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EUROPEAN

POLYMER
JOURNAL

European Polymer Journal 43 (2007) 30363041

www.elsevier.com/locate/europolj

Inuence of N,N,N 0,N 0 -tetraalkyl terephthalamide on


isothermal crystallization kinetics and morphology
evolution of polypropylene
Baoqing Shentu *, Jipeng Li, Tengfei Gan, Zhixue Weng
State Key Laboratory of Chemical Engineering, Zhejiang University, Hangzhou 310027, China
Received 21 December 2006; received in revised form 4 April 2007; accepted 4 April 2007
Available online 14 April 2007

Abstract
The inuence of N,N,N 0 ,N 0 -tetraalkyl terephthalamide (TATA) on the isothermal crystallization kinetics of polypropylene (PP) was studied using dierential scanning calorimetry (DSC). It was found that TATA shows a heterogeneous nucleation eect and leads to the formation of b-PP. TATA can not only shorten the crystallization time but also heighten the
crystallization temperature of PP. The crystallization rate constant of PP containing TATA is larger than that of pure PP.
The evolution of crystalline morphology of PP was investigated on a polarized optical microscopy (POM) equipped with a
hot stage and the results showed that the introduction of TATA into PP can quicken the crystallization of PP, which is
consistent with DSC results. TATA also leads to a substantial decrease in the spherulite size of PP and the boundaries
of spherulites are hardly distinguished.
2007 Elsevier Ltd. All rights reserved.
Keywords: Polypropylene; N,N,N 0 ,N 0 -Tetraalkyl terephthalamide; Isothermal crystallization kinetics; Morphology; Evolution

1. Introduction
Polypropylene (PP) is a most common commodity plastic, which is of practical use in many areas,
such as home appliances, automotive, construction
and other industrial applications. The structure
and morphology of PP have a direct impact on its
mechanical properties. Therefore, there is growing
interest in understanding the structure and morphology of PP [1].

Corresponding author. Tel./fax: +86 571 87951612.


E-mail address: shentu@zju.edu.cn (B. Shentu).

PP is a typical semicrystalline polymer and has


three crystalline forms: monoclinic a, hexagonal b
and triclinic c [2]. Under actual processing conditions PP usually crystallizes in a-form. However,
PP with a-form shows poor impact strength at lower
and room temperature.
In comparison with a-PP, b-PP has high ductility
and strength. Therefore, PP with b-form has
attracted much attention due to its unique properties. However, b-PP is pseudostationary in thermodynamics, and it is dicult to form in dynamics
[3]. Turner-Jones [4] reported that b-PP was formed
when PP was melted between 190 C and 230 C and
cooled abruptly to 100120 C. Fujiyama [5] got the

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B. Shentu et al. / European Polymer Journal 43 (2007) 30363041

high content of b-PP using the temperature gradient


method. Hong [6] found that under shearing stress aPP was partly transformed into b-PP. Leugering [7]
rstly reported that c-quinacridon was used as a
nucleating agent to produce b-PP. However, the
degree of crystallinity for b-PP formed was low.
Varga [8] found aliphatic dicarboxylic acids resulted
in the high degree of crystallinity for stable b-PP.
Therefore, the addition of b-nucleating agents is
one of the eective means to form b-PP. Kimura
found that N,N,N 0 ,N 0 -dicyclohexyl-2,6-naphalenedicarboxamide can be used as a b-nucleating agent
of PP and induce PP to form b-form [9]. Recently,
we observed that N,N,N 0 ,N 0 -tetraalkyl terephthalamide (TATA) was also an eective b-nucleating
agent. However, there are few reports about the
inuence of TATA on the isothermal crystallization
kinetics and morphology evolution of PP.
The objective of this study was to analyze the
inuence of TATA on isothermal crystallization
kinetics and morphology evolution of PP using differential scanning calorimetry (DSC) and polarized
optical microscopy (POM), respectively. Avramis
equation [10] was used to study the isothermal crystallization kinetics of PP and crystallization kinetics
parameters of pure PP and PP containing 0.3 wt%
TATA were estimated.
2. Experimental
2.1. Materials
Commercially available PP (grade F401, tacticity P 97%, melt index = 2 g/10 min, supplied by
Yangzi Petrochemical Corporation) was used in this
study. N,N,N 0 ,N 0 -Tetraalkyl terephthalamide (TATA,
supplied by Shanxi Institute of Chemical Engineering) was a white powder with a particle size of
<250 lm and its structure is as follows:

here both R1 and R2 are alkyls.


