You are on page 1of 8

An infra-red spectroscopic study of molecular

orientation and conformational changes in
poly(ethylene terephthalate)
A. Cunningham and I. M. Ward
Department of Physics, University of Leeds, Leeds LS2 9JT, UK

and H. A. Willis and Veronica Zichy
Research Department, Imperial Chem&al Industries Ltd, Plastics Division,
Welwyn Garden City, Hefts AL7 1HD, UK
(Received 8 March 1974)

Polarized infra-red (i.r.) spectroscopy has been used to study the changes in molecular
orientation and conformation which occur on drawing poly(ethylene terephthalate) sheets.
The i.r. data provided orientation functions (P2(0)~ir where 0 is the angle between the
molecular chain axis and the draw direction for these uniaxially oriented sheets. Excellent
agreement was obtained between the i.r. orientation functions for absorption bands
associated with benzene ring mode vibrations, and orientation functions obtained from
optical birefringence. Infra-red orientation functions for absorption bands associated
with the trans and gauche conformations of the glycol residue, were then combined with
i.r. estimates of the trans/gauche concentrations to examine the changes occurring in
drawing. For drawing at 80°C up to a draw ratio of about 3-5, there was good agreement
with expectations based on the deformation of a rubberlike network.

INTRODUCTION have been given particular attention. First, there is the
molecular orientation. In one way drawn films this is
Although the examination of polymers by infra-red (i.r.)
complicated by preferred orientation of the (100) planes
spectroscopy with polarized radiation has been under- of the crystalline regions 5, 6. We have taken particular
taken for many years, it is only comparatively recently care to reduce this effect to a minimum in the films
that the measurements have been used to obtain an prepared for the present investigation. Secondly, there
absolute measure of molecular orientation in terms of
are the changes in rotational isomer content with
orientation functions similar to those employed in
changing degrees of deformation or draw ratio. It is
optical, X-ray diffraction and n.m.r, studies. Most of
now generally accepted that these are primarily associated
these quantitative i.r. studies have been carried out on with the trans and gauche isomerism of the ethylene
polyethylene, notably by Read, Stein and their colla- glycol linkage 7-9, and there have been a number of
borators, and extensive measurements have been made
publications where it has been shown that the trans
on low density polyethylene 1, oxidized polyethylene 1,
content increases and the gauche content decreases with
ethylene-carbon monoxide copolymers ~ and crosslinked increasing draw ratio or density 10-12. In the present
amorphous polyethyleneS.
paper, by combining quantitative measures of both
The particular value of assessing the i.r. data in
molecular orientation and rotational isomer content,
terms of orientation functions, rather than dichroic we are able to carry the analysis forward to a greater
ratios, is that they can then be used to compare with
degree of sophistication than has hitherto been achieved.
other measures of orientation. In this paper we describe
an i.r. spectroscopic study of poly(ethylene terephthalate)
(PET) where the i.r. results are combined with measure- THEORY
ments of refractive indices to provide quantitative As the theory to be used has been described in detail
information regarding both molecular orientation and in the previous paper 4, only a brief summary will be
conformational changes. The i.r. data will be analysed given here.
using the theoretical results derived in the previous The measurements are made with the electric vector
paper 4, which take into account both the reflectivity of the polarized i.r. radiation along the draw direction
correction and the internal field effect. (z) or perpendicular to the draw direction in the plane
There have been several previous i.r. structural of the film (x). Absorption coefficients kz and kx are
studies of oriented PET fibres and films. Two aspects then calculated from equation (12) of the previous

