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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.
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
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)
_o., / [ ....
/o, I o/ o.o
~ 0'3
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
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
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289
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