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Article history:
Received 30 August 2013
Accepted 4 November 2013
Available online 14 November 2013
Keywords:
Poly (ethylene terephthalate)
Annealing
FTIR spectroscopy
DSC
Lamellae thickening
Secondary crystallization
a b s t r a c t
Poly (ethylene terephthalate), PET, crystallized isothermally at 234 C has been annealed
above the crystallization temperature in regimes II, below the onset of melting, and in
regime III, in the range of observable melting [1,2]. The mechanism has been analyzed
by differential scanning calorimetry and FTIR spectroscopy and shown to be one of the limited recrystallization nucleated by crystalline regions which survived melting followed by a
process of lamellae thickening.
Annealing above the crystallization temperature in regime II where melting and recrystallization did not occur involved lamellae thickening by growth of the lamellae along the
chain direction. This was a diffusion controlled mechanism involving either diffusion of
non-crystallizable impurities or chain entanglements. The process of stem thickening
was the same as that of secondary crystallization previously observed in isothermal crystallization [3] and which is responsible for the observed melting point of the polymer being
dependent on the annealing time as well as the temperature.
In regime III melting of the polymer occurred initially followed by recrystallization on
the residual lamellae acting as seeds by one dimensional growth along the original growth
direction. This was later accompanied by thickening of the lamellae with the same characteristic time dependence of diffusion control as observed in regime II and with secondary
crystallization. This involves reptation of the molecular chain from the entangled melt onto
the growth face.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Annealing has a profound effect on the material properties of partially crystalline polymers by increasing the
melting point, fractional crystallinity, stiffness, yield stress
and brittleness, as well as decreasing the elongation to
break, and fracture toughness [4]. It is invariably associated with a change in morphology and a re-organization
of the distribution of lamellar stem lengths which results
in a reduction in chain mobility as measured by NMR line
width and dynamic mechanical thermal analysis [14]. An
understanding of these changes is vital for the end users
point of view if material properties are to be maintained
Corresponding author. Tel.: +44 121 414 4544; fax: +44 121 414
5232.
E-mail address: j.n.hay@bham.ac.uk (J.N. Hay).
0014-3057/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.eurpolymj.2013.11.004
236
2. Experimental
PET lms, 1.513 lm thick, were obtained from Goodfellow Ltd., UK. These were used in spectroscopic analyses
as outlined elsewhere [9]. The lms were dried in a vacuum oven at 100 C for 12 h prior to use. These were stress
relieved by melting between KBr plates and quenched to
produce amorphous samples, as measured by DSC [10,11].
FTIR spectra were measured on a Nicolet model 8700
spectrophotometer with a DTGS-KBR detector on thin lms
samples mounted between KBr plates and contained within the furnace of a Linkam hot-stage [9,12]. The furnace
temperature was controlled by a Unicam PR600 thermal
controller. All spectra were recorded at a resolution of
2 cm1 and total of a 100 scans were accumulated for each
spectrum along with the background. The spectra were
analyzed for peak resolution and area. Thin lms were
cut into small pieces, placed between KBr plates and
melted at 270 C for 1 min. mounted in a Linkam PS600
hot-stage and placed vertically in the IR beam. In this
way, shrinkage and orientation of the lms were removed
and the lms adhered to the KBr disks. The temperature of
the hot-stage was controlled to an accuracy of 0.1 C. The
kinetics of isothermal crystallization have been studied,
previously over the temperature range 230240 C and
the same experimental procedures adopted [9].