2.2. Sample preparation
TATA was dissolved easily in volatile solvent
and was mixed with PP in a high-speed mixing

3037

machine. After the solvent had evaporated completely, the mixture was extruded in a twin-screw
TE35 extruder (Keya Plastic Mechanical Factory
of Jiangsu, China) at the temperature of 195
210 C with a screw speed of 40 r/min. The extruded
products were frozen in-line in a water bath and
granulated to a size of less than 3 mm. PP alone
was also treated similarly and used as a blank
sample.
2.3. Apparatus and experimental procedures
Crystallization behavior and melting characterization of samples were studied by dierential
scanning calorimetry (DSC) using a PerkinElmer
DSC-7 in a nitrogen atmosphere. The meltedmixed
PP sample was heated from 30 C to 200 C at a
heating rate of 10 C/min, and melting parameters
were obtained from the heating scan. The sample
was held at that temperature for 5 min to eliminate
thermal history, and was jumped to temperatures of
125 C, 127 C, 129 C, 132 C, 134 C, 135 C,
137 C and 139 C for the isothermal crystallization.
The temperature scale of DSC was calibrated using
an indium (mp, 156.63 C).
Wide angle X-ray diraction (WAXD) measurements were performed at room temperature using
a Shimazu XD-3 A X-ray diractometer. The experiments were carried out using Cu Ka radiation operating at 30 kV and 15 mA at a scanning rate 2/min.
The isothermal crystallization of PP was also carried out on a Nikon-E600 polarized optical microscopy (POM) equipped with a hot stage controlled
by a computer program under 132 C.
3. Results and discussion
3.1. Inuence of TATA on the crystalline form
of PP
The inuence of TATA on the melting behavior
of PP was studied at a heating rate of 10 C/min,
and the results were shown in Fig. 1. It was found
that after the introduction of TATA into PP, there
are two peaks at 150 C and 165 C corresponding
to the melting peaks of a-PP and b-PP, respectively
[11]. Moreover, PP containing TATA crystallizes
mainly in b-form and only a small peak referring
to the presence of a-form appears in the melting
curve, while there is only one melting peak at
165 C referring to the presence of a-form for pure

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B. Shentu et al. / European Polymer Journal 43 (2007) 30363041

Endo (mW)

(300)

(301)

(110)

(130)

(040)

10
130

140

150

160
T (C)

170

180

Fig. 1. Melting behavior of pure PP (a) and PP containing 0.3


wt% TATA (b).

PP, indicating that TATA can induce the formation


of b-PP.
The values for the crystallinity degree (xa and xb)
were calculated using DH0(a) = 209 J/g and DH0(b) =
151.2 J/g [12]. The inuence of TATA on x
(x = xa + xb), xa and xb of PP was shown in Table
1. It is obvious that xb or PP containing 0.3 wt%
TATA is very high in comparison with xa and
TATA causes more PP chains to crystallize, resulting in the increase of the total crystallization degree
of PP (x) due to the heterogeneous nucleation. xb
increases with the increase of TATA content. When
TATA content is 0.3 wt%, xb remains constant,
which indicates that the optimum TATA content
is 0.3 wt%. Therefore, the isothermal crystallization
kinetics and morphology evolution of PP containing
0.3 wt% TATA were studied.
WAXD studies were also carried out to obtain
information on the crystalline form of PP. The
diraction angle (2h) curves were shown in Fig. 2.
Diraction peaks at 2h = 14.1, 18.4, and 21.7
ascribe to the (1 1 0), (0 4 0), and (1 3 0) plane, respectively, suggesting that pure PP crystallizes only in
a-form (monoclinic) because there are no peaks at
2h = 16.1 associated with b-PP (hexagonal) and
2h = 20.1 associated with c-PP (triclinic) [13].
Whereas, there are two diraction peaks at
2h = 16.1 and 21.2 ascribed to the (3 0 0) and

15

20

25

2 ()
Fig. 2. X-ray diraction proles of pure PP (a) and PP
containing 0.3 wt% TATA (b).

