A Kinetic Study of the Benzene-induced

Crystall&ation of
Polyethylene Terephthalate
R. P. SHELDON
A study has been made into some o f the factors associated with the kinetics
o f the benzene-induced crystallization of polyethylene terephthalate. Four
thicknesses o f the film were used at temperatures o f 25", 30", 35* and 40"C
and in one case at 55"C. T h e rate was f o u n d to increase with increase o f
temperature and within the restricted range studied no tendency towards a
m a x i m u m was detected. M a k i n g the usual assumptions between density and
crystallinity the mathematical expression relating to the major part of the
rate curves was f o u n d to have the form
A'- V/A'=Cexp [ - (C'/xz) (e-AE/Rr) t]
where A" and V are the volume fractions of crystallinity at equilibrium and
after time t respectively, C and C' are constants, x is the specimen thickness,
T is the temperature on the absolute scale, R the gas constant and E, which
has the value of 10"3 kcal/mole, is identified with an activation energy term.
It is believed that the crystallization process is diffusion controlled in that it
probably occurs along a progressive front accompanying liquid diffusion.

IT HAS recently been shown that a number of organic liquids will induce
substantial degrees of crystallization in amorphous polyethylene terephtha-
late (PET) at temperatures well below those at which appreciable air or
normal crystallization occurs 1. For example, a 50 per cent degree is achieved
within a few minutes by immersion of an 8 mil thick specimen in dioxan at
25°C, whereas in the absence of organic liquids a temperature of the order
of 100°C higher would be necessary for a comparable effect. It is probable
that this property is by no means restricted to PET but is one characteristic
of those crystallizable polymers which may, by suitable treatment, be
obtained in the amorphous form since cellulose triacetate appears to show
the same behaviour ~ whilst stereoregular polymethyl methacrylate, like
PET, may only be crystallized with liquids whose solubility parameters lie
within a certain rang@.
From the previous work x it was seen that the rates and extent of
crystallization may vary widely from one system to another and since no
information is available, so far as the author is aware, upon the kinetics of
such induced crystallization an investigation has been made using one
liquid, benzene, preliminary studies having shown that at ambient tempera-
tures this system produced changes at a rate convenient for measurement. It
is proposed at a later date to extend the work to other liquids.
In normal thermal treatment extensive investigations have been carried
out" and it has been shown that crystallization occurs within a range of
temperatures intermediate between the glass temperature and the melting
point as may be expected and the rate curves have the typical sigmoidal
27
 R. P. SHELDON

characteristics to be expected on the basis of the Avrami treatment which

considers growth concomitant with nucleation~. It may also be noted that
the time exponents of the experimentally derived Avrami equations have
the values of 2, 3 or 4.
With the present system, however, the behaviour may be more ditticult to
predict owing to lack of adequate theory but it appears reasonable to assume
that the factors which might exert an influence will include such parameters
as are determined by the nature of the liquid, thickness of sample, tempera-
ture and previous history of the polymer, e.g. temperature of the melt prior
to extrusion,, dwell-time, etc. Some information is already available upon
the first of these points, as previously mentioned1, in that the density at
equilibrium may be interpolated from a knowledge of the solubility para-
meter of the liquid. The contribution due to the history of the polymer has
largely been ignored, although this aspect is intended to be the basis of some
future work.
EXPERIMENTAL
Materials
The PET used in these studies was in the form of transparent film of low
density (1 "340 g/cm a) corresponding to a calculated crystaUinity of 4"2 per
cent by volume. It was also unoriented showing no evidence of birefringence
under a polarizing microscope. Four thicknesses were taken, each being
measured with a micrometer and were fotmd to be 2-1, 2-7, 3-4 a n d
4-1 x 10 -2 cm, subsequently referred to as A, B, C and D.
The benzene used as immersion liquid was of A.R. quality and was dried
and fractionally distilled before use, as were also the carbon tetrachloride
and ethyl alcohol for the density measurements.