POLYMER, 1974, Vol 15, November 749
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et aL
paper, where the absorbance A is given by: tion function (P2(0))lr. An absolute measure of the
chain axis orientation can therefore be obtained either
A = log10/~=0"4343{~-t 2k2 -/ if Ora is known or if the method can be calibrated by
(n+nKBr)2j (1) comparison with another method of measuring molecular
orientation. In this investigation we have combined
where It, I~ are the incident and transmitted intensities
the i.r. measurements with refractive index measure-
respectively at the peak of the absorption, n and k are
ments to examine the validity of the i.r. method and to
the real and imaginary parts of the complex refractive
provide a possible measure of absolute calibration.
index of the polymer at the free space wavelength )~,
For a transversely isotropic sample, the refractive
and nr:Br is the refractive index of the potassium bromide
indices nz and nx can also be used to calculate (P2(0)).
plates used to contain the sample (assumed constant
Since this is a different measure, we introduce the
and real). The thickness of the sample is y0, and the
subscript 'opt'. Following the previous paper, letting
free space wavelength at the absorption peak is )~.
The value of k can be found directly from equation n~-I "e
(1). This equation is a quadratic in k and has two solu- ~=¢i (4)
tions, one of which may be rejected by inspection, We then have:
since an approximate value of k can be obtained in
the absence of the reflectivity correction term
2k2/(n+n~zBr) 2. ¢~ + 2¢~ = (P~(0))opt (5)
These values for kz and kz are then combined with
the optical values of nz and nx, to obtain the imaginary Ae/3e0 can be estimated from measurements on highly
parts of the corresponding average complex polariz- oriented samples where (P2(0))--*l. We have used the
abilities ( %*) = ( % ).- ~ ( .% ) . and
. (.~ * ).= ( ~.) - z ( o ~ ) (see value 0.105 calculated from data in ref 6.
ref 4), using the Lorentz-Lorenz equation. We have: It can be appreciated that if the i.r. method provides
an accurate measure of chain axis orientation then a
2 4 4zrN ,
6nzkz{n4z + 2n~zk~+ 4n~ - 4k~ + k z + 4}- 1 = _ i f _ ( % ) plot of P2(Om)(P2(O))ir against (P2(0))opt will be linear.
Moreover, the optical measurements can be regarded
as providing a calibration of the i.r. technique, by
and allowing P2(0m) to be calculated. Alternatively, if an
independent estimate of 0m can be obtained (say from
6nxkx{n~ + 2n~k~+ 4n~- 4k~ + k) + 4}-1 = ~ - ( a ~ ) (2) crystallographic data) then the i.r. data can be directly
converted to an absolute measure of chain axis
orientation.
These polarizabilities, where N is the concentration
of absorbing species/unit volume, relate to the distribu-
tion of molecular orientations as follows. It is assumed EXPERIMENTAL
that an individual transition moment direction makes Sample preparation
a fixed angle Ora with the chain axis, and that the cor-
The starting material for all the samples investigated
responding chain axis makes an angle 0 with the draw
was isotropic amorphous PET film (intrinsic viscosity
direction.
0.61) of thickness 30/~m. This film was prepared by
It was shown in the previous paper that for a uniaxially
melt extrusion and quenching onto a chill roll. Two
oriented polymer:
series of oriented films were studied. Series (i) was
prepared by drawing strips of the isotropic film to a
~ x = P2(Om)(P2(O))ir (3) constant draw ratio of 4:1 at temperatures in the range
60°C to 100°C. Series (ii) was prepared by drawing at
It is perhaps worth commenting that this equation is constant temperature (80°C) to different draw ratios in
very closely related to the more familiar relationship the range 1.5: 1 to 5: 1. Details of the sample dimensions,
in terms of the absorbances Az and Ax, which follows and the extensometer crosshead speeds used are listed
directly from the molecular gas approximation without in Table 1. For convenience a range of cross-head
taking into account reflection losses and the internal speeds was utilized in the sample preparation. Subsidiary
field effect. In this case we have: experiments showed that this did not significantly affect
the degree of molecular orientation achieved.
Az--A~ The sample thicknesses were measured with a pre-
Az~ = P2(Om)(P2(O))lr
cision dial indicator and were checked by near i.r.
interference fringe measurements. These results are also
In these equations P~(Om)=½(3cos2Om-1) and is shown in Table 1, together with density measurements
assumed to be a constant quantity depending only on obtained using a density column prepared from an
the molecular structure of the polymer. It is, of course, aqueous solution of sodium bromide and water.
quite possible that this assumption does not hold if
there are changes in molecular conformation on drawing.
(P2(O))ir=½(3(cos2O)ir-1), defines the mean value of Refractive index measurements
P2(0), determined by the i.r. method for the molecular The measurements of refractive index were undertaken
chain axes and is the orientation function which we using an image splitting interference microscope (Zeiss
will be primarily concerned with in this paper. The Zena Interphako) with accurately calibrated immersion
measurement thus provides a direct measure of the liquids. All measurements were made at 551 nm. The
product of the constant quantity P2(Om) and the orienta- results are shown in Table 2.

