25], that is,
0
Xc DHc/DHm  100%. The crystallization and melting
behavior of iPP depends on the TMC content. As seen in
Fig. 2a, with the addition of 0.05 wt% TMC, the value of Tp is
about 7  C higher than that of pure iPP. The crystallization
exotherm peak shifts to higher temperature successively
with increasing TMC content. The values of Xc keep almost
constant at 5557% for the blends, irrespective of the TMC
content. In Fig. 2b, all iPP/TMC blends show a single
endothermic peak and the melting temperature of iPP increases, in general, with increasing TMC content.
3.2. Nucleation efciency
To directly understand the effectiveness of TMC, the NE
was estimated based on the methodology developed by
Fillon et al. [23] according to the following equation:

NE 100

TcNA  Tc1
Tc2max  Tc1

(1)

65

where TcNA, Tc1, and Tc2max are crystallization peak temperatures of the nucleated, non-nucleated and self-nucleated
polymer, respectively. It should be noted that the Fillon
method assumes that the highest crystallization temperature is achieved with self-nucleation. Thus, the crystallization temperature of a non-nucleated polymer is considered
as the lower boundary of the nucleation efciency scale,
and that of the self-nucleated polymer as the upper
boundary. According to this scale, the NE of nucleated iPP by
TMC was calculated considering a value of Tc2max 145.7  C
[9], and the results are shown in Fig. 3. The value of NE
reaches 30% even at a very low loading of 0.05 wt% TMC.
With further increase of the TMC content, the value of NE
increases gradually and reaches 52% at 1 wt% of TMC. Note
that the values of NE reported in the literature vary from 5
to 70% [9,23,26]. For instance, with 1 wt% nucleating agent,
the values of NE for iPP nucleated by talc [26] and PPZn [9]
are 32 and 50%, respectively. These results indicate that
TMC acts as an effective nucleating agent for iPP.
3.3. Isothermal crystallization
The effect of TMC on the isothermal crystallization kinetics of iPP was further investigated using DSC. Fig. 4
shows the DSC curves for pure iPP and its blends crystallized at various temperatures (Tc). As can be seen, the

log(-ln(1-X(t)))

log(-ln(1-X(t)))

0
-1
132
134
136
138
140

-2
-3
0.0

0.4

0.8

1.2
log t

1.6

C
C
C
C
C

2.0

-1

2.4

-0.4

-2
-3

C
C
C
C
C

log(-ln(1-X(t)))

-1
134
136
138
140
142

134
136
138
140
142

-2

log(-ln(1-X(t)))

0.0

0.4

0.8
log t

1.2

C
C
C
C
C

1.6

0
-1
136
138
140
142
144

-2

C
C
C
C
C

-3
-0.8

-0.4

0.0

0.4

log t

0.8

1.2

1.6

-0.4

0.0

0.4
log t

0.8

1.2

1.6

Fig. 5. The representative Avrami plots of iPP and iPP/TMC blends at different Tcs for (a) pure iPP, (b) TMC0.05, (c) TMC0.1, (d) TMC0.5.

66

T. Xu et al. / Polymer Testing 36 (2014) 6268

crystallization peak of pure iPP is very broad. With the


incorporation of TMC, the crystallization peak sharpens and
the crystallization time shortens.
The relative crystallinity, X(t), can be obtained from the
ratio of the area of exotherm at crystallization time, t, to the
total area of exothermal peak, i.e.

,Z

Xt

dH=dtdt
0

dH=dtdt

(2)

Table 2
Parameters obtained from isothermal crystallization with different contents of TMC.
Sample

Tc ( C)

k (minn)

Pure iPP

132
134
136
138
140
134
136
138
140
142
134
136
138
140
142
136
138
140
142
144

2.3
2.4
2.6
2.4
2.3
2.4
2.4
2.6
2.4
2.4
2.7
2.3
2.5
2.6
2.6
2.3
2.3
2.3
2.5
2.7

2.37
5.61
4.92
3.13
2.90
5.36
1.67
2.68
1.95
7.12
7.34
2.90
5.89
1.05
3.62
1.44
6.51
1.60
2.66
4.29

TMC0.05

where dH/dt is the heat ow rate.