(3 0 1) plane for PP containing TATA, which further


indicates that TATA eectively induces the formation of b-PP.
3.2. Inuence of TATA on the isothermal
crystallization behavior of PP
The isothermal crystallization behavior of PP
was investigated by DSC, and crystallization curves
of pure PP and PP containing 0.3 wt% TATA under
various temperatures are shown in Fig. 3.
It was found from Fig. 3 that for both pure PP
and PP containing 0.3 wt% TATA with the increase
of the crystallization temperature the crystallization
exothermal peak signicantly shifts to the right side,
indicating that the crystallization time prolongs and
the crystallization rate decreases with the increase of
the crystallization temperature. It takes PP about
60 min to complete the crystallization process at
132 C, while it only takes PP containing TATA
about 5 min to nish the crystallization process at
the same crystallization temperature, indicating that
TATA can quicken the crystallization rate and signicantly shorten the crystallization time of PP
due to the heterogeneous nucleation. PP containing
TATA can crystallize at a temperature over 134 C,
while there is no crystallization exothermal peak for
pure PP at 134 C, which shows that TATA can
widen the scope of the crystallization temperature.
3.3. Inuence of TATA on the isothermal
crystallization kinetics of PP

Table 1
Inuence of TATA on x,xa and xb of PP
Samples

x (%)

xa (%)

xb (%)

PP
PP containing 0.3 wt% TATA

46.3
62.8

46.3
3.4

0
59.4

The relative degree of crystallinity of PP after


time t of the crystallization process (xt) can be calculated according to Eq. (1) from the experimental
curves of Fig. 3.

B. Shentu et al. / European Polymer Journal 43 (2007) 30363041

Endo (mW)

Endo (mW)

d
c
a-125 C
b-127 C
c-129 C
d-132 C
e-134 C

b
a

15

3039

30

45
t (min)

60

c
b

a-132 C
b-135 C
c-137 C
d-139 C

75

9
t (min)

12

15

Fig. 3. Isothermal crystallization curves of pure PP (left) and PP containing 0.3 wt% TATA (right) at various temperatures.

xt

dH =dtdt

Z

dH =dt; dt

where dH/dt is the heat ow.


Fig. 4 showed the change of the relative crystallinity degree of PP (xt) with time (t). It was found
that xt increases with the increase of time.
The isothermal crystallization kinetics of PP can
be characterized based on the Avrami Equation
(Eq. (2)).
1  xt expKtn ;

where n is the Avrami exponent, K is the crystallization rate constant involving both the nucleation and
growth rates of crystals.
Eq. (3) is obtained by taking the double logarithm of Eq. (2).
ln  ln 1  xt  ln K n ln t

Then ln[ln[1  xt]] was plotted as a function of lnt


(Fig. 5). If Eq. (3) is valid, the curve must be a
straight line whose slope is the exponent n and

whose intercept is K. Fig. 5 showed good agreement


between the experimental results and theoretical
predication at various crystallization temperatures,
indicating that the Avrami Equation can be used
to study the inuence of TATA on the isothermal
crystallization kinetics of PP.
In the case of xt = 1/2, the time which is termed
the half-time of crystallization (t1/2) can be calculated according to the Avrami Equation, as shown
in Eq. (4).
 1=n
ln 2
t1=2
4
K
The reciprocal of t1/2, represented by G1/2 (Eq. (5))
can be used as a parameter characterizing the crystallization rate of PP.
G1=2 1=t1=2

n, K, t1/2, and G1/2 were determined and listed in


Table 2. It was shown from Table 2 that at the same
crystallization temperature (132 C) the value of n
for PP containing TATA is smaller than that for
100

100

80

80

60

xt (%)

xt (%)

a b

a-125 C
b-127 C
c-129 C
d-132 C

40
20
0

10

20

30

40 50
t (min)

60

70

60
a-132 C
b-135 C
c-137 C
d-139 C

40
20

80

12
t (min)

16

20

Fig. 4. Plots of xt versus t for pure PP (left) and PP containing 0.3 wt% TATA (right) at various crystallization temperatures.