751) POLYMER, 1974, Vol 15, November
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.
Table I Details of sample preparation

Average
thickness
Crosshead Gauge after
Temp. Draw speed length Width drawing
(°C) ratio (cm/min) (cm) (cm) Shape (/zm) Density

Series (i)
60 4:1 5 8 3 Strip 11.5 1.362
65 4:1 5 8 3 Strip 12 1 '362
70 4:1 5 8 3 Strip 14 1 '362
75 4:1 5 8 3 Strip 14 1.358
80 4:1 5 8 3 Strip 16 1.358
87 4:1 5 4 3 Strip 16 1.355
94 4:1 5 4 3 Strip 11 1 '356
100 4:1 5 4 3 Strip 12 1 '356

Series (ii)
80 1.5:1 Unknown 10 3 Taper 25 1-339
(dead-loaded)
80 2.3:1 Unknown 10 2-5 Taper 20 1.340
(dead-loaded)
80 2.7:1 Unknown 10 2 Taper 14 1.343
(dead-loaded)
80 3.4:1 Unknown 10 1-5 Taper 16 1-354
(dead-loaded)
80 3.7:1 Unknown 10 1 Taper 16.5 1-356
(dead-loaded)
80 4.5:1 20 4 1 Dumbbell 12-5 1.365
80 5:2 20 4 1 Dumbbell 12.5 1.365
Isotropic 1:1 . . . . 30 1.337

2C
;a Infra-red measurements
975crn-~ The i.r. measurements were carried out using a Hilger
875cm~
H800 double beam i.r. spectrometer, with a wire grid
polarizer Cambridge Consultants Limited type 1CR 55.
The measurements were made at normal incidence and
4C
the film sample was sandwiched between potassium
o bromide plates with a very thin film of Nujol between
795cm"1 ~ /~ 896 Cm-' { I
Ln
each surface. This reduces the reflection at the polymer
surface, which for an isolated polymer film gives rise
to interference fringes. The Nujol forms an approximate
~- 6C
match for the refractive index of the polymer and has
a low absorption in the region 750-1300cm -1. The wire
grid polarizer was assumed to transmit radiation with
the electric vector in one plane only, and the chart
recorder was calibrated as a linear vertical scale so that
80
the ratio IT/I~ could be determined directly from
the curves, using a pseudo-base line as shown in
b 875cm -~ Figure 1.
For each sample, two spectra were recorded in the
2C
normal incidence case, one with the electric vector
parallel to the z direction and the other at right angles
in the x direction. For each polarization the spectro-

/
meter was scanned through the range 750-1100cm -1 at
~ 4C a speed of 42-5 cm-1/min and the slit width was gradually
o
reduced from 0.9 m m at 750 cm -1 to 0-5 m m at 1100 cm -1.
Typical examples of such spectra, obtained from a

•k'X•
E
sample of intermediate draw ratio, are shown in Figures
c
6cm'' i la and lb.
795 cm-i
6C

Absorption band assignments
The detailed assignment of the absorption bands in
80
the i.r. spectrum of PET has been the subject of much
pseudo base lin~"~ ~ -~. ~ .1 . / attention and controversy. Some of this stems from the
proposal originally made by one of us 7-9, that the major
Figure 1 The infra-red spectrum of PET in the region 700-1000 differences between the i.r. spectra of amorphous and
cm -z. Electric vector parallel to (a) z direction or (b) x direction partly crystalline samples of PET are due to rotational