Procedure
The experimental procedure was similar to that previously describedL
Samples of polymer of the various thicknesses were cut into smaU pieces of
approximately 1 cm2 in surface area. Four pieces from the four samples
were weighed on a balance capable of reading to 0"01 mg and introduced
into test-tubes containing benzene, each tube itself being immersed in a
thermostatically controlled bath, at a temperature of 25 +0.01°C. After
predetermined intervals of time the pieces were removed, surface dried and
transferred to an evacuated desiccator where they remained for at least
48 hours before being reweighed. The apparent density was determined by
a flotation method in which alcohol is run in from a microburette to 10 ml
of carbon tetrachloride until the polymer sample is on the point of sinking.
Allowance was made for the residual benzene to convert the apparent
density to a corrected value, the former being interpolated from a calibration
curve of various mixtures of the flotation liquids and their densities.
The procedure was repeated at 30 °, 35 ° and 40°C and in the case of
sample B, at 55°C. The temperature control at this latter temperature was
of the order of + 0" 1°C.
RESULTS
The rate curves showing the increase of density as a function of time are
shown in Figure 1. Investigation shows that, within experimental error, in
28
 CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE

~" 1-40 4 days 16 h--~--~_=. ~ 4 days 16 h "-~-~-_~.~

a_...---------~'~ 1---=~1 I a~-.~---...-...-...-_-----..-==~e
.... ___.

>, 1.37

¢¢,e 25 *C F / 30 *C

I"3~ r

4 days 16 h a 4d a y s ~
~ 1"40
/" .p .... - . ---"

•~ 1"37
r-
¢'41
a 35 °C 40 °C

1-3z,
1' ~ ~ I ~
~" 1 "40 Time days
o~
E

i
>,
!
~ ~.3~
Q
Q Figure /--Rate of increase of density with
550C time
1"34 I I I
I 2 3
Time days

those cases where equilibrium has apparently been reached the equilibrium
density has the value 1"396 g / c m 8, independently of sample thickness and
temperature. Taking this to be the value for all cases a plot is made of
log (doo-dt) versus time where d,oo and d, are the density values at
equilibrium and after time t respectively (Figure 2). The magnitudes of the
slopes of the straight lines obtained are measures of the rates of attainment
of equilibrium and thus may be identified with rate constants (Table 1).
Following the usual kinetic procedure the dependence of rate constant upon
temperature is obtained by means of a plot of log k versus T-1 where k is
the rate constant at a particular temperature T (Figure 3). Again by analogy
with normal kinetic procedure, where an Arrhenius relationship is usually
valid, an activation energy term and a temperature-independent term may
be evaluated (Table 2). The relationship between rate constant and sample
thickness is obtained from a plot of log k versus log (thickness), the thick-
ness being measured in centimetres (Figure 4). The corresponding slopes
and ordinate intercept values are given in Table 3.
It may be relevant at this stage to point out that in view of the similarities
in the slopes in Figure 3, and yet where a small divergence can have a
significant effect upon ordinate intercept value, in order to obtain the values
quoted (Table 2), an average was taken of the slopes followed by extrapola-
tion from the value of log k at T - ~ = 0 . 0 0 3 0 ° K -1. In Figure 4 the slopes
were found to be identical and thus a similar treatment was unnecessary.
29
 R. P. S H E L D O N

Time h Time h
8 16 24 8 16 2/,
t
,-.-.~.:~-~
--.--.--.__~. N~:~.....~ /

-1.4 ~ I I I I I
";,~'~..~
\ '\ "-- ~o~
i
\ "~',,.~'~.~
o -2.0
~'~.~ -\ "'x,+
"x,\o - ~ 40°C
35 °C

-1.4 t I I I

,\
1
8
-2.C
I7}
Q
Figure 2 - - L o g (d~-dt) versus time

\
"2"q
55 °C

Inverse temperature (°K)'+

3.0 3'1 3.2 3"3 xlO"3
-1.0 • I ~o I

Figure 3 - - L o g k versus inverse

temperature
0

-,0% ~o
-2,0 - "%e ~

30
 C R Y S T A L L I Z A T I O N OF P O L Y E T H Y L E N E T E R E P H T H A L A T E

Table 1. Rate constants of induced crystallization

Sample Temp. (°C) k (h-1) Sample Temp. (°C) k (h -1)

25 0"039 25 0-010
A 30 0.046 C 30 0"0125
35 0" 068 35 0"016
40 0.096 40 0.023

25 O' 022 25 0.006

30 0"025 D 30 0.007
35 0-032 35 0"010
40 0,044 40 0"014
55 0"092

Table 2. Activation energies and frequency factors

of crystallization (k=Ae-AE/a~:

