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Crystallinity in Poly(ethylene terephtha

-
late)." A Comparison of X-ray, Infra-red
and Density Measurements
G. FARROW and I. M. WARD

Crystallinities have been measured in oriented poly(ethylene terephthalate)
fibres by methods based on density, infra-red spectra and X-ray diffraction.
The results have been compared and no correlation exists between the three;
the values from infra-red spectra are high, thosd from X-ray measurement
low, and those from the density fall roughly between the two.
The crystallinity of a polymer fibre is by definition the relative amount of
three-dimensional ordered material present in a sample and this is most directly
measured by X-ray diffraction. The results reported here show that in poly-
(ethylene terephthalate) the infra-red measurements are only correlated with
configurational changes affecting the order within individual molecules. Using
the X-ray measurements to define crystallinity it i~ found that the density of
non-crystalline material increases with orientation so that density measurements
bctsed on the concept of constant non-crystalline density (equal to the density
of amorphous material) are inevitably in error when applied to oriented
samples.
The results also show that highly oriented pin-drawn yarns of low draw ratio
have no appreciable crystallinity which is in contradiction to the view that the
limiting stress built up in the drawing process is caused by the onset of
crystallinity. Although the onset of crystallinity may well increase the rein-
forcement, it is clear that it is not essential to it. Dynamic loss data which had
previously been correlated with crystallinity measured by the infra-red method
may also be interpreted in a different light.

INTRODUCTION
IT rIAS long been recognized that the physical properties of textile fibres can
be considerably affected by the orientation of the molecular chains and the
proportions of crystalline and non-crystalline material. The measurement
of the crystallinity is, therefore, an important part of the characterization
and several physical methods have been proposed and developed for the
determination of crystallinity in polymers and fibres. These include X-ray
diffraction, density measurements, infra-red spectroscopy, nuclear magnetic
resonance spectra and moisture sorption, of which the first three will be
considered in this paper.
The interpretation of all these methods is a matter of some discussion,
but we have adopted the view that by definition the crystallinity of a fibre
is directly related to the presence of three-dimensional order which may be
determined directly by X-ray diffraction. Clearly, this view is open to the
question of the exact degree of three-dimensional order required, i.e. the
minimum number of adjacent unit cells ~aecessary to give a discrete X-ray
reflection, perfection of crystallites, etc. This point is now being investi-
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CRYSTALLINITY IN POLY(ETHYLENE TEREPHTHALATE)

gated quantitatively by Taylor and Robinson using the optical diffracto-
meter. This technique exploits the analogy between the diffraction of light
by a set of holes and of X-rays by a set of atoms ~. It may, therefore, be
possible in the future to define the minimum amount of order detectable by
X-ray diffraction. In the meantime we shall accept that, within the limits
of error set by experimental technique, the ratio of the total integrated
intensity of the X-ray diffraction maxima (typical of three-dimensional
order) to the intensity of the diffuse halo always present in partially
crystalline samples (and typical of the entirely non-crystalline material),
gives a measure of the crystallinity.
The work to be described in this report is the comparison of crystallinity
determined by X-ray diffraction with the crystallinity determined by infra-
red and density measurements on poly(ethylene terephthalate) fibres
subjected to different stretching and heat treatments.

EXPERIMENTAL
X-ray determination o[ crystallinity
The method is described in detail elsewhereL Oriented fibres are chopped
and made into a randomized sample by a pelletting technique. The sample
is placed on the circumference of a focusing camera (evacuated to eliminate
'air scatter') and exposed to a strictly monochromatic beam of X-rays.
The X-ray diffraction lines are recorded on film which, after processing
and drying, is scanned with a microdensitometer. From the resultant trace
the crystallinity is determined by measuring the integrated area of the
crystalline reflections and the integrated area of the non-crystalline back-
ground and comparing the two.

Infra-red measurements
When amorphous poly(ethylene terephthalate) is heat-crystallized or
stretched, considerable changes occur in the intensity of many of the infra-
red absorption bands. The infra-red spectra of fibres are most simply
studied when the fibres are mounted as a grid between rock-salt plates and
an immersion medium (in this case liquid paraffin) is used to reduce the
amount of scattered radiation. A grid of poly(ethylene terephthalate) fibres
(of say 50 denier yarn, 2 denier per filament) absorbs too intensely in the
range 5-10/, for any changes in band intensities to be useful here, but in
the range 10-15# there are several bands whose intensities can be con-
veniently measured. We have therefore followed the method of Miller and
Willis 3 and measured the intensity of the band at 898 cm -1, using the
intensity of the band at 875 cm -1 as a measure of the thickness of the
sample. The 898 cm -1 band has been assigned to a gauche (Figure lb)
configuration of the - 4 9 CHz~CH~---O--- group in poly(ethylene tereph-
thalate) (possibly the C H ~ rocking vibration) 4. The 875 cm -x band has
been assigned to the aromatic - - C H out-of-plane deformation4, and although
small changes in peak intensity may occur on crystallization these are very
small (,~ 10 per cent) compared with the changes observed in the intensities
of absorptions assigned to vibrations of the --O---CH2--CH~--O-- group.
331
G. FARROW and I. M. WARD