POLYMER, 1974, Vol 15, November 1'51
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.
isomerism of the where/~ and p0 are the densities of the isotropic polymer
and the oriented film respectively. Table 2 shows that
0 CH2 the predicted values of nl8o correspond very closely to
/\/ \/ the experimental value of 1.582, confirming that these
CHz O samples are transversely isotropic to a very good
group. Crystallographic studies lz, showed that the approximation.
conformation of this group in the crystalline regions The optical data have also been used to calculate
is trans. It was proposed that in the amorphous regions the overall molecular orientation function (P2(O)ovt) on
the gauche conformation of this group is present as the basis of equations (4) and (5) above, and the results
well as the trans conformation. Although this proposal are shown in Table 2.
was initially not generally accepted TM 15, in most later The i.r. measurements on the bands at 875, 795 and
paperslZ, 16-18 there is a general consensus that certain 896cm -1 were first used to calculate the absorbances
absorption bands can be identified with the trans and Az and Ax, corrected for reflection at the interfaces
gauche conformations. In this paper we have chosen using equation (1). These absorbances were then used
the 975 cm -1 trans band and the 896 cm -1 gauche band to calculate the quantities Cz and ~x, on the basis of
for quantitative analysis. equations (4). Finally values of the i.r. orientation
It is also valuable to analyse the behaviour of absorp- function product P2(Om)(P2(O))ir were calculated using
tion bands associated with the terephthalate group, and equation (3).
more particularly the benzene ring. Here we have It is also possible to calculate the orientation functions
chosen the 795 cm -1 and 875 cm -1 bands. The 875 cm -1 ignoring the local field correction, by assuming that
band has the added advantage that it can be assigned (c¢*)ocn'2-1, i.e. (~")ocnk. Values of P2(Om)(P2(O))ir
with some certainty to an out-of-plane C - H deformation so calculated for the 875cm -1 band are shown in
vibration, in which the transition moment vector lies Figure 4.
normal to the plane of the benzene ring. From the
crystallographic data lz, 0m the angle which the transition Compar&on of the i.r. and optical orientation functions
moment vector makes with the chain axis would then
The 875 and 795cm -1 bands are both associated
be about 86 °.
with vibrations of the benzene ring. They are therefore
not directly affected by conformational changes in the
same way as the 975 and 896 cm -1 bands, and might be
RESULTS AND DISCUSSION
expected to give an indication of the overall chain
The optical measurements of the refractive indices nz orientation. The optical orientation functions are de-
and nx were used to calculate the refractive index of the rived on the premise that they relate to the orientation
isotropic polymer ni8o, on the basis of averaging the of an extended repeat unit. Figures 2 and 3 show values
polarizabilities and assuming that the samples were
transversely isotropic. As before, the Lorentz-Lorenz
equation is used to relate polarizabilities and refractive ,%
index. We have:
n~so - 1 1 p, t n ~ - 1 , 2 ( n ~ - l)]
n ~ s o - 2 - 3 p0 ~ n z ~ - v ~ ]
0"20

Table 2 Refractive index measurements

Temp. Draw ni
(°C) ratio nz nx (predicted) (Ps(O))opt
,_ .0"15
Series (i)
60 4:1 1-713t 1.540 1-582 0.729 -$
65 4:1 1.709 1,540 1.590 0.715
70 4:1 1-703 1-542 1.580 0.682 V
75 4:1 1-695 1.540 1.579 0-663
80 4:1 1.679 1-549 1.580 0.557
87 4:1 1.660 1-555 1.580 0-453 <o, o.lo
94 4:1 1.620 1.570 1.576 0.219"
100 4:1 1-587 1.576 1.570 0-049* 0