A PerkinElmer differential scanning calorimeter, DSC7, interfaced to a computer was used as described elsewhere [10,11] to follow the rate of heat evolution with
time. The temperature scale of the DSC was calibrated from
the melting point of high purity metals; tin (230.06 C) and
indium (155.58 C). Power response of the calorimeter was
237
T = 234 C
c
0.6
0.4
1717 cm-1
0.2
0.8
0.8
0.6
T = 250 C
0.6
0.4
0.4
o
T = 250 C
c
0.2
0.2
o
T = 234 C
2.5
3.5
4.5
2.5
log (time / s)
1
) and
0.4
T = 244 C
c
0.2
0.2
o
T = 234 C
c
3.5
4.5
1
o
234 C
0.6
T = 244 C
2.5
252 C
0.8
0.8
0.6
0.6
0.4
0.4
o
234 C
0.2
0.2
252 C
2.5
3.5
4.5
0.8
0.8
4.5
Tc = 234 C
0.4
0
3.5
log (time / s)
0.6
1727 cm -1
0.8
Absorbance
Tc = 234 C
log (time / s)
log (time / s)
Fig. 2. The change in fractional crystallinity, Xc,t, and amorphous content,
Xa,t, with time on crystallizing at 234 C for 50 min and then on annealing
at 244 C (time was reset to zero on heating to 244 C).
238
0.5
Ta = 244 C
inf
0.4
0.3
Fractional Crystallinity, Xt
0.5
Ta = 250 C
0.2
0.1
Tc = 252 C
2.5
3.5
4.5
Ta = 252 C
-1
o
Ta = 250 C
-1.5
-2
Ta = 244 C
-0.5
2.5
log (time / s)
3.5
4.5
log (time / s)
X t X o X 1 X o 1 exp Zt n
1.4
1.2
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
Extent of Crystallization
1
0.8
A linear dependence was observed for Eq. (2) and n values in the range 0.7 0.1 at 244 and 250 C and 1.0 0.2 at
252 C.
Deviations from linearity were observed towards the
end of the annealing process and in order to determine if
this was due to the presence of two consecutive processes
the data was re-analyzed to determine instantaneous n
values as a function of the extent of crystallization, see
Fig. 7, using the differential form of Eq. (2),
0.6
n Value
X t X 1 X 0 =2
250 C
n Value
where Xt is the crystallinity at time t, Xo the fractional crystallinity initially present and X1 the nal crystallinity
achieved; n is the Avrami exponent whose value depends
on the crystallization mechanism [13], and Z the composite
rate constant.
Since
244 C
0.4
0.2
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Extent of Crystallization
n t dX t =dt=1 X t ln1 X t
dXt=dt aX b
t
Table 1
Avrami rate parameters for annealing.
Annealing temperature/C
244
250
252
n Value 0.2
Rate constant Z/sn 104
Xo
X1
Half life t1/2/s 103
0.67
19.5
0.31
0.49
18.2
0.79
9.59
0.14
0.39
4.28
1.03
0.00756
0.047
0.23
64.3
239
100 min
30
10 min
25
1.5 min
20
15
10
0 min
5
0
235
240
245
250
255
260
265
270
Temperature / C
Fig. 8. Change in melting endotherm with time at 250 C (0 min refers to
the starting material crystallized at 234 C for 50 min).
70
0.4
50
250 C
40
30
0.2
252 C
20
Fractional Crystallinity , Xt
60
10
0
0.5
1.5
2.5
0.0
275
252 C
270
Melting Point / C
1000 min
250 C
265
260
255
200
400
600
800
1000
Time / min
Fig. 10. Change in melting point with time on annealing at 250 C.
240
10 min
3 min
Relative Weight
20
1.5 min
15
0 min
10
10
12
14
16
observed above. It was also observed that material annealed at higher temperatures had consistently higher
melting points at the same annealing time and at each
temperature the melting point increased with time.
In a previous publication [3] we have attributed the
thermal stability of the lamellae to their thickness, in that
the thicker the lamellae the higher the melting point, Tm In
particular,
T m T om 1 2RT m lnn=nDh . . .
T om
where
is the equilibrium melting point, Dh the heat of
fusion per monomer unit, R the gas constant and n the
number of monomer units per lamellae stem. For each value of Tm in the melting range n was determined as outlined before [3] and the melting endotherms converted
into a weight distribution of lamellae stem lengths, see
Figs. 11 and 12. It can be seen from these distributions that
the sample crystallized at 234 C for 50 min. had stem
lengths from about 5 to 14 monomer units and on heating
to 250 C the lamellae had lengths from about 5 to 11. On
subsequent crystallization and annealing the lamellae
thickened progressively but the change with time was
more obvious above 200 min.
