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Poly(ethylene terephthalate

)
H Morphological Changes on Annealing
R. C. ROBERTS

Morphological changes which occur when partially crystalline poly(ethylene
terephthalate) is annealed were aerected and followed quantitatively using
differential scanning calorimetry. These changes appeared as an additional
fusion endotherm at a temperature intermediate between the annealing tem-
perature and the melting point. The magnitude of this endotherm increased
with both annealing time an d temperature and was found to be associated
with decreases in the original fusion endotherm and not with crystallization
of amorphous material. These changes are discussed in relation to present
concepts of the morphology o/ bulk crystallized poly(ethylene terephthalate).

WHEN amorphous poly(ethylene terephthalate), PET, is heated above its
glass transition temperature spontaneous crystallization occurs in the solid
state. The overall rate at which this occurs has been studied extensively as
a function of temperature, polymer structure and molecular weight (see
ref. 1 for earlier literature references). Crystallization occurs most rapidly
in the temperature range 140--220°C with 50 per cent of the resulting
crystallinSty developing in less than 30 seconds. The overall degree of
crystallinity achieved~, however, depends on the annealing temperature and
to attain the highest degree of crystallinity one must anneal at temperatures
approaching the melting point. The availability of non-equilibrium tech-
niques, such as differential thermal analysis (DTA), in which the sample is
subjected to a rapid temperature scan, has enabled studies to be made of
the intermediate stages of such annealing treatments. Thus Gray and
Casey8 demonstrated that discontinuous crystallite size distributions could
be induced in polymers by appropriate thermal treatments and that earlier'
DTA multiple fusion endotherms could be explained on this basis. An
exception here is trans-polyisoprene which exists in two different crystalline
forms and shows corresponding fusion endotherms. Multiple fusion endo-
therms have since been reported for annealed samples of high and low
density bulk crystallized polyethylenes5 and polyethylene single crystals6,
66 and 6 nylons 7,1°, polypropylene~, polypropylene oxide8, poly(ethylene
terephthalatey and poly(4-methyl pentene-1) single crystals1~. Detailed
quantitative measurements of these morphological changes on annealing are
presented here for poly(ethylene terephthalate).

EXPERIMENTAL
Poly(ethylene terephthalate) was the same sample as described previously~1.
Annealing was carried out in the cell of a Perkin-Elmer model 1B differ-
ential scanning calorimeter. 5 to 15 mg samples of polymer were accurately
weighed into a sample pan and the cell purged with nitrogen. After holding
in the melt at 270°C for five minutes the temperature was lowered to 100°C
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R. C. ROBERTS

at 64 deg. C/min in order to crystallize the samples in a standard way and
then raised to the annealing temperature at 64 (leg. C/rain. After the
required annealing the samples were again cooled to 100°C at 64 deg.
C/min and finally scanned at 16 deg. C/min.
Low angle X-ray patterns were recorded photographically with a Kratky
low angle camera using 1 mm sample thickness. The camera entrance slit
was I00/~m and the specimen to film distance 23.5 era. The films were
measured by microdensitometer and the slit-smeared scattering curves thus
obtained were unsmeared by the method of Schmidt and Hight n. No cor-
rection was made for the width of the primary beam or of the micro-
densitometer slit.

RESULTS
(i) Effect of annealing temperature
Differential scanning calorimetry (DSC) fusion endotherms of samples
annealed for 16 hours at temperaturesbetween 135 ° and 220°C are shown
in Figure 1. Besides the original melting endotherm of peak temperature
(Tin), an additional endottierm ( T ' ) is seen at eemperatures 25-40 deg. C
above the annealing temperature. These melting points and their associated
heats of fusion, AH and AT-/', respectively, are given in Table 1. AH is seen
to decrease with annealing whilst ~r-/, increases markedly. Thus the ovexall

(5)

I d.._.HH,
dT

(

(21

0)
I I I I I I ~ J I I
1SO 180 200 220 240 260
T,oc
Figure 1--DSC fusion endo~hcrms of PET annealed for 16 h
at (1)135°C (2)170°C (3)1850C (4)200°C (5)220°C
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POLY(ETHYLENE TEREPHTHALATE) II

effect of the formation of this low melting species is almost to double the
original sample degree of crystallinity.
Table 1. Effect of annealing PET for 16 hours at different temperatures
Annealing
T',n Tm AH" AH AH + AH'
temperature °C oC
°C cal / g cal / g cal / g