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B. Shentu et al. / European Polymer Journal 43 (2007) 30363041

1.0

1.2

0.6

ln[-ln(1-xt)]

ln[-ln(1-xt)]

0.8
d

0.4
a-125 C
b-127 C
c-129 C
d-132 C

0.2
0.0

-0.2

0.8
a

0.4

a-132 C
b-135 C
c-137 C
d-139 C

0.0
-0.4

2.0

2.5

3.0

3.5

4.0

4.5

ln t

0.5

1.0

1.5
ln t

2.0

2.5

Fig. 5. Plots of ln[ln (1xt)] versus ln t for pure PP (left) and PP containing 0.3 wt% TATA (right) at various crystallization
temperatures.

Table 2
Isothermal crystallization kinetic parameters of pure PP and PP
containing 0.3 wt% TATA at various crystallization temperatures
Samples

Tc/C

K/minn

t1/2/min

G1/2/min1

PP

125
127
129
132

3.00
2.68
2.44
2.18

0.0033
0.0018
0.0010
0.0004

5.94
9.22
14.6
30.6

0.17
0.11
0.07
0.03

PP containing
0.3 wt%
TATA

132
135
137
139

2.43
2.25
2.22
2.18

0.252
0.080
0.048
0.013

1.52
2.61
3.33
6.20

0.66
0.38
0.30
0.16

pure PP due to the heterogeneous nucleation. The


values of K for all samples decrease with the increase of the crystallization temperature, which indicates that crystallization rate decreases with the
crystallization temperature within the experimental
range. K for PP containing TATA is larger than that
for pure PP, which further indicates that the crystal-

lization of PP is accelerated by the addition of


TATA.
t1/2 for PP containing 0.3 wt% TATA is shorter
than that for pure PP at the same crystallization
temperature, while G1/2 is longer, indicating that
the crystallization rate of PP increases by the addition of TATA.
3.4. Evolution of the crystalline morphology of PP
with time
The morphological features of semi-crystalline
polymers, such as the spherulite size, can aect the
mechanical properties. Morphology development
during the isothermal crystallization of PP under
132 C was studied using a polarized optical microscopy equipped with a hot stage. Fig. 6 shows POM
micrographs of pure PP and PP containing 0.3 wt%
TATA. Clearly, the presence of TATA signicantly
inuences the crystallization process and morphol-

Fig. 6. Evolution of the crystalline morphology during isothermal crystallization at 132 C with time for PP (left) and PP containing
0.3 wt% TATA (right).

B. Shentu et al. / European Polymer Journal 43 (2007) 30363041

ogy of PP. Firstly, the introduction of TATA into


PP can quicken the crystallization of PP and shorten
the crystallization time, which is consistent with the
DSC results. Secondly, the addition of TATA leads
to a substantial decrease in the spherulite size of PP
and the spherulites in b-PP exhibits a distinct morphology. Sheaf-like aggregates of lamellar crystals
are generally observed. Furthermore, the boundaries of spherulites are hardly distinguished. This
morphological feature was consistent with Tjongs
results [14]. On the other hand, the spherulites of
a-form of pure PP consists of an aggregate of lamellae that radiates from the center outward and the
spherulites have distinct boundaries.

4. Conclusions
TATA is an eective b-nucleating agent for PP
and causes signicant changes in the isothermal
crystallization and melting characteristics of PP.
PP crystallizes mainly in b-form at a TATA concentration of 0.3 wt%. The total crystallinity degree of
PP containing TATA is markedly higher than that
of pure PP due to the heterogeneous nucleation.
Avrami theory can be used to study the isothermal
crystallization of PP containing TATA. The crystallization rate constant of PP containing TATA is larger than that of pure PP, which indicates that the
crystallization of PP is accelerated by the addition

3041

of TATA. TATA also results in a substantial


decrease in the spherulite size of PP.
Acknowledgement
The authors gratefully acknowledge nancial
support from the Scientic Research Foundation
for the Returned Overseas Chinese Scholars, State
Education Ministry.
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