Sample AE (kcal/mole) A (h -1)

A 10.6 10.5 × l0 s
B 9"7 5'6 × l0 s
C 10.4 2.8 x l0 s
D 10-4 1.7 × 105

Table 3. Slopes and ordinate intercept values from the relationship

log k = x log (thickness) + log K

Ordinate
Temp. Slope intercept K
(°c) (x) (log K)

25 3.0 -6.31 4.90 × 10-7

30 3-0 -6"22 6.03 × 10-7
35 3.0 -6'10 7.94 × 10-,v
40 3.0 --5"96 1.10 x 10-e

log (thickness)
[Q
-1"5 -1"0
I 1 ] I I -1"0

b,
i

Figure 4 - - L o g k versus log

(thickness)
O~
_ o

-2-0

31
 R. P. SHELDON

DISCUSSION
The first noticeable feature of the results is that the crystallization rate is
dependent upon sample thickness, the rate at any one temperature decreas-
ing with increase of thickness. Also attention is drawn to the apparent
absence of the sigmoidal type rate curve characteristic of normal crystalliza-
tion; this appears to be a facet of a more general phenomenon in liquid-
induced crystallization. If it occurs at all, it must be in a time interval too
small for normal measurement. Moreover, the curves are of a regular shape
with no superimposition of one curve seemingly on top of another, indicative
of a secondary process found in normal crystallizations4, ~. These features
alone immediately suggest a different mechanism as might of course be
expected on other grounds.
It is interesting to note, as mentioned previously, that at least in the
temperature range studied, the equilibrium density, and hence presumably
the equilbrium crystallinity, is independent of temperature. This is useful in
that it gives a more reliable value for d ~ at 25°C which slightly modifies the
value previously quoted but without prejudicing the conclusions ~. This result
implies that the maximum degree of crystaltinity at these temperatures is
the same independent of temperature suggesting that the previous history of
the polymer has some bearing upon the crystallization process. (Preliminary
results on samples recently received indicate visual confirmation of this
hypothesis in that the samples, which were prepared under different melt
conditions, showed different degrees of brittleness after identical treatment
with liquid and subsequent vacuum.)
The results also indicate that the rate increases with increase of tempera-
ture and that if a situation obtains such as occurs in normal crystallization
where the overall rate increases to a maximum and then decreases as the
melting point is approached then in the present case the system must be
well below the maximum. On the other hand, as discussed below, if a
different type of mechanism applies then the variation of rate with
temperature will not be simply described as above.
It is shown in Figure 2 that log (doo-dr) is a rectilinear function of the
time which enables a kinetic study to be made since the slope is a measure
of the rate at which equilibrium is attained. Careful inspection, however,
shows that this statement is not entirely true in that, although the derived
rate equation holds over the major part of the curve, the initial rate
occurring over the first five per cent or so of the effective time interval is
greater than would be expected from the equation, since the extrapolated
zero-time density is greater than the measured value. Figure 3 shows another
rectilinear relationship, this time between log k and T-1. This relationship
may be expressed mathematically as k = A e -~/Rr where A E is identi-
fied as an activation energy term although the final equilibrium state does
not correspond to one usually considered in kinetic studies, and A is sub-
stantially a temperature-independent constant. The value of the activation
energy, to which reference will be made later, is roughly the same
irrespective of sample thickness, and this factor has been utilized in the
extrapolations for the A values. Figure 4 shows that there is a relationship
between k and sample thickness (x), of the form k = K / x s where K is a
constant which, f o r the sake of a physical picture, may be regarded as a
32
 • CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE

rate constant for a sample 1 cm thick. To obtain the combined effect of the
two equations upon the rate of density increase and at the same time
substituting experimental numerical values we can write
doo- dt=2-63 x 10 -2 × exp [ - (23"03/x 3) x e -z~/nr . t]
Comparison may be made with the form of the equation obtained from
the Avrami treatment which can be expressed 7 as
A'_ V / A'=e-Bt"

where A', which should not be confused with the A of the Arrhenius type
equation, is the limiting volume fraction of crystallinity, V is the volume
fraction after time t, B is a constant and n is an integer having theoretical
values of 1, 2, 3 or 4 depending on the mode of nucleation and crystalliza-
tion. Making the usual assumptions between density and crystallinity it may
easily be shown that
d ~ - dA, dt - dA,
A - de - da, and V = dc - da,
and that
d~o B at
A" - V / A " - d o o - da,