Series (ii)
80 1-5:1 1- 592 1" 576 1.580 0.071
80 2.3:1 1" 621 1.563 1- 580 0- 256 0"05
80 2.7:1 1" 623 1.563 1- 580 0" 264
80 3.4 ."1 1.658 1.553 1- 578 0.455
80 3.7:1 1" 684 1" 547 1.581 0.586
80 4.5:1 1" 704 1" 540 1" 578 0.696
80 5:1 1.705 1" 540 0-578 0" 700
Isotropic ~ 1.582 1 "582 1 "582 0 I I I I I
0 d.2 0-4 d.6 o'.e
* These samples were not used in the subsequent i.r. analysis gP2 (el> opt
because of the poor predicted value of ni
"l'These values were obtained by extrapolation of the higher Figure 2 Values of P=(Sm)(P=(8))ir for the 875cm -1 band as a
temperature nz data function of (P2(e))opt. O, Series (i); I I , series (ii)

752 POLYMER, 1974, Vol 15, November
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.
degree of anisotropy in absorbance. In the case of the
875 cm - t band, if it is assumed that the optical measure-
ments provide an absolute calibration, the value of Om
is found to be 85 ° . This agrees well with the value
expected on the basis of the band assignment*. Hence
we can make the following identity, (P2(O))~[ 5=
- 0 - 4 0 d 2 ~ (P2(0))opt.
These results were obtained using the Lorentz-Lorenz
internal field correction. Figure 4 shows a comparison
~- -0-3 of the optical orientation functions with those deduced
from the i.r. data for the 875cm -1 band ignoring the
,a.,,, local field correction. The solid line shows the expected
V
correlation for Ore= 85 °. The experimental correlation is
now less good, and it appears that the value of (P2(0)}
"~-0-2
v
a.,,, •
is an underestimate. These results give some support for
the validity of our treatment.
The orientation behaviour of the 975 and 896cm -1
bands associated with the trans and gauche conforma-
-o.i tions respectively, is much more complicated than for
the 875 and 795cm -1 bands. Figure 5 shows values of
P2(Om)(P2(O))ir for the 975 cm -1 trans band as a function
of (P2(0))opt. In this case there is not a linear relationship,
I I I I I I I I I but the trans orientation function increases rapidly for
0 0.2 04 0.6 0.8 1.0 low optical orientation function values to achieve an
<P2 ( O}> opt almost constant value for (P2(0))ovt>0"5. This result
shows that the orientation of the trans conformation is
Figure 3 Values of P~(Srn)(P~(O)>ir for the 795em-1 band as a not representative of the overall chain axis orientation.
function of (P2(8)>opt. O, Series (i); II, series (ii) Figure 6 shows the corresponding results for the 896 cm -1

* In view of the possible errors in A~13~0 such close agreement may
well be fortuitous.
/

_o., / [ ....
/o, I o/ o.o

~ 0'3

0 0'2 0'4 0"6 0,8 I-0

f:onrrC:ic~7oOf<(~:(~,e>l?3:;(~;SUlllBt::blea,:~i~ ignoring the internal field O l~

of P2(Om)(P2(O)>ir plotted as a function of (P2(0)>opt for
the 875 and 795cm -1 bands respectively, for the two , ~ , , ~ , ,
series of oriented samples. There is an excellent linear O 0.2 0.4 0-6 O18 I-©
relationship between these two parameters for both
bands, confirming that both are measuring similar <P2(O)>oPt
quantities. The greater consistency of the results for Figure 5 Values of P~(Om)(P~(O))irfor the 975cm-1 trans band
the 875cm -z band can be attributed to its greater as a function of(P2(O)>opt.(3, Series(i); II, series (ii)

