Journal of Polymer Research 10: 133137, 2003.

2003 Kluwer Academic Publishers. Printed in the Netherlands.

133
Kinetics of Solvent-Induced Crystallization of Poly(ethylene terephthalate)
at the Final Stage
Wen-Hao Lee, Hao Ouyang

, Ming-Chih Shih and Ming-Huang Wu

Department of Materials Engineering and Department of Physics, National Chung Hsing University, 250,
Kuo Kuang Rd., Taichung 402, Taiwan, ROC
(

Author for correspondence; E-mail: houyang@dragon.nchu.edu.tw)

Received 28 December 2002; accepted in revised form 14 April 2003
Key words: crystallization kinetics, FTIR spectroscopy, PET, solvent-induced crystallization
Abstract
The quantitative analysis of Fourier-transform infrared (FTIR) spectra was employed to elucidate the kinetics of solvent-
induced crystallization (SINC) in poly(ethylene terephthalate) (PET). A previous study on the isothermal crystallization of
PET by Koenig et al. showed that the crystallization process could be divided into two stages, the rst followed a sigmoidal
increase in crystallinity (or the primary crystallization) and the second exhibiting a linear increase in crystallinity (or the
secondary crystallization). In the present study, multiple stages of phase transformation were found in the solvent-induced
crystallization. The kinetics of the secondary crystallization was studied in detail. Finally, the variation of morphology of
PET during crystallization was also discussed in terms of structure observed by an atomic force microscope.
Introduction
British chemists Whineld and Dickson synthesized the
poly(ethylene terephthalate) (PET) from terephthalic acid
(TPA) and ethylene glycol (EG) in the laboratory, back in
1941 [1]. PET received a British patent in 1946. Later, ICI
and Dupont developed the commercial production process
for PET. PET, in its early days, was used mostly as textile
ber used in the production of clothing, curtains, sheets
and carpets. Now, PET is widely applied in the production
of containers because it is lightweight, strong and trans-
parent [2]. Hence, PET is a very important engineering
polymer. PET is usually crystallized to an extent that meets
a particular demand, since crystallization greatly affects the
properties of polymers. Amorphous polymer is transparent
but not sufciently exible, while crystalline polymer is
fragile and opaque [3, 4].
FTIR spectroscopy is an important tool for studying
semi-crystalline polymers because IR spectra provide a sen-
sitive probe for the conformation and molecular environ-
ment. The crystallization behavior of PET can be analyzed
through the conformational changes reected by the FTIR
spectra. Koenig et al. discussed the FTIR spectrum of PET
in detail [5]. The band sensitive to the crystallinity was as-
sociated with the Trans conformation of the oxygen group
relative to the CC bond; the Gauche conformation corre-
sponded to a lack of crystallinity. Their research found that
the crystalline Trans isomer fraction increased with anneal-
ing time and temperature, while the amorphous Trans isomer
fraction decreased [6].
The mass transport of organic solvent in the polymer
has already been well studied. Amorphous PET can exhibit
solvent-induced crystallization after it absorbs an organic
solvent because an appropriately chosen solvent may de-
crease the glass transition temperature (T
g
) by reducing
the activation energy for segmental motion. Consequently,
solvent-induced crystallization provides a tool for control-
ling the surface of a semi-crystalline polymer [79]. Exten-
sive research on solvent-induced crystallization of polymers
has been conducted [1012].
Since G. Binning and H. Rohrer invented the scanning
tunneling microscope (STM) in 1982, atomic images from
a sample surface have been much easier to obtain. Follow-
ing STM, many types of scanning probe microscopy (SPM)
were developed, such as atomic force microscopy (AFM),
magnetic force microscopy (MFM), near-eld scanning op-
tical microscopy (NSOM), and others. These microscopes
all employ a special microprobe to detect certain interac-
tions between the probe and the surface of the samples [13].
Among them, AFM is the most widely used because of its
adaptability to all kinds of materials and environments, not
just conductive materials to which STM is limited. AFM
also has atomic resolution. In this study we employ both
AFM and FTIR spectroscopy to study the novel aspect of
solvent-induced crystallization of PET. The kinetics and the
morphology evolution of the crystallization process will be
discussed in detail here.
134 W.-H. Lee et al.
Experimental
Sample Preparation
An amorphous PET (ES301445) sheet was obtained from
Goodfellow Co. (Cambridge, England). The intrinsic vis-
cosity (IV) of 0.722 dL/g determined in phenol/1,1,2,2-
tetrachoroethane(60/40) at 25