135 160 253 0"2 8"9 9"1
170 202 253 if3 9"0 9-3
185 227 253 5"2 8'2 13"4
200 236 254 8'0 6"8 14"8
220 246 254 14-4 1"7 16"1

(ii) Effect of annealing time
The rate of formation of the low melting form is seen to increase with
annealing temperature. The effect of annealing time at a constant annealing
temperature could therefore conveniently be studied at a temperature of
220°C. Samples were annealed for times between 1 and 2600 rain as pre-
viously described. DSC endotherms are shown in Figure 2 and the observed

(I0)

~)
dH

(3)

220 240 260
J
240 260
Loc T,oc
Figure 2 - - D S C fusion endotherms of PET annealed at 220°C
for (1) 0 (2) 5 (3) 30 (4) 60 (5) 90 (6) 180 (7) 240 (8) 400
(9) 1 000 (10) 2 600 minutes

melting points and heats o f fusion a r e plotted as a function of l o g (time) in
F i g u r e 3. I t can be seen t h a t whilst the m e l t i n g point (T'~) increases a l m o s t
linearly with l o g (time) the heats of fusion follow a m o r e c o m p l e x sequence.
T h e heat of fusion (AH) of the original f o r m decreases m o n o t o n i c a l l y to
zero at times between 1 000 a n d 2 000 minutes. T h e rate of decrease is,
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R. C. ROBERTS

260

o 250

240

230

15
3:
w
o
10

10 o~
1-
15 .gl

10

.¢1 5 -1

° 1 101 ~ 102 103
Time, rain
Figure 3--Effect of annealing time at 220°C on PET
I T',., [] (AH+AH'), © AH', ~ AH

however, initially greater than the increase in the heat of fusion (AH') of
the low melting form so that the total observed heat of fusion (AH + AH')
decreases slightly over the first 70 minutes annealing time. In the region
100 to 1 000 minutes annealing AH" and (AH + AH') increase linearly with
log (time) consistent with a secondary crystallization mechanism. For times
longer than 1 000 minutes the rate of increase in AH' appears to be slowing
down as the polymer attains its maximum degree of crystallinity. Thermal
degradation is also almost certainly beginning to affect the results at this
stage.

(iii) Isothermal melt crystallization
If, instead of annealing in the solid state, the polymer is isothermally
crystallized from the melt the same overall effect is seen. Thus, Figure 4
shows fusion endotherms of PET which has been held in the molt for five
minutes, cooled at 64 deg. C/min to 220°C and held isothermally for
various times, followed by cooling at 64 deg. C/min to 100°C and scanning
at 16 deg. C/min. With a five minute annealing time a peak at 277°C
appears and, as the annealing time is increased, the peak increases in size
and moves to higher temperatures. The rate of increase is faster than that
of the solid state annealed PET as can be seen from Table 2 which lists the
relative heats and temperatures of fusion. Comparison with Figure 3 shows
that the low temperature peak is not well resolved in the melt annealed
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POLY(ETHYLENE TEREPHTHALATE) II

(6)

I L I 1 : i P

220 240 260 240 260
r, oc T,°C
Figure 4--DSC fusion endotherms of PET crystallized from
the melt isothermally at 2200C for (1) 5 (2) 15 (3) 60 (4) 200
(5) 300 (6) 450 minutes

samples and hence some of the peak areas of Table 2 are only approximate;
the total heat of fusion is, of course, accurately determined. The sample
annealed for as little as 450 minutes shows only a single fusion endotherm

Table 2. 220°C isothermal crystallization of PET from the melt
Time T'~ T,n AH" AH ~H" + AH
rain °C °C cal/g cal/g cal/g
5 227 250 0-8 8.8 9.6
15 234 251 2.0 8.3 10-3
60 244 252 3.7 7.5 11.2
200 250 254 ~-.~8.0 ~.~6.3 14.3
300 251 253 ,-~8-0 ,~,5.6 13.6
450 251 -- 14.2 0.0 14-2
1 000 254 -- 15.0 0-0 15.0

at the melting point of the original polymer and it would therefore seem that
at the stage when T',, has increased to equal Tm the original P E T is
completely converted into the new form.

