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Calculations of Elastic Moduli of

Polymer Crystals." II. Terylene*
L. R. G. T~ELO~
The value oJ Young's modulus E for the crystal of Terylene in the direction of
the chain axis is calculated from the force constants for bond stretching and
valence angle deformation. The presence of the benzene ring in the structure
makes this problerr~ less str~ghtforward than that of the simple linear chain
structures, polyethylene and nylon, considered in a previous paper by the
author. The resultant value of E is 1"22 x 1012 dyn/cm 2.

INTRODUCTION
IN THIS paper the type of analysis set out in Part I of this series 1 is applied
to the calculation of the modulus of elasticity of the Terylene crystal in the
direction of the chain axis. The Chain parameters (Figure 1) are taken
from the structural determination of Daubeny, Bunn and Brown ~, but the
benzene ring is assumed to be a regular hexagon of side 1.35 A, equal to
the mean of the two slightly different values (1'34 and 1-36) quoted by
these authors. The remaining angles are tetrahedral. The only significant
departure from the structure of Daubeny, Bunn and Brown is that the
whole system is assumed to lie in one plane. In their structure the O---C--O
group was rotated through an angle of 12 ° out of the plane of the benzene
ring (though this deviation could not be definitely established) while the
CH~--CH2 bond was rotated through an angle of 20 ° about the adjacent
O--CH2 bonds. Any such departures from planarity must arise from the
action of secondary forces either within the molecule or between molecules,
and since the effect of such forces cannot be taken into account in a theory
based on the deformation of primary bonds and valence angles alone, they
will be ignored, the chain being assumed to have its fully-extended (i.e.
planar) configuration. This simplification will lead to an underestimate of
the total deformation, and hence to an overestimate of the modulus.
The presence of the benzene ring in the Terylene structure renders the
mechanical analysis more complicated than for the straight-chain structures
discussed in Part I. Apart from this complication the treatment is generally
similar. In the following presentation the problem of the deformation of
the ring, with its associated terminal bonds, will therefore be considered
in detail before the deformation of the chain as a whole is dealt with.

FORCES ACTING ON B E N Z E N E RING
AS in Part I the applied force F (Figure 1) will be considered to act along
the chain axis PP', which passes through the ring centres. If the chain be
broken at carbon atom number 3 the forces which have to be applied to
the right-hand portion to maintain equilibrium are (1) a tensile force F
parallel to the chain axis, and (2) a couple equal to the product of the
force F and the distance of its line of action from the chain axis. The same
*Part I, Polymer 1960, 1, (1) 95.
279
L. R. G. TRELOAR

forces act on the left-hand portion if the chain is broken at the symmetrically
situated carbon atom to the right of the ring. The forces acting on the
ring, with its associated terminal bonds, are therefore as shown in Figure 2.
The effect of these forces on the terminal bond JA (or the symmetrically
disposed bond DK) is to produce (a) an extension and (b) a rotation with
respect to the adjacent ring bonds. The extension can be treated in the
usual way. The rotation takes place against the restoring couple arising
from the unequal deformation of the angles B1 and B~. This restoring
couple is zero when /3x=/32, i.e. when the bond JA is collinear with the
bisector of the angle ~. This is true whether or not the angle ~ is deformed

IP//'~,
1 2~1"3~
L9
3 ~',"'-")
J 1 O p,,/CH2
F~ ~ ~ 0
. . . . . . . . . . . . .
2 _ _-7--"

o
Figure/--The repeating unit of Terylene
from its stress-free value. It is therefore convenient to express the couple
r on the bond JA in terms of the angle -/(initially 180 °) between this bond
and the bisector of the angle ~ (Figure 1). The couple is then proportional
to the angular displacement ~y, i.e.
~=k~ (1)
where k~ is the corresponding angular force constant. The value of k~
may be derived from the frequency of vibration of the bond JA about the
point A in a molecule of the appropriate type. The couple 7 is the mutual
couple between the terminal bond AJ and the two ring bonds AB, AG.
Since the angles/31 and/3s are equally deformable, the total couple acting
on the ring at the point A may be represented by couples r/2 acting on
each of the bonds AB, AG.

B
F ~ C

E

Figure 2--Force~ acting on ring with adjacent bonds
If the chain is broken at the points A and D, so as to isolate the ring,
an argument similar to the above shows the forces acting at A (or at D)
to consist similarly of a force F parallel to the chain axis and a couple ~"
equal to the product of the force F and the distance of its line of action
from the chain axis. Resolving the force F into components Fx and F~,
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C A L C U L A T I O N S OF ELASTIC M O D U L I O F P O L Y M E R CRYSTALS: 11

respectively parallel and perpendicular to the ring diameter AD, we arrive
at the system of forces represented in Figure 3. Since the sum of the
couples acting at A and D is equal to the moment of the applied forces,
the couple r is given by
r =F~I (2)
where l is the length of the side of the regular hexagon.
The forces applied to the ring produce changes in both the bond lengths
and the valence angles. These changes may be calculated either by a
direct resolution of the forces into components acting on the individual
bonds and valence angles, or by a consideration of the change in the
potential energy of the system due to specified changes in the parameters.
The second of these methods is presented here; it has, however, been
verified that the first leads to an identical solution.
DEFORMATION OF THE BENZENE RING
For a regular hexagonal structure in which the deformability of the bond
angles is defined by a single angular deformation constant ko and the
deformability of the bond lengths by a single stretching constant k~, and
which is subjected to the system of forces represented in Figure 3, the