where dc and dA, are the densities of completely crystalline and amorphous
P E T respectively and have the values 8, 9 1-455 and 1-335 g/cm 3. The
equation may now be written
A ' - V / A " = C exp [ -(C'/xZ)(e-ZX~/nr). t]
where C and C' are constants having values of 0.44 and 23"03 respectively.
There appears to be a superficial similarity between the two equations but
the situations are not considered to be strictly analogous since in the present
case crystallization presumably occurs on a progressive front accompanying
liqoid diffusion whereas the Avrami treatment is based on random hetero-
geneous or homogeneous nucleation with subsequent crystallite growth.
However, the time exponent of unity is, on the latter treatment, indicative
of diffusion controlled crystallization following heterogeneous nucleation,
which may well be the behaviour in the present example.
Perhaps a more reasonable comparison may be made with diffusion and
for this purpose we can consider the equation for diffusion into a plane
slab I°
Coo - C t / C o o = A " e-a"otlx" + B,, e - V , Dt/x, + . . .

where Coo and Ct are the concentrations of diffusing substance at equilibrium

and after time t, respectively, A " , B " , . . . and a", b ' , . . . are constants
peculiar to the system (not to be confused with any previous constants), and
D is the diffusion coefficient. Ignoring the less signficant secondary terms
on the RHS, the form of the equation bears a striking resemblance to the
experimental equation particularly when it is remembered that the diffusion
equation is derived on the basis of Flick's law type of diffusion with
constancy of diffusion coefficient, an assumption not always valid for
polymers 11, and although no evidence is available to contradict this assump-
tion at the low concentration end of the scale for diffusing substances such
33
 R. P. SHELDON

as dyes in P E T 1~, the same may not be true for the relatively high
concentrations (,-~ 10 per cent) encountered in these studies. Because of this
the theoretical equation may have to be modified, the modification perhaps
accounting for the discrepancy in the thickness indices, and at the same time
suggesting a better plot for the experimental equation which may thus
include the initial part of the curves.
On the basis of this the picture is now possibly one in which the benzene
presumably induces some relaxation which enables suitable juxtaposition of
polymer chain units for crystallization to occur. It is not clear at this stage
to what extent established crystallization will affect further diffusion, nor at
higher temperatures with suitable diffusing liquid what would be the
influence of temperature alone. In the present case the activation energy
mentioned will be associated with diffusion, the value of 10"3 kcal/mole
perhaps not being an unreasonable one for this system. It is imagined that
the value of A E for any diffusing substance will be strongly dependent upon
the size and nature of the substance 12.
The extension of this work to include a wider range of liquids might
confirm these postulates and at the same time throw more light on the
mechanism of liquid-induced crystallization.

The author wishes to thank I.C.1. Ltd, Plastics Division for their generous
gift of the polyethylene terephthalate film used in these studies.

Polymer Research Laboratories,

Department of Chemical Technology,
Institute of Technology, Bradford, Yorkshire
(Received August 1961)

REFERENCES
1 MOORE,W. R. and SHELDON,R. P. Polymer, Lond. 1961, 2, 315
2a SPicy., J. J. phys. Chem. 1941, 45, 401
b B~E~, W. O., FULLER,C. S. and PACE,N. R. J. Amer. chem Soc. 1942, 64, 776
a A us. Pat. No. 36 684
4 a KELLF-R,A., LESTm~,G. R. and MORGAN,L. B. Phil. Trans. 1954, 247, 1
b MORGAN,L. B. Phil. Trans. 1954, 247, 13
c H , ~ Y , F. D., LORD,F. W. and MORGAN,L. B. Phil. Trans. 1954, 247, 23
5 AVRAMI,M. J. chem. Phys. 1939, 7, 1103; 1940, 8, 212
s HJU~TLEV, F. D., LORD, F. W. and MOROAN,L. B. Ric. sci. (Suppl. A), 1955,
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10See e.g. VICK~STAFF, T. The Physical Chemistry of Dyeing. 0liver and Boyd:
London, 1954
11 KOKES,R. J., LONG,F. A. and HOARD,J. L. J. chem. Phys. 1952, 20, 1711
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34