(iv) Annealing at temperatures approaching T,,
This transformation is seen more clearly when the effect of annealing at
higher temperatures is studied. A comparison of the effect of annealing P E T
at 220 °, 230% 240 ° and 2 5 0 ° C for 3, 10 and 32 minutes at each temperature
is shown in Table 3. Annealing for three minutes produces an endotherm
some 6-8 deg. C above the annealing temperature, for ten minutes an
endotherm s o m e 8-11 deg. C above the annealing temperature and for
32 minutes an endotherm 10-15 deg. C above the annealing temperature.
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R . C . ROBERTS

T h e magnitude of these endotherms is seen to increase with both time and
annealing temperature; thus. annealing at 240°C for as little as 32 minutes
is sufficient to convert all the material to the new form and at an annealing
temperature of 250°C the P E T was completely converted by only three
minutes annealing.

Table 3. Effect of annealing time and temperature on PET
Annealing Annealing T'm T,n AH" AH All" + AH
time temp. °C °C
min *C cal/g cal/g cal/g

220 227 255 1"3 10"2 11"5
230 238 255 3-1 8"2 11"3

240 247 255 ,~,5"0 ,-.,5"9 10"9
250 256 -- 9"5 0.0 9"5
220 231 255 2"1 8"5 10"6
230 241 255 4"1 7"3 11"4
I0
240 249 255 ,~o8-3 ,--,4"0 12"3
250 258 -- 10"3 0-0 10"3
220 235 255 3"9 7"6 I 1"5
230 244 255 5"9 6"2 12-1
32
240 253 -- 13"2 0-0 13"2
250 260 -- 11"6 0-0 11"6

On annealing for longer periods of time (up to 4 000 minutes) at 250°C
the melting point of the P E T was raised to 276°C, approaching that of
278°C determined by Hartley (see ref. 13) but lower than 284°C predicted
by Taylor/3 from oligomer melting points and by I k e d a and Mitsuishi 1~f r o m
crystallization studies. The observed heat of fusion, however, did not
exceed 16-5 cal/g.

(v) lrreversibility o f observed changes
It is interesting to note that these morphological changes on annealing
are not reversible as detected by DSC. Inspection of Table 4 shows that
annealing for ten minutes at 240°C transforms 67 per cent of the crystal-

Table 4. Irreversibility of morphological changes
T,n AH T-- AH"
Annealing conditions °C cal / g °C cal / g

2400C/10 mm 255 4-0 249 ,~,8-3
250°C/10 min 258 10-3 -- --
250°C/10 rain followed by 240°C[ 10 rain 259 11"3 251 1"7
250°C/120 min 264 12"8 -- --
250°C/120 min followed by 240°C/10 rain 264 13"5 251 0-1

linity. Prior annealing for ten minutes at 250°C reduces this to 13 per cent
and prior annealing for 120 minutes at 250°C to less than one per cent.
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POLY(ETHYLENE TEREPHTHALATE) II

Table 3 shows that all the sample crystallinity is transformed by the 250°C
annealing and hence the appearance of a low melting peak on further
annealing at 240°C is associated with an increase in crystallinity and not
reorganization of the material produced by the 250°C annealing. Thus as
the overall degree of crystallinity is increased by annealing for longer times
at 250°C the amount of amorphous material available for crystallization on
further annealing at 240°C is decreased and hence AH'---->-0 for this
process.

(vi) Low angle X-ray measurements
The low angle X-ray diffraction patterns of the amorphous PET show
broad scattering corresponding to spacings of 100 to 300 A. Superimposed
on this amorphous scattering annealed samples showed small shoulders or
peaks at 120-130 A and 150-160 A and in addition, a peak or shoulder
which varied between 2(K)--500 A but was of low intensity.