B POLYMER, 1974, Vol 15, November "/53
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.
(P2(0)>opt= 1) for both the trans and gauche bands.
If we combine these extrapolations (shown in Figure 7)
with the assumption that there is 100 ~ trans concentra-
tion at full overall orientation, we have a very simple
picture. The extrapolation of the 975cm -1 band then
gives us the value of the polarizability for 100~o trans
-0"2 concentration; hence we can find the trans concentration
.L for an isotropic sample and thus the corresponding
gauche concentration. We are then able to calculate
the trans and gauche concentrations for each sample,
q.
which, of course, should total 100~. In fact, we chose
the value of 40 for 100K trans concentration, which
(3)
gave the best overall fit to the data so that the sum of
C "f , the trans and gauche concentration totalled as close to
(Y 100~o as a least squares fit would provide. Table 3 lists
these intermediate concentration values and it can be
seen that there is very good internal consistency. A
remarkable result, which is not to be expected, is that
absolute values obtained for the polarizabilities of the
trans and gauche species by this fitting procedure are
+O'1 L identical. It can readily be appreciated that this is so
0 0.2 0"4 0-6 0"8 1.0
<P2(el>opt I00
//
Figure 6 Values of P2(Sm)<P~(O)>irfor the 896cm -z gauche band
as a function of (P2(0)>opt. O, Series (i); I I , series (ii) 0'1~: /
/
/ E
/ o,2
gauche conformation band. In this case a completely c

different pattern is observed. The gauche orientation 75 o
function is small and positive for (P2(0))opt<0-45 and
then becomes negative, the numerical value increasing
rapidly in the highly oriented samples.
These results, taken together, suggest the following.
0 = g
First, that the molecular segments which contain the
trans conformation possess at low overall orientation
!so
much higher orientation than those segments which
0.06 2" r

contain the gauche conformation. Secondly, that up to $y" S I S %0 0

(P2(O))opt~0.45 the gauche orientation distribution is
very close to isotropic. There is even an indication that U
the gauche segments for low orientation may be oriented 0.03 'zY'" t s ° 2s
transversely to the draw direction. However, it is difficult
to study the 896cm -1 band quantitatively in terms of
orientation because it overlaps with the strong 875 cm -1
band. The i.r. data must therefore be regarded as incon-
clusive in this particular detail. Finally, it is clear that ! I I I I I I I I 0
at high degrees of overall molecular orientation there 0 0.2 0.4 0-6 08- J.o
is appreciable alignment of the gauche segments. <P2 (e)>opt
Figure 7 Values of ~o and concentration for the trans conforma-
The concentration of the absorbing groups tion (975cm -1 band) and the gauche conformation (896cm -1
The concentration of the absorbing groups can be band) as a function of <P~(O)>opt. - - - - , trans; , gauche.
estimated from a calculated value of 40. O, Series (i); I--1, series (ii)
It was found that the calculated values of 40 for the
875 and 795cm -1 bands are approximately constant Tab/e 3 trans and gauche concentrations
for all degrees of molecular orientation. This result is
an expected one, since these bands have been assigned % trans % gauche
(P~(O)~>opt (xi) (yi) (xi"l-yi)
to vibrational modes which are independent of the
conformational state of the molecule. 0"0 24 76 100
On the other hand, the values of 40 for the 975 cm -1 O"1 28 72 100
trans band and 896cm -1 gauche band show a strong O"2 3£ 67 99
dependence on the degree of overall molecular orienta- O"3 38 61 99
0"4 44 56 100
tion. This can be seen in Figure 7 where 40 is shown as O"5 50 49 99
a function of (P2(8))opt, and we observe a smooth 0.6 58 42 100
increase in trans content and a smooth decrease in 0-7 68 34 102
gauche content with increasing overall molecular orienta- 0"8 77 24 101
0.9 88 13 101
tion. We have attempted to make the extrapolations 1.0 100 0 100
of 4o t o full overall molecular orientation (i.e.

754 POLYMER, 1974, Vol 15, November
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.
by noting that the q~0 curves for the trans and gauche I'0
species (Figure 7) cross at a point corresponding to
50 ~ trans. It should perhaps be pointed out that although
the absolute values of the polarizabilities of the trans
and gauche species are identical for the present series
of samples this may not hold for other samples where K
O
high degrees of crystallinity are obtained. In the samples A

examined here the crystallinities were always very low, ~05
and usually less than 10~o. V

Relationship between molecular orientation and changes in Draw r a t i o ~ 4 0
molecular conformation
It has already been remarked that the gauche orienta-
tion is very low over most of the orientation range. I / .....