The band at 898cm -1 exhibits a maximum absorption for a sample
which is completely amorphous (density l'335g/cm 3) but on heat-
crystallising or drawing a reduction in the absorption of this band
occurs owing to a change in configuration from gauche to trans of
a number of --O--CH2--CH2--O-- groups. It is known from the crystal
structure of poly(ethylene terephthalate) 5 that the configuration of the

(a)

Trans (C) Gauche

Oxygen •Carbon OHydrogen
Figure 1--(a) The crystalline trans
configuration; (b) proposed addi-
tional gauche configuration, which
is present in amorphous material;
(c) end views

---O--CH2---CH2--O--- group in the crystalline regions is trans. It is
suggested that in the amorphous regions both the gauche and the trans
configurations occur. It is assumed in this method, however, that the
intensity of the gauche bands alone gives a measure of the amorphous
content. Thus, by measuring the reduction in intensity of the 898 cm -~
band, the reduction in the amophous content due to various treatments can
be estimated.
Miller and Willis remarked that their method might not necessarily measure
crystallinity because it only measured the 'pure amorphous content" and
there might be many molecules in an intermediate form, described as
ordered amorphous material. In spite of this proviso, the data have been
used to calculate the densities of 'amorphous' material in drawn yarns.
In the papers of Woods and Thompson 1°.17, the measurements are used to
calculate crystallinities, and as we are principally concerned with re-
examining their conclusions, we shall also calculate the crystallinity.
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CRYSTALLINITY IN POLY(ETHYLENE TEREPHTHALATE)

BireIringence
Birefringences were measured using polarized light and a Berek compen-
sator. Each fibre was cut with a razor blade at 45 ° to the fibre axis to
produce a wedge of fibre. The black interference fringe, which occurs at
the edge of the fibre at zero compensation, could then be followed to the
centre of the fibre as the Berek compensator was moved to values corres-
ponding to higher birefringence. This method removes the difficulty that
owing to the difference in dispersion between calcite and poly(ethylene
terephthalate) the correct interference fringe will in general be colouredL

Density
The physical densities of the filaments were measured by observing the
point to which the samples sank in a graded density column7. Some of
the densities of oriented fibres which had been subsequently heat-crystallized
were found to be rather high and were checked by the flotation method,
using a centrifuge to increase the sensitivity. The density of amorphous
poly(ethylene terephthalate) obtained by quenching rapidly from the melt
is 1"335 g/cm ". The density of the crystalline material calculated from the
X-ray crystal structure~ is 1,455 g/cmL If it is assumed that the density
of the amorphous material remains constant, even when oriented, then by
measuring the density of the sample and applying simple proportion the
crystallinity of the sample can be inferred.

Preparation of samples
The filaments used in this investigation were prepared by the conventional
two-stage process 8. Molten polymer is first extruded and collected as non-
crystalline filaments with slight molecular orientation (melt spun yarn).
Filaments of high orientation are then produced by the application of
continuous extension to a pre-set limit (the draw ratio). This second drawing
stage, as it is commonly called, is carried out either by passing the spun
yarn over a heated cylindrical pin alone or over such a pin and then over
a heated plate. A machine is used which, in essence, consists of two pairs
of rolls with the heating device somewhere in between. One pair of rolls
feeds the undrawn yarn from the spinning machine forward at a constant
rate and the second pair moves at a higher velocity, drawing the yarn over
the heated surfaces. Yarns of different draw ratios (i.e. ratios of velocity
of feed rolls to velocity of draw rolls) were produced; the temperature of
the pin was maintained at 80°C and of the plate, when used, at 180°C.
A further heat treatment of yarns was carried out in a silicone oil bath.
The yarns (pin-drawn and pin- and plate-drawn) were held under tension
in the oil and brought up to the required temperature slowly to avoid
sudden stress, and then held at the desired temperature for half an hour.
After cooling, the samples were washed with carbon tetrachloride, to remove
any oil adhering to the surface, and dried.
In this paper details are also given of a comparison of crystaUinities
between spun yarn (0"006in. diameter) and thin poly(ethylene terephthalate)
film (0"005 in. thick), of little or no birefringence, which were heat-treated
at different temperatures. A silicone oil bath was again used but care had
to be taken that the heat treatment and method of immersion did not produce
333
G. F A R R O W and I. M. W A R D