The increase in stem length with increasing fractional
crystallinity is shown in Fig. 13. There are clearly two
1000 min
Relative Weight
40
200 min
500 min
100 min
30
50 min
20
0 min
10
10
15
20
25
30
50
35
40
25
20
15
10
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Fractional Crystallinity
Fig. 12. The change in stem length with time at 250 C on further
annealing (0 min refers to the starting material crystallized at 234 C for
50 min).
Fig. 13. The changes in average stem lengths with increasing crystallinity, on annealing at 250 C.
during the secondary crystallization of the isothermal crystallization at 234 C. The data was displaced by the amount
of fractional crystallinity corresponding to the onset of the
stem thickening process (see Fig. 15).
30
Stem Length / nm
252 C
25
4. Conclusions
20
o
250 C
15
10
10
15
20
25
30
35
Table 2
Diffusion control.
Annealing
temperature/C
Intercept fractional
crystallinity
Rate constant
104/s
Degree of
t R2
250
0.777a
0.254b
0.661a
0.377b
0.727a
0.307b
8.46
6.67
6.77
4.83
6.59
4.51
0.995
0.992
0.995
0.996
0.987
0.988
244
234
a
Amorphous
Fraction, Xa
0.7
o
250 C
0.6
234 C
o
244 C
0.5
Crystalline
Fraction, Xt
241
0.4
244 C
o
234 C
o
250 C
0.3
160
180
200
220
240
260
280
Yeh et al. [2] have listed three well separated temperature ranges in which different mechanisms are operational
in the annealing of partially crystalline polymers. These are
rstly refolding of the polymer crystals in the solid state by
which the lamellae thicken by migration of chain defects
within thin lamellae, secondly melting and recrystallization of the thicker lamellae already present in the original
sample and thirdly partial melting of the lamellae surface
inwards towards the core along the chain axis followed
by recrystallization at the annealing temperature producing thicker lamellae. We have not observed these different
mechanisms.
Ageing partially crystalline polymers [4,12] at temperatures well below their crystallization temperature was observed not to increase .the melting point of the polymer, as
would be apparent if stem thickening had occurred, but instead the increase in crystallinity was due to the production of thin lamellae which melted at temperatures
below the observed melting of the sample created in the
original crystallization. Moreover the melting point of the
thin lamellae increased with annealing temperature in line
with Hoffman-Weekes nucleation theory [15].
Annealing above but close to the crystallization temperature did not result in any detectible melting of the polymer
and was accompanied by a progressive increase in crystallinity due entirely to the thickening of the lamellae along
the chain direction. This process was diffusion controlled
in that growth increased linearly with square root of the
annealing time. The thickness increased with annealing
temperature and with time and had all the characteristics
of secondary crystallization observed previously in PET [3].
Annealing within the temperature range of melting was
accompanied rst by melting of the polymer and then by
recrystallization limited in extent by the amount of melting which had occurred. The rate to which this developed
was dependent on the amount of residual lamellae which
survived at the annealing temperature as these acted as
seeds. The initial n value observed in the kinetics analysis
was 1.0 0.1 and consistent with the re-growth of lamellae
in their original form [16,17] but with increased thickness
consistent with the increased temperature. This re-growth
is followed by one of thickening of the lamellae as outlined
above and with diffusion control of growth.
The dependence of the increase in stem length on the
square root of the time implies increasing restriction to
growth as the lamellae develop into adjacent amorphous
regions and reduction in mobility of the chains as the
lamellae surfaces approach one another. Translational
mobility in the amorphous inter-lamellar regions of a
chain is restricted by entanglements with other chains
and according to reptation theory [1821] can only escape
from these entanglements by Brownian motion within a
virtual tube. The mobility of the chain, S, reptating in a
242
0.7
o
244 C
1.02
o
234 C
0.5
1.01
0.4
Xc,t + Xa,t
0.6
250 C
0.3
0.99
0.2
0.98
0.1
0
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.97
0.4
0.9
1/2
1a
2a
0.7
0.8
0.9
4a
0.6
0.5
3a