This implies that the overall molecular orientation 0 I0 20 30
k2_ /
arises largely from those molecular chains possessing
the trans conformation. Moreover, at high overall
Figure 8 Plot of <P2(0)>opt against [A2-(1/A)] for series (ii)
molecular orientation there is little further increase in (samples drawn to a series of draw ratios at 80°C)
the trans orientation. The values of the orientation
function for the 975 cm -1 trans band, <Pz(0)>lr trans ×
P2(0~an') can be extrapolated to give a constant value
for high overall molecular orientation. If it is assumed
that this value corresponds to complete orientation of
the trans conformers, this gives a value for 0- -t'a""
m

With this result we can then calculate absolute values
of 32 °.
~ 0'4

8 o-3
of <P2(O)>irtrans for intermediate degrees of overall
molecular orientation. These results are shown in
Table 4. 0"2
Furthermore, recalling that the orientation of the
gauche conformers is very small, it can be suggested
that to a good first approximation the optical orientation b O'l
c
function (Pz(O)>opt which reflects the overall orientation
is given by: ' l I I I I I i i

0 I 2 3 4 5 6 7
<P2(O)>opt = f trans<P2( O)>ir trans
where titans is the trans mass fraction. The results
Figure 9 The change in trans conformation for series (ii) as a
shown in Table 4 confirm that this is a reasonable function of [1/3{,V+(2/A)}-t]
approximation.
A more remarkable feature of all the results, however,
of a rubberlike network, and we will discuss two pieces
is the exact similarity of the data for the two series
of evidence which support this view. First, there is the
of samples, and this suggests that there is a unique
development of orientation in a rubberlike network.
relationship between the concentration of trans and
If it is assumed that the network can be considered as
gauche conformers and the overall orientation as re-
a network of freely jointed chains of identical links 19
vealed by optical measurements or by the orientation
(the so-called random links), it can be shown z0 that the
of the 875 or 795cm-Z bands.
orientation function <P2(0)>randora link for the random
A possible explanation of this remarkable result is
links is given by:
that both the conformational content and the molecular
orientation relate only to the overall strain, irrespective
of the temperature and conditions of draw. This explana- < P 2 ( 0 ) > r a n d o m link = ~ A -- + terms in N-z, etc.
tion would certainly hold for a given temperature if
the drawing process can be regarded as the extension where N is the number of random links between the
network junction points (the entanglements) and h is
Table 4 Comparison of <P2(O)>opt with the extension or draw ratio. Stress-optical data on
ftrans<P2(O)>ir trans PET in the temperature range 60--90°C showed 2a that
the behaviour fitted this model to a good approximation,
(P2(O)>opt <P:~(O)>lrtrans ftrans<P2(O)>ir trans and a value of about 6 was obtained for N. A plot of
0.0 0"0 0.0
the present 80°C results for <P2(O)>, based on the
0.1 0.2 0"06 values obtained for the overall molecular orientation,
0.2 0.4 0.13 is shown in Figure 8. It can be seen that there is a good
0.3 0.6 0"23 linear relationship between <P2(O)> and [Az-(1/A)] up
0.4 0.8 0-35
0.5 0.9 0"45
to a draw ratio A of 3.5, and this gives a value for N of
0.6 0.9(5) 0"55 about 5, in reasonable agreement with the previous
0.7 1 "0 0-68 stress-optical results.
0.8 1-0 0.77 A second piece of evidence comes from a considera-
0.9 1 "0 0.88 tion of the conformational content as a function of
1.0 1.0 1.00
draw ratio. According to Abe and Flory z2, the average

POLYMER, 1974, Vol 15, N o v e m b e r 755
I.r. study of molecular orientation and conformational changes in PET: A. Cunningham et al.

molecular orientation by polarized Raman spectroscopy
and polarized fluorescence are also presented.