C corresponded to an average
molecular weight, M
v
25, 000. Samples of 10 3
0.25 mm were cut from the sheet and polished using 800-,
1200-, 1500-, 2400-, 4000-grid carbimet papers. They were
then annealed in a high vacuum of 10
3
Torr for 4 hours at
70

C, before being furnace cooled to ambient temperature

(approximately 25

C). This process was performed in an

EYELA VOS-200SD vacuum oven to remove the residual
stress resulting fromsample preparation. Final polishing was
followed. The second annealing process was then performed
under the same conditions as for the rst annealing. The two
annealing processes eliminated the internal stress caused by
grinding and polishing.
Thermal Annealing
The prepared sample was placed in the EYELAVOS-200SD
vacuum oven for 6 hours at 80

C and then furnace-cooled

to the ambient temperature, before being taken out.
Solvent Transport Measurement
A test tube that contained acetone was placed in a Neslab
RTE-111 refrigerated bath/circulator to maintain a constant
temperature to within 0.1

C. The sample was preheated in

vacuum for 15 minutes before the samples were put into the
test tubes at different temperatures (30, 40 and 50

C). After
a predetermined time in the experiment, the samples were
stored at room temperature in the vacuum oven for three
days to extract the solvent residuals from the sample.
FTIR Measurement
The 10 10 mm samples (with a thickness of around
0.25 mm) were placed in a Bruker Equinox55 FTIR spec-
trometer to measure the IR absorption intensity. For room
temperature measurements each spectrum was the average
of 100 scans at a resolution of 4 cm
1
over the range of
4004000 cm
1
, IR Mentor Pro (Bio-Rad) software was for
the data analysis. For PET, the 973 cm
1
band due to the
stretching mode of the asymmetric CO, was associated with
the Trans isomer of the OCC group. Its intensity was
very sensitive to the ordered state of the polymer [14, 15].
Therefore, it was used to observe the variation of crys-
tallinity in the crystallization experiment. Additionally, the
conformation-insensitive band at 795 cm
1
was used as an
internal thickness standard [14, 16], enabling the intensity of
the 973 cm
1
band to be analyzed quantitatively by dividing
the area of the 973 cm
1
band by that of the 795 cm
1
band.
The method for the baseline subtraction was described in the
previous publication [17].
Figure 1. Relative percentage of the Trans isomer of PET vs. annealing
time.
AFM Measurement
An AFM (Topmetrix, 10 (Z), 100 100 (X Y):
MX199802) was used to observe the morphology and
roughness. Using the contact mode with a scan region of
20 20 m, a speed of 40 m/s, and resolution of 300 pix-
els. The force constant of cantilever (ThermoMicroscopes,
Sunnyvale, CA) was 0.05 N/m, and the resonance frequency
was 22 kHz. All experiments were conducted under room
temperature of around 21

C.
Results and Discussion
Figure 1 shows the development of Trans isomer (directly re-
lating to the crystallinity development) PET during the mass
transport process at different temperatures. The process can
be divided into four different regions. At 30 and 40

C,
the primary crystallization process related to mass trans-
port is manifested by the S curve that covers O, I, II
regions [6, 18, 19]. Region III is the secondary crystalliza-
tion region in which the Trans fraction increased linearly
with the logarithm of the mass transport time; No region O
is observed at 50

