Академический Документы
Профессиональный Документы
Культура Документы
Polymer Testing
journal homepage: www.elsevier.com/locate/polytest
Material behaviour
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
63
O
HN
HN
O
HN
O
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
60
NE (%)
40
20
0
0.0
0.2
0.4
0.6
0.8
TMC content (wt %)
1.0
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.
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
,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
TMC0.1
1 Xt exp kt n
TMC0.5
(3)
t1=2 ln 2=k
(5)
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
0.6
-1
(4)
1/t1/2(min )
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.
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).
4. Conclusions
68
References
[1] S.S. Ray, M. Okamoto, Polymer/layered silicate nanocomposites: a
review from preparation to processing, Prog. Polym. Sci. 28 (2003)
1539.
[2] J. Menczel, J. Varga, Inuence of nucleating agents on crystallization
of polypropylene, J. Therm. Anal. 28 (1983) 161.
[3] T.L. Smith, D. Masilamani, L.K. Bui, Y.P. Khana, R.G. Bray,
W.B. Hammond, S. Curran, J.J. Jr. Belles, S. Binder-Castelli, The
mechanism of action of sugar acetals as nucleating agents for
polypropylene, Macromolecules 27 (1994) 3147.
[4] M. Dong, Z.-X. Guo, J. Yu, Z.-Q. Su, Study of the assembled
morphology of aryl amide derivative and its inuence on the nonisothermal crystallizations of isotactic polypropylene, J. Polym. Sci.,
Part B: Polym. Phys. 47 (2009) 314.
[5] M. Naffakh, C. Marco, G. Ellis, Novel polypropylene/inorganic
fullerene-like WS2 nanocomposites containing a b-nucleating agent:
isothermal crystallization and melting behavior, J. Phys. Chem. B
116 (2012) 1788.
[6] W. Hao, W. Yang, H. Cai, Y. Huang, Non-isothermal crystallization
kinetics of polypropylene/silicon nitride nanocomposites, Polym.
Test. 29 (2010) 527.
[7] P.M. McGenity, J.J. Hooper, C.D. Paynter, A.M. Riley, C. Nutbeem,
N.J. Elton, J.M. Adams, Nucleation and crystallization of polypropylene by mineral llers: relationship to impact strength, Polymer 33 (1992) 5215.
[8] A. Usuki, N. Hasegawa, M. Kato, Polymer-clay nanocomposites, Adv.
Polym. Sci. 179 (2005) 135.
[9] T. Xu, Y. Wang, D. He, Y. Xu, Q. Li, C. Shen, Nucleation effect of
layered metal phosphonate on crystallization of isotactic polypropylene, Polym. Test. 34 (2014) 131.
[10] G.-S. Jang, W.-J. Cho, C.-S. Ha, Crystallization behavior of polypropylene with or without sodium benzoate as a nucleating agent, J.
Polym. Sci., Part B: Polym. Phys. 39 (2001) 1001.
[11] D. Libster, A. Aserin, N. Garti, Advanced nucleating agents for
polypropylene, Polym. Adv. Technol. 18 (2007) 685.
[12] M. Kristiansen, M. Werner, T. Tervoort, P. Smith, M. Blomenhofer,
H.-W. Schmidt, The binary system isotactic polypropylene/bis(3,4dimethylbenzylidene)sorbitol: phase behavior, nucleation, and optical properties, Macromolecules 36 (2003) 5150.
[13] T.A. Shepard, C.R. Delsorbo, R.M. Louth, J.L. Walborn, D.A. Norman,
N.G. Harvey, R.J. Spontak, Self-organization and polyolen nucleation efcacy of 1,3:2,4-Di-p-methylbenzylidene sorbitol, J. Polym.
Sci., Part B: Polym. Phys. 35 (1997) 2617.
[14] M. Blomenhofer, S. Ganzleben, D. Hanft, H.-W. Schmidt,
M. Kristiansen, P. Smith, K. Stoll, D. Mader, K. Hoffmann, Designer
nucleating agents for polypropylene, Macromolecules 38 (2005)
3688.