CONCLUSIONS
(1) Polarized infra-red spectroscopy can provide accurate
0.6-
measures of overall molecular orientation in PET.
There is confirmation that corrections for reflectivity
w
a and the internal field effect are required.
0 -
h (2) The combination of measurements of molecular
0 orientation with concentration of conformers can throw
light on the deformation mechanisms occurring during
5 drawing.
0.3-

ACKNOWLEDGEMENTS
During the period of this research A. C. held a Science
Research Council CAPS studentship. We are indebted
to Imperial Chemical Industries, Plastics Division as
I I I I I I t I

2 3 4 5
the industrial sponsor. We also wish to thank Mr P. I.
Draw ratio, A
Vincent for useful discussions and for assistance with
sample preparation, and to Dr G. R. Davies for his
Figure 70 (Pz(B))ept of draw ratio, showing fit
as a function advice on some of the theoretical aspects.
to rubberlike (number of random links, N=4*8) network (-)
at low draw ratios and turn over to pseudo-affine deformation
scheme (- ---) at high draw ratios REFERENCES
1 Read, B. E. and Stein, R. S. Macromolecules 1968, 1, 116
change in the content of a particular conformer, Amtrans, 2 Phillips, P. J., Wilkes, G. L., Delf, B. W. and Stein, R. S.
say, relates to the extensional strain h, by an equation J. Polym. Sci. (A-2) 1971, 9, 499
of the form: 3 Read; B. E. and Hughes, D. A. Polymer 1972,13,495
4 Cunningham A.. Davies. G. R. and Ward. I. M. Polvmer
1974,15, 143 . ’
5 Heffelfinger, C. J. and Burton, R. C. J. Polym. Sci. 1960, 47,
289
where v is the total number of chains in the network 6 Kashiwagi, M., Cunningham, A., Manuel, A. J. and Ward,
and DZ is a constant of proportionality which can in I. M. Polymer 1973,14,111
theory be calculated provided that the internal energies 7 Ward, I.-M. Chem. I&i. 1956, p 905
8 Ward, I. M. Chem. Ind. 1957, p 1102
of the different conformational states is defined. 9 Grime, D. and Ward, I. M. Trans. Faraday Sot. 1958, 54,
In Figure 9 the change in the concentration of the 959
tram conformer is plotted as a function of [l/3 x 10 Miller, R. G. J. and Willis, H. A. J. Polym. Sci. 1956, 19,485
(h2+ (2/h)} - l] for series (ii). Again a reasonable straight 11 Farrow. G. and Ward. I. M. Polvmer 1960.1.330
12 Schmidt, P. G. J. PO&m. Sci. (2) 1963, l,‘li71
line relationship is obtained up to a draw ratio of
13 Daubeny, R. de P., Bunn, C. W. and Brown, C. J. Proc. R.
about 35. Sot. (A) 1954,226,531
These results suggest, therefore, that it is not un- 14 Liang, C. Y. and Krimm, S. J. Mol. Spectros. 1959, 3, 554
reasonable to obtain a good correlation between mole- 15 Boye, C. A. .7. Polym. Sci. 1961,55,261
cular orientation and conformer content in the low 16 K&m, S. Adv. Pblym. Sci. 1960, 2, 51
17 Daniel. W. W. and Kitson. R. E. J. Polvm. Sci. 1958.I 33.I 161
draw ratio range where the extension of the polymer 18 Miyakk, A. J. Polym. Sci. ,1959, 38, 419
is akin to that of a rubberlike network. It is perhaps 19 Kuhn, W. and Griin, W. Kolloid-2. 1942, 101, 248
more remarkable that the correlation holds to high 20 Roe, R. J. and Krigbaum, W. R. J. Appl. Phys. 1964,35,2215
draw ratios where the behaviour fits the pseudo-affine 21 Pinnock P. R. and Ward. I. M. Trans. Furuduv Sot. 1966.
62, 1308
deformation scheme23 more closely, as shown by the 22 Abe, Y. and Flory, P. J. J. Chem. Phys. 1970,52,2814
broken line in Figure IO. This aspect will be discussed 23 Ward, I. M. ‘Mechanical Properties of Solid Polymers’, Wiley,
in detail in a future paper, where measurements of London, 1971, p 258

756 POLYMER, 1974, Vol 15, November