Table 1. Crystallinities of unoriented film (0"005 in. thick) and yarn
(0"006 in. diameter) samples from X-ray, infra-red and density
measurements
Temp. Density Crystallinity (%)
(°C) (g / cm 3) Density Infra-red l X-ray
Film
117 1'359 20 61 29
146 1"378 36 55 35
186 1"385 41 59 37
213 1"395 50 73 46
227 1"391 48 73 48
Yarn
117 1"356 18 41 31
146 1'382 38 35 33
186 1"384 41 37 38
213 1-398 52 46 49
227 1"358" 19" 54* 41"
*The~e results are inconsistent.
Table 2. Crystallinities of oriented fibres from X-ray, infra-red and density
measurements
Density
Sample Bire- Density Crystallinity (%) (g/cm 3)
draw ratio fringence* (g/cm 3) Density Infra-red X-rw Oriented,
non-cryst.
3"0 0'138 1'356 1"356
3'5 0"165 1'361 22 / 59 / 2'0 1"359
4"0 0'180 1"369 28 / 72 [ 8"0 1"359
4"5 0"191 1"360 21 / 76 [ 7"0 1"352
Pin- and plate-drawn yarns
3"0 0" 148 1'385 42 58 27 1'354
3'5 0"163 1"385 42 63 27 1-354
4'0 0"179 1'385 42 77 25 1"355
4"5 0"187 1'382 39 75 24 1-354
5"0 0"187 1'382 39 84 28 1"348
*Figures supplied by D. W. Woods.
Table 3. Measurements on the same oriented fibres as in Table 2 but heat-
crystallized for half an hour at 212 ° under tension*
Density
,Sample Density Crystallinity ( %) (g / cm 3)
draw ratio (g/c m3) Density Infra-red X-ray Oriented,
non-eryst.
3"0 1 '402 56 81 39 1"355
3"5 1"402 56 77 41 1"353
4"0 1"404 58 80 38 1-359
4"5 1 "409 62 85 38 1"364
Pin- and plate-drawn yarns
3"0 1"408 61 75 40 1"359
3"5 1"412 64 80 39 1"365
4-0 1'412 64 86 41 1"365
4"5 1'412 64 83 41 1"365
5"0 1"406 59 86 41 1"356
*Previous work on oriented fibres, heat-treated under tension, has shown that only small changes occur
in birefringence at temperatures less than 225°C. It was. therefore, assumed that this applied also to
the fibre samples listed in this table.
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CRYSTALLINITY IN POLY(ETHYLENE TEREPHTHALATE)

any preferential orientation of molecular chains. This was checked by
birefringence measurements on the treated material.

RESULTS AND D I S C U S S I O N
T h e results a r e g i v e n in Tables 1-3. T h o s e i n Table 2 are also s h o w n
in g r a p h i c a l f o r m i n Figure 2.

.~100 (a) 200

BO +.J J 180

:E u
C:
60 .Io I" ~ "°~ 160 g( -
g t_

/+" A
40 x x 140 :~
x

----o ....... o . . . . . . ~] . . . . . . t~ . . . . . . ~---
C
2O - 120

0 I I I I I 100
2.5 3"0 3"5 4-0 4'5 5"0
Draw ratio

_~I00 200

i
~" ..1 t " B 180
80 ¸
7"o1111o
/÷'/.
60 /o 160 Co~

/t"/"o / / " t,.

~ 40 /+ 140 m
e,~ x
/ o

20 120

__p_. . . . . . o. . . . . . C
0 . - ~ - . . . . . . l a. . . . . I I I 100
25 3-0 3'5 4"0 4-5 5"0
Draw ratio
Figure 2---Crystallinity as a function of draw ratio for
oriented samples o'f poly(ethylene terephthalate) yarn: (a)
drawn over heated pin and heated plate; (b) drawn over
heated pin. A, density, B, infra-red, C, X-ray, D, birefrin-
gence measurements