B 12 c

F, - Figure 3--Forces applied to ring

symmetry of the system (i.e. of the ring together with the applied forces)
requires that pairs of opposite angles and opposite sides deform equally.
It can be seen that, with this system, changes in bond length can take place
independently of changes in valence angle. The deformation of each of
these sets of variables may therefore be considered separately.
Angular variables
To determine the deformation of the ring due to changes in bond angles,
with all the bond lengths held constant, it is convenient to distinguish the
three pairs of opposite angles by the symbols al, ~= and a3 as in Figure 3.
(Initially a1=~==~3). The variations ~1, ~a~ and ~a~ are, however, not
independent, but must satisfy the geometrical condition
~1 + ~2 + ~8 =0 (3)
There are thus two independently variable angular parameters.
It is not immediately obvious how these two independent variables are
to be chosen. It is not possible to consider ~ and % as independent
variables, since a variation of ~,~ at constant ~, for example, involves a
variation of ~. This leads to difficulties in expressing the change in the
potential energy of the system in a manageable form. The only satisfactory
way which has been found of treating the problem is to consider two basic
types of deformation which are consistent with the symmetry conditions
and with the geometrical restriction (equation (3)). These, which will be
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L. R. G. TRELOAR

referred to as type A and type B, respectively, are defined by the relations
A:
~=~= ~=~= - ½8=i (4a)
B:
&,==-8=~; ~%=0 (4b)
Type A, represented in Figure 4(a), results in a displacement of the point D
(with respect to A) in the direction of the force component F~, and is
analogous to a 'tensile' strain, while type B (Figure 4b) yields a displacement
of the point D in the direction of the force component F~, and is analogous
to a 'shear' strain. It is easy to show that any deformation, involving
arbitrary variations of =~, % and % (consistent with equation (3)), may be
resolved into two component deformations, one of each of the above two
basic types. For, from equation (4a), the value of 8~x determines the
amount of A, while from (4b), the value of ~ - ~% determines the amount
of B. These two variational parameters therefore have the properties of
mathematically independent variables.

_ _B C - B ~

A~a'l- . . . . . ")0~ A D
__ _ / /
G E G E
(o) (b)
Figure4--(a) Type A and (b) type B deformations
In considering the displacements due to the above angular variations we
are not concerned with any translation or rotation of the ring as a whole,
which, for a system of forces in equilibrium, involves h o n e r performance
of work. We are therefore at liberty to fix any one point and any one
direction arbitrarily. In the forms of displacement shown~in Figures 4(a)
and 4(b) and in the following analysis, the point A and the direction of
the bisector of the angle =1 at A are taken as fixed.
The quantitative relations between the components of force and the
deformations of type A and type B will now be examined.
'Tensile' deformation (Type A)--The amount of type A deformation
due to the system of forces represented in Figure 3 is obtained by equating
the angular potential energy to the work done by the applied forces in the
corresponding displacement. It is convenient to introduce the variable
0 = = - %. Then, for a variation 80,
~% =2~0; ~ % = ~ 8 = -~0 (5)
The potential energy associated with a change ~= in one of the angles being
½ka (8=)2, the total energy associated with the deformation of the six ring
angles is therefore
V=½ka [2 (~,)2 + 2 (~.2)*+ 2 (8%)2] =6k. (~0)' (6)
The components of displacement for the point D referred to x and y
axes, respectively parallel and perpendicular to the diameter AD are
~x=-2IsinO$O; By=0 (7)
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CALCULATIONS OF ELASTIC MODULI OF POLYMER CRYSTALS: 1I

The work done by the applied forces is
W = ½ [Fx3x + F~3y+ ~r:50~] (8)
where r~ is the couple applied to a bond which rotates through the angle
30~. In the present case (type A) each of the bonds DC, DE is acted on
by the couple r/2, but the rotations ~ are in opposite senses; the net work
done by the couples is therefore zero. Similarly no net work is done by
the couples acting on AB and AG. Hence, with (7)
W =½Fx3x= - (I sin 080) F~ (8a)
The energy equation is therefore
6 k . (80) 2 = - (/sin 0 80) F ~ (9)
whence
8 0 = - lsind
~
F~ (10)