DISCUSSION
When PET is subjected to heat treatment above its glass transition tempera-
ture and below its melting point (Tin) morphological changes occur which
can be detected as an additional fusion endotherm appearing at a tempera-
ture (T',~) up to 40 deg. C higher than the annealing temperature. The
magnitude (AH') and melting point of this additional endotherm increase
with treatment time at a particular temperature or with treatment tempera-
ture for a fixed annealing time. At the same time the magnitude of the
original fusion endotherm (h/-/) decreases until as T~ ---->-T,~, AH ~ 0 and
the sample is completely converted into the new form. The same effect is
seen on isothermal crystallization from the melt although the rate of change
is more rapid. This is further evidence for a reorganization mechanism in
the solid state of the existing crystallites and not merely secondary crystal-
lization effects. Isothermal crystallization from the melt will not involve
such reorganizations to the same extent. The different nucleation or growth
mechanism producing the low melting form ~ill proceed without prior
melting of pre-formed crystallites and hence the overall growth rate of the
low melting species will be faster.
These changes are not reversible and further annealing at temperatures
below the maximum annealing temperature only brings about crystallization
of existing available amorphous polymer. Thus the phenomenon of mul-
tiple fusion endotherms produced by annealing will only be detected in
samples having relatively imperfect crystallites which can rearrange to a
more ordered form, not necessarily having a higher degree of crystallinity.
Wide angle X-ray measurements 9,17detect no difference in crystal lattice
on such annealing. Changes in crystallite size, however, do occur as indica-
ted by narrowing of the diffraction peaks. PET crystallizes from the melt
and in the solid state in the form of spherulites. The crystal morphology
within such spherulites is not clear although lamellae of thickness about
100 A and 1 000-2 000 A in lateral dimension have been observed~.le in
PET crystallized from the glass at 97 ° and 154°C. Low angle X-ray
scattering of annealed PET has been studied in some detaiP6,~7. The ob-
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R. C. ROBERTS

served long spacing is found to increase with annealing temperature but it
decreases with time at any particular annealing temperature. The increase
in spacing could be interpreted as an increase in thickness of lamellae with
annealing temperature as is observed for other bulk crystallized polymersTM.
The origin of the decrease of long period with time is more obscure but is
thought to be associated with the incorporation of loose chain ends into the
lamellae, ordering of folded chains and hence closer packing of the lamellae.
Further evidence for a chain folded structure of the lamellae has been pre-
sented by Koenig and Hannon TM who associat~ an i.r. absorption band at
988 cm -1 with a fold conformation.
Thus, although the evidence for a chain folded lamellar structure within
the PET spherulite is by no means complete it is illustrative to consider the
present results on the basis of this model. The initial crystallization of the
PET brought about by cooling rapidly from the melt would be expected to
produce imperfectly ordered spherulites and the overall morphology would
be of 'fringed-micelle' type. The individual crystallites would be small, have
large surface free energies and hence low melting points. Annealing would
increase the perfection and size of these crystallites by the formation of thin
lamellae and bring about further crystallization of amorphous polymer.
The DSC results indicate that this occurs by the initial formation of
crystallites having even larger surface free energies and hence lower melting
points than the initial imperfect crystallites. This could be due to a smaller
size or a large surface free energy of the folded ends of the lamellae. Further
annealing would increase the thickness of these lamellae and decrease the
total surface free energy until the ultimate melting point was reached when
the surface energy would be negligible. The X-ray low angle measurements
showed three spacings; the two at 120--130 A and 150--160 A being common
to all crystalline samples and an additional spacing of much lower intensity
which varied between 200 and 500 A. Identification of this spacing with the
thickness (/) of a lamella and further identification of the DSC detected T',~
with the lamella melting point would lead to values of 100-200 ergs/cm 2 for
the folded surface free energy, o-e, on application of Hoffman's ~° equation
T" = T°~(1 2o-,/AH,/)
-

These are much larger than previously1.,21 reported values of 40 ergs/cm ~
which have indicated a loosely folded end of the lamellae. Reported values
of o-, for polyethylene of similar molecular weight, however, vary from
50-200 ergs/cm ~ and thus comparison of the difference in free energies of
a polyethylene and PET fold is not possible.

The author thanks Dr H. A. Long ]or the low angle X-ray measurements
and Mrs E. Charles for experimental assistance with DSC.

NOTE ADDED IN PROOF
Further low angle X-ray measurements on samples showing two fusion
endotherms have been carried out by Dr I. M. Ward, University of Bristol,
using a Franks camera. Only a single low angle spacing was observed
which w~s no~ resolved into two or more peaks. This would appear to be
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POLY(ETHYLENE TEREPHTHALATE) II

surprising in view of the distinct crystal size distributions indicated by DSC;
although theoretical calculations by D r D. J. B l u n d e l l of this laboratory
predict that only one low angle diffraction is likely t o be observed from
such a system if r a n d o m l y dispersed. T h e r e is therefore at present some
a m b i g u i t y over the low angle m e a s u r e m e n t s a n d further work is p l a n n e d to
clarify the situation.

Imperial Chemical Industries Limited,
Petrochemical & Polymer Laboratory,
P.O. Box 11, The Heath,
Runcorn, Cheshire.
(Received Ianuary 1968)

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