Comparison oi X-ray and infra-red measurements
It can be seen that the infra-red measure of crystallinity is higher than
the X-ray measure for the unoriented samples (Table 1), particularly for
thin film, and very much higher for drawn yarns. In fact, a value of
50 per cent (Table 2) is obtained for a sample of draw ratio 3"0, which
shows no crystallinity on the basis of the X-ray measurements. An
335
O. FARROW and I. M. WARD

explanation of this divergence has already been suggested4. If the
898 cm -1 band is correctly assigned to the gauche configuration of the
--O--CH2---CH2---O~ group, the intensity of this band is related to only
part of the amorphous material, since the trans configuration can be present
both in amorphous and crystalline material. It was assumed previously
that in unoriented, heat-crystallized material the ratio of trans and gauche
isomers in amorphous material remained constant and thus a decrease in
the concentration of the gauche isomer gave a measure of the decrease in
amorphous content. However, there is a marked difference between the
crystallinities determined from infra-red measurements on spun yarn and
thin film, which is not apparent in the X-ray measure, or in the density,
and implies that the ratio between gauche and trans configurations does not
remain constant. It is possible that surface orientation (which is hard to
detect) may exist, and this would affect the ratio of the trans to the gauche
configuration. This explanation could account for the difference between
film and fibre where very different surface areas are involved.
With drawn yarns, the drawing process will tend to produce fully extended
trans configurations, without necessarily producing crystallinity. Thus it can
easily be seen that the infra-~d measure of crystallinity would be very much
higher than the X-ray measure.

Comparison of X-ray and density measurements
It has been shown previously2'9 that a reasonable correlation exists
between crystallinities measured by X-rays and density for unoriented
specimens of poly(ethylene terephthalate). This is again confirmed in
Table 1, the only discrepancy occurring with samples that have been heat-
crystallized below 120°C.
No similar agreement exists between the crystallinities measured by
density and X-rays for drawn yarns. It is suggested that this arises from
the fact that in drawn oriented yarns it is no longer permissible to regard
the non-crystalline material as having a constant density of 1.335g/cmL
With drawn yarns, of draw ratio 3-0 and less, no discrete X-ray reflections
appear; there is only a 'thickening' of the intensity on the equator of the
X-ray photograph. This is in disagreement with the previously held viewx°,
based on the infra-red method of measuring crystallinity, that the non-
crystalline density decreased on drawing, owing mainly to the formation of
microscopic voids. It is suggested not that voids are no longer formed at
high draw ratios but that the increase in density due to the orientation of
molecules (without the formation of crystallinity) is far in excess of the
reduction in density caused by the formation of microscopic voids.
From the X-ray measure of crystallinity and the density of the crystalline
regions (calculated from the crystal structure as 1"455 g/cm3), the density
of the non-crystalline material in oriented fibres can be calculated (last
columns of Tables 2 and 3). In most cases the value is about 1.355 g/cmL
It is a little higher for the yarns which were heat crystallized.

Molecular orientation measurements
Measurements of the molecular orientation in poly(ethylene terephthalate)
filaments were made in a previous investigation 11 by using the dichroism
336
CRYSTALLINITY IN POLY(ETHYLENE TEREPHTHALATE)

of dyestuffs extruded with the molten polymer during the spinning of the
filaments. Orientation factors obtained in this way were then compared
with those obtained from birefringence measurements, which depend on
the polarization of the molecules. The changes occurring on stretching the
filaments over a hot pin at 80°C were studied, together with the effects of
subsequent shrinkage of these drawn filaments. It was concluded from
this work that up to draw ratio 2-96 orientation occurred without crystal-
lization. At higher draw ratios the orientation factors derived from
birefringence and dichroism measurements did not agree, the latter values
being lower. If crystallization occurs and the crystalline regions are free
from dyestuff then the dichroism measurements will relate only to the
orientation of the non-crystalline regions. These regions are, therefore, less
oriented than the crystalline regions. This would be expected since the non-
crystalline regions will contain all the entanglements and the non-ordered
molecules. In addition the shrinkage in boiling water was very dependent
on draw ratio: below a draw ratio of 4'0 the shrinkage was very large,
suggesting that the crystallinity was very low or non-existent.
The general picture which emerged from these results was that at low
draw ratios a yarn of high orientation and little or no crystallinity was
produced. This picture is confirmed by the present X-ray measurements.
In the absence of hot-plate drawing the crystallinities (Table 2) of drawn
yarns are very small.