The well-known Avrami equation [21,22] was adopted
to describe the overall isothermal crystallization kinetics,
which assumed that the relative crystallinity developed
with the crystallization time,

TMC0.1

1  Xt exp  kt n

TMC0.5

(3)

where n is the Avrami exponent depending on the nature


of nucleation and growth geometry of the crystals, k is the
crystallization rate constant involving both nucleation and
growth rate parameters. For convenience, Eq. (3) is
generally rewritten in a double logarithmic form as
follows:

The Avrami parameters n and k can be obtained from


the slopes and intercepts, respectively, of the plots of log
[ln(1  X(t))] against log t. Fig. 5 shows such plots for
isothermal crystallization at indicated Tcs. The evaluated
results of n and k are summarized in Table 2. It can be seen
that the values of n range from 2.3 to 2.6 for pure iPP, which
is similar to the literature (2.32.6 at Tc 125137  C by
Manchado et al. [27], 2.43.7 at Tc 120135  C by Chen
et al. [28]), and range from 2.3 to 2.7 for the blends, irrespective of the TMC content. This indicates that the presence of TMC does not change the crystallization
mechanism of iPP matrix. A similar conclusion has been
drawn for a iPP/PPZn system [9]. It is clear that, the higher
the crystallization temperature, the smaller is the value of k
for all samples studied. Meanwhile, the value k of iPP/TMC
blends is higher than that of pure iPP at a given temperature, and increases with increasing TMC content.
The value of half-time of crystallization can also be
determined from the measured kinetics parameters, and is
calculated by the following equation:
1=n

t1=2 ln 2=k

(5)

The values of t1/2 calculated through Eq. (5) are listed in


Table 2. For 0.1 wt% TMC, the value of t1/2 of the blend
decreases from 39.41 to 3.97 min at 136  C, compared with
pure iPP. This indicates that the isothermal crystallization
of iPP can be enhanced signicantly by the incorporation of
TMC.
For more clarity, the crystallization rate can be
described further by the reciprocal of t1/2. The crystallization temperature dependence of 1/t1/2 for pure iPP and iPP/
TMC blends is shown Fig. 6.
Clearly, the crystallization rate of all the samples decreases with increasing Tc. Additionally, it can be seen that

t1/2 (min)

103
104
105
105
105
102
102
103
103
104
102
102
103
103
104
101
102
102
103
104

11.81
19.42
39.41
64.65
80.05
2.91
4.69
8.47
11.57
17.59
2.30
3.97
6.73
12.16
18.29
1.98
2.80
5.15
9.26
15.42

the overall crystallization rate presents a progressively


rising trend with increasing TMC content for a given Tc,
suggesting that TMC accelerates the crystallization of iPP
under isothermal conditions.
3.4. Spherulite morphology
The spherulite morphology of TMC-nucleated iPP was
compared with that of the pure iPP by POM analysis. Fig. 7
presents the POM photographs of pure iPP and iPP/TMC
blends crystallized at 140  C for 20 min. As shown in Fig. 7,
the pure iPP exhibits a larger size and lower density of
spherulites compared to its blends with TMC, indicating
that the nucleation density has been enhanced by the
addition of TMC. This observation further conrms that the
nucleation ability of TMC is very prominent on the

0.6

-1

(4)

1/t1/2(min )

log  ln1  Xt log k n log t






















Pure iPP
TMC0.05
TMC0.1
TMC0.5

0.4

0.2

0.0
132

134

136

138

140

142

144

Tc( C)
Fig. 6. Crystallization temperature dependence of 1/t1/2 for pure iPP and iPP/
TMC blends.

T. Xu et al. / Polymer Testing 36 (2014) 6268

67

Fig. 7. Polarized optical micrographs of (a) pure iPP, (b) TMC0.05, (c) TMC0.1, (d) TMC0.5, isothermally crystallization at 140  C for 20 min. The scales for all the
graphs are the same as image (a).

crystallization of iPP, which is in accordance with the


aforementioned DSC results.

crystal structure of iPP is unaffected by the addition


of TMC.

3.5. Crystalline structure

4. Conclusions

Fig. 8 shows the WAXD proles of iPP samples with


different TMC contents. Several diffraction peaks are seen,
which can be indexed as (110) at 2q 14.3 , (040) at
2q 17.0 and (130) at 18.7 of the typical a-form
monoclinic structure of iPP [29,30], indicating that the

TMC-nucleated iPP was prepared via melt-blending at


various TMC contents from 0.05 to 1 wt%. The crystallization behavior, crystalline structure and nucleation ability of
pure iPP and TMC-nucleated iPP were investigated in detail.
The quantitative analyses of NE reected that a small
amount of TMC can promote the nucleation of iPP effectively. The isothermal crystallization results revealed that
the overall crystallization rate is much faster in TMCnucleated iPP than in pure iPP and roughly increases with
the TMC loading level. The values of the Avrami exponent
of the blends are comparable to that of pure iPP, indicating
that the presence of TMC does not change the crystallization mechanism of iPP. The presence of TMC increases
signicantly the nuclei density of iPP but has no discernible
effect on its crystalline structure. The above observations
indicate that TMC is an efcient nucleating agent for iPP.
Acknowledgement

Fig. 8. WAXD patterns of iPP samples with different TMC contents.

This work is nancially supported by the National Basic


Research
Program
of
China
(973
Program)
(2012CB025903), the National Natural Science Foundation
of China (501100001809) (50873094), and the Key Project
of Science and Technology of Education Bureau of Henan
Province (14A430037).

68

T. Xu et al. / Polymer Testing 36 (2014) 6268

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