Substituting this value in (7), and introducing the numerical value
sin 2 0=3/4, the displacement components become
l 2 sin 2 0 _ 12 F •
3x= ~ /~x=~ ~, 3y=0 (11)
The result (11) implies that the deformation of type A is in equilibrium
with the force component Fx alone, and is unaffected by the presence of
the force component F~, with the associated terminal couples r/2.
'Shear' deformation (Type B)--For the type B deformation defined by
equation (4b) and represented in Figure (4b) the angular potential energy is
V = ½k~ [4 (3a~)2] = 2k~ (3%)2 (12)
The displacement components for the point D are
~x=0; 3y=/3% (13)
The terminal bonds AB, AG and DC, DE do not rotate. The work done
by the applied couples, as well as that due to the force F~, is therefore
zero. Hence
2k. (3%)2= ½F~13% (14)
I
3~, = ~ F~ (15)
The corresponding displacement components are obtained by substitution
of thisvalue of 3% in (13),i.e.
3x=O; 3y= ~-~F,, (16)
This result implies that the deformation of type B is in equilibrium with
the force component F~ (together with the associated terminal couples
introduced to prevent rotation of the system as a whole), and is unaffected
by the presence of the force component F~.
The combined effect of the components Fx and F~ (with associated
couples) acting together is to produce a displacement whose components in
the x and y directions are the sum of the displacements produced by these
force components acting separately.
283
L. R. G. TRELOAR

Length variables
In this section we consider the deformation of the ring due to changes
in bond length, assuming all the angles to be held constant. As already
stated, the deformations of opposite bonds are equal. Furthermore, the
lengths of each of these pairs, which may conveniently be distinguished by
the symbols Is, 12 and 13 (Figure 3) may be varied independently of the
remaining two. Thus ll, l~ and ls are the three independent length variables
defining the system. (Initially 11= 12= la.)
To find the change in any one of these variables under the action of the
system of forces represented in Figure 3, the work done by the applied
forces in the deformation associated with this variable is equated to the
change in potential energy of the system.
The co-ordinates of the point D, referred to A as origin, are
x = (Is + Is) cos 0 + 12 1
(17)
y=(ll -Is) sin 0 J"
For a change in Is of amount 8ll the corresponding displacements are
therefore
8x=cosO~ls; ~y=sin081l (18)
Since no rotation is involved, the work done by the applied couples is zero.
The total work done is therefore
W= ½(Fx~x+ FvSy) (19)
Introducing the values of ~x and ~y given by (19) the energy equation for
the two bonds of length l~ is therefore
½ks [2 (~/~)2] = ½ (Fx cos 0 + F~ sin 0) ~ll (20).
Hence
1
~I~ = ~ (Fx cos 0 + Fy sin 0) (21)

For a variation of l~ the displacement components are
~x = ~I2; ~y = 0 (22)
The energy equation for these two bonds is therefore
½kl [2 (~/~)2] = ½F~312 (23)
~12=Fx/2kl (24)
For a variationof Is the displacement components (equation 17) are
~x=cos 0~13; ~y=-sinO6la (25>
Hence
½kx '[2 (81s)2] = ½ (F~ cos 0 - Fu sin #)Sls (26)

81s = ~ 1 (F ~ cos 0 - Fu sin 0) (27)

Equations (22), (24) and (27) represent the changes in each of the
independent length variables due to the action of the applied forces. The
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CALCULATIONS OF ELASTIC MODULI OF POLYMER CRYSTALS: II

total displacement components due to the three variables together are
~x ~x ~x )
8x= ffi~ ~l, + -~2~12+ ff~381*
(28)
~y ~y ~y
~y = ~ ~l~+ ~ ~12+ ~ ~I~

Introducing the above values of ~l 1, 812 and 813 together with values of the
partial derivatives obtained from (17), the result is
1
~x = ~ ' [ ( F . cos O+ F~ sin 0) cos 0 + F. + (F. cos 0 - Fu sin 0) cos 0]

1 (2cos20+ 1)F~= 3---F (29)
- 2kl 4k~
:since cos 2 0 = 1/4. Similarly
~y [(Fx cos,0+ F~ sin 0) sin O- (F~ cos 0 - F~ sin 0) sin 0]

1 3
= ~ (2 sin ~ O)F~ = ~ F~ (30)

since sin 2 0 = 3/4.

Total deformation
The total deformation due to the combined effects of the angular and
length variables is obtained by summation of their individual contributions.
In terms of the components of displacement ~xx and Ay in the x and y
directions we have therefore, from (11) and (16) with (29) and (30)
respectively

&x= [ ~12+ ~ 3 I Fx and A y = [ ~l'+
~ T k - 3~ 3 F= (31)

The resultant displacement is the vector sum of the two component
,displacements. Since each of the displacement components is related to
the corresponding force component by the same factor of proportionality,
it follows that the resultant displacement ~s is in the direction of the
resultant force F, and is given by

8s=E I4-~+~-[~3F (31a)

This result will be applied in the calculations which follow.

VALUES OF FORCE C O N S T A N T S
The values of bond stretching and valence angle deformation constants
given in Table 1 will be used. The latter may be expressed in terms