Drawing of poly(ethylene terephthalate) filaments
The essential feature of the drawing of poly(ethylene terephthalate)
filaments is the sigmoid shape (dependent on the rate of straining) of the
stress-strain curves. The final rise in modulus in these curves implies that
reinforcement occurs and it is of some interest to consider how this arises
at molecular level. It has been shown by Treloar 1~ that a network of long
chain molecules will exhibit this form of stress-strain characteristics and
it is usual to assume that the network is formed by chemical cross!ink.~ and
entanglements. It would now appear, therefore, that the principal cause of
reinforcement in poly(ethylene terephthalate) is the presence of
entanglements, since chemical crosslinks do not occur. Independent
evidence for the existence of such entanglements has come from the results
of nuclear magnetic resonance investigations of poly(ethylene terephthalate)
and related polyesters13'14. The measured second moments at 20°K and
90°K (which are a measure of the interatomic distances of the hydrogen
atoms) are greater than the calculated values for wholly crystalline samples.
This was attributed to the tangling of molecules in the amorphous regions
and consequent very close approach of some of the hydrogen atoms.
In the case of poly(ethylene terephthalate) it was previously considered
that the reinforcement occurring in the drawing process arises from stress-
induced crystallization1~. Although the onset of crystallization may well
increase the reinforcement, it is clear that it is not essential to it. This
has been confirmed by production of oriented fibres of poly(ethylene
methylterephthalate) of birefringences up to A=0"06 (draw ratio 6-5). The
drawn fibres exhibit drawing characteristics similar to those of poly(ethylene
terephthalate) and have quite reasonable tenacities (2-2"5g/denier). If it
337
G. FARROW and I. M. WARD

is assumed that the maximum birefringence, ~Xm~xof this polymer can be
calculated from the polarizability of the bonds 1~, an approximate figure of
Amax= 0 ~14 is obtained. In this calculation it was assumed that the molecule
is planar and that the packing of the molecules corresponds to a density of
l'170g/cm 3, the density of amorphous poly(ethylene methylterephthalate).
It seems, however, that birefringences approaching 0.14 are unattainable
because the bulky nature of the methyl side-group prevents the molecular

Figure 3--X-ray photographs of poly(ethylene methylterephthalate) yarn: (a)
undrawn; (b) drawn (A = 0"06)

chains from extending fully. X-ray photographs (Figure 3) of the fibre
before and after drawing show a non-crystalline pattern, although in the
latter case there is a 'thickening' on the equator of the X-ray film, indicating
that an alignment of molecular chains has occurred, but without the
production of crystallinity. The density also increased to a value of
1-199g/cm 3. Various heat treatments have been applied to the polymer
in an attempt to induce crystallization, but, so far, without success.
Dynamic mechanical measurements
Poly(ethylene terephthalate) undergoes two dynamic mechanical loss
processes, one associated with the glass-rubber transition which occurs at
about 80°C in amorphous polymer and the other at .about - 4 0 ° C (at
-~ 100c/s). The high-temperature dynamic loss process is considerably
affected by orientation and crystallization of the polymer, as shown by
Woods and Thompson 15. It was found that the temperature of maximum
work loss moved to higher temperatures with increasing fibre crystallinity,
as determined by the infra-red method of Miller and Willis 3. As the
changes in infra-red spectra are directly related to configurational changes,
and correlate more closely with the extent of molecular orientation in the
fibres, it would appear that a better interpretation of the results obtained
from the dynamic mechanical measurements is that the upper loss peak
is affected by the cordigurational changes or the molecular orientation rather
than by crystallinity per se. This result is in agreement with the conclusions
eached by Ballou and Smith is in some earlier work on the measurement
of the dynamic modulus of poly(ethylene terephthalate) fibres. It is intended
to test this point in detail in the immediate future by making dynamic
mechanical measurements on the range of samples characterized in this
investigation.
338
CRYSTALLIN1TY I N 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 )

Recent nuclear magnetic resonance measurements on' poly(ethylene
terephthalate) have shown that the n.m.r spectra are considerably affected
by crystallinity and orientation 19. These changes have been related qualita-
tively to corresponding changes in the dynamic mechanical properties. It is
intended to make further comparisons between n.m.r, spectra and X-ray
crystallinity data to obtain more detailed information concerning the
relationship between the dynamic mechanical properties and molecular
structure.
CONCLUSIONS
The measurements of crystallinity in oriented poly(ethylene terephthalate)
fibres by methods based on density, infra-red spectra and X-ray diffraction
have been compared. There is no correlation between the results of the
three methods. By definition, the X-ray measure has been considered as
the standard, and it is then concluded that
(1) the infra-red method measures configurational changes, more related
to the orientation of molecular chains than to crystallinity;
(2) the density of the non-crystalline material can no longer be assumed
constant and therefore the measurement of crystallinity in drawn fibres by
density is unreliable.

We wish to thank Mr D. W. Woods for his co-operation in providing
quantities of drawn filament yarns.
Research Department,
Fibres Division,
Imperial Chemical Industries Ltd,
Harrogate, Yorks
(Received 7th March, 1960.
Revised version received 13th April, 1960)

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