C.
Figure 2 schematically depicts four regions involved in
the solvent transport process. Crystallization can be viewed
as structural change under the following conditions; reorga-
nization of the amorphous region through chain transport,
emergence of a well-aligned, small crystalline region from
amorphous chain segments, and reorganization of crystalline
regions, including lamellar thickening and rejecting defects
from crystals [6]. The rearrangement of the amorphous re-
gion is reected in the initial stage of the crystallization;
therefore, no apparent difference exists in the Trans confor-
mation. The schematic model of Figure 2 crosschecks with
the O region in Figure 1, in which, the temperature of sol-
vent transport enhances the mobility of the chains and hence
induces the mutual motion. However, the velocity is low,
so there is no organized crystalline region formed in a short
period, as shown in Figure 2(a). After a certain period of
solvent transport, the chains folded and became crystalline.
Kinetics of Solvent-Induced Crystallization of Poly (ethylene terephthalate) 135
Figure 2. Schematic illustration of the microstructure evolution during sol-
vent-induced crystallization: (a) region O; (b) regions I and II; (c) region
III; and (d) crystalline and amorphous polymer.
However, the region was not large; the kinetics [19] of the
primary crystallization and mass transport diffusion then be-
came the main mechanism for the change in crystallinity, as
illustrated in Figure 2(b).
After the solvent transport reaches saturation, the mole-
cular chains can form small crystallites dispersed in the
amorphous regions through folding, as shown in Figure 2(c).
The black portion indicates the lamellar structure gener-
ated from the primary crystallization. The gray portion
(region III) represents the smaller lamella generated from
the so-called secondary crystallization. Chain folding during
crystallization could occur in the following ways: (i) sharp
folding [20], (ii) loose folding [20], (iii) switchboard fold-
ing [21], and (iv) a mixture of all three, as shown in
Figure 2(d). Though amorphous regions still exist during the
primary crystallization, the amorphous chains and crystals
may still be strongly connected, restricting their crystalliza-
tion. Data from SAXS were used to explain the logistics
of this type of model. The development of Trans fraction
during PET isothermal crystallization at low temperature
(<160

C) reported by Koenig et al. is indeed very simi-

lar to that shown in Figure 1, where in Koenigs study the
crystallization process was divided into the primary crystal-
lization stage (characterized by the S curve) and a secondary
crystallization stage in which the Trans fraction increases
linearly with the annealing time. Regions O, I and II in
Figure 1 are assumed to involve the primary crystallization,
while region III involves with the secondary crystallization.
Hence, the solvent-induced crystallization reported here can
be regarded as a low-temperature process.
Phase transformation particularly crystallization usually
involves an activation energy. Regardless of the tempera-
ture of solvent transport, the primary crystallization occurred
and reached a relatively high Trans fraction level within a
short time period. Seemingly, the activation energy is much
smaller than that associated with the secondary crystalliza-
Figure 3. Relative crystallization rate constant A as a function of annealing
temperature.
tion. Hence, the mutual motion of chains is assumed to be
much more localized. Once the solvent has penetrated and
lowered the energy barrier of chain motion, most of the
Trans isomers are formed in this stage. In other words, pri-
mary crystallization can be seen as a process of local chain
rearrangement (Figure 2(b)).
When solvent transport occurs at 50

C, the crystalliza-
tion in region O occurs so quickly that the rate is hardly
measurable. From the curves of 30 and 40

C in Figure 1, it
can be seen that most of the crystallization (say, about 88%)
had been completed during the primary crystallization. Since
the complicated solvent transport kinetics involved in the
crystallization in regions I and II has been established in our
previous study [19], the present article focuses on the analy-
sis of the secondary crystallization (i.e., region III). The
relation between the linear portion of the secondary crystal-
lization and the logarithm of the time of mass transport can
be expressed as
T
r
(t ) = T
r
(t
o
) +Alog(t /t
o
), (1)
where t represents annealing times; t
o
is the time of the onset
of the secondary crystallization; T
r
(t ) is the fraction of Trans
isomer at time t ; T
r
(t
o
) is the Trans isomer fraction at t
o
, and
the slope A is the parameter related to rate of crystallization.
The dotted line in Figure 1 illustrates the determination of
t
o
from the intersection of the two straight lines using linear
regression. It can be seen that t
o
decreases as the solvent
transport temperature increases, corresponding to the ear-
lier occurrence of the secondary crystallization. However,
as the temperature increases, t
o
becomes very difcult to
measure. The result of Koenig et al. showed that t
o
is dif-
cult to measure above 160

C, indirectly supporting that the

mass transport process reported here can be regarded as a
low-temperature process.
Figure 3 presents the relationship between mass transport
temperature and A determined by regression analysis. The
speed of crystallization is seen to increase with the tempera-
ture of solvent-induced crystallization. The rate of Gauche-
Trans transformation involved in the solvent-induced crys-
136 W.-H. Lee et al.
Figure 4. ln(A

/t

)vs. 1/T plots (Equation (4)) at various Trans confor-

mational levels.
tallization V
T
r
, can be expressed by the following equation:
V
T
r
=
dT
r
(t )
dt
=
1
t
dT
r
(t )
d ln t
=
A
2.303t
=
A

t
, (2)
where A[= dT
r
(t )/d log t ] is the parameter related to tem-
perature. Neglecting the process prior to secondary crys-
tallization and using the Arrhenius equation to describe
the solvent-induced crystallization at a given temperature
[6, 18], V
T
r
can be expressed as
V
T

r
= K
0,T

r
exp(E
a,T

r
/RT ), (3)
where E
a,T

r
represents the solvent-induced crystallization
activation energy at the chosen fraction of Trans isomer T

r
;
K
0,T

r
is the frequency factor related to the intrinsic nature of
the polymer system, and R is the gas constant. Combining
Equations (2) and (3) yields
ln

= ln K
0,T

r

E
a,T

r
RT
, (4)
where t

represents the time needed to reach T

r
during the
linear crystallization process and is related to temperature.
t

can be determined by either interpolation or extrapola-

tion using the data in the linear crystallization process [6].
Figure 4 is a plot based on Equation (4). The three sets of
data were the times needed to attain 23.4%, 25%, and 30.7%
Trans fractions at different mass transport temperatures. The
three sets of curves were found to be quite similar to the low
temperature portion of the isothermal crystallization curve
reported by Lin and Koenig [6].
The activation energy of the solvent-induced crystalliza-
tion can be calculated from the slope of the straight lines
in Figure 4. As shown in Figure 5, the activation energy
increases from 241.6 kJ/mol for the 23.4% Trans fraction to
447.7 kJ/mol for the 30.7% Trans fraction. Clearly, the acti-
vation energy is related to the specied Trans conformation.
That is, different Trans conformational levels have different
activation energies.
AFM was also used to analyze the PET morphological
changes at surface during solvent-induced crystallization.
Jameel, Durning and Desai [22, 8, 9] pointed out that voids
could be generated after PET contacts with more active
Figure 5. Activation energies of the secondary crystallization process as a
function of assigned conformational level.
solvents (with solubility parameter similar to that of PET)
such as dioxane, dichloromethane, dibromethane, dimethyl
formamide (DMF) and nitrobenzene. This process is the
so-called cavitation and the sizes of the spherulitic texture
generated was about 35 m. Although the solubility pa-
rameter of acetone is similar to that of PET, PET/acetone
system seems to behave quite differently [22]. As shown in
Figure 6, no spherulitic texture is observed on the surface of
PET after mass transport at 30

C as only bumps [23] were

observed. AFM observation can yield the surface average
roughness, R
a
, given by
R
a
=
1
N
N

i=1
|Z
i

Z|, (5)
where N represents the number of points along the X-axis
at which measurements were made; Z
i
is the height of the
ith point and Z is the average height of the surface. The sur-
face average roughness values, R
a
, were 4.32 nm, 26.37 nm,
43.51 nm and 42.49 nm for the solvent transport for 0 min,
1 min, 60 min and 600 min, respectively, implying that
the average surface roughness increases with transporting
time. However, further solvent transport in regions II and
III did not induce further change in roughness, as Desai and
Wilkes [9] pointed out, the cavitation only occurred at the
initial stage of contact with the solvent and was limited only
to the surface region.
Conclusions
The following conclusions have been drawn from this
study:
1. The solvent-induced crystallization kinetics analyzed
based on FTIR spectroscopy indicated that the process
can be described by four stages, i.e., the O, I, II regions
as the primary crystallization and the III region as the
secondary crystallization.
2. The time for inducing the secondary crystallization de-
creased as the temperature increased, and the rate of
crystallization increased with temperature.
Kinetics of Solvent-Induced Crystallization of Poly (ethylene terephthalate) 137
Figure 6. AFM micrographs of PET samples during solvent transport process: (a) t < 0 min; (b) 1 min; (c) 60 min; and (d) 600 min.
3. Regardless of the history before the secondary crys-
tallization, the activation energy for attaining a certain
degree of Trans conformation increased linearly with the
degree of Trans conformation.
4. According to the model presented in Figure 2, the poly-
mer chains were restricted between the primary crys-
tallite so the chain movement was more difcult, such
that the associated activation energy increased during the
secondary crystallization.
5. The AFM micrographs veried that cavitations in
PET/acetone system could be ignored, as reported by
others. The surface average roughness was in the order of
tens of nm, not 35 m as documented for other solvent
systems.
Acknowledgements
This work was supported by the National Science Coun-
cil, Taiwan, Republic of China. We would like to thank
Mr. W. C. Lee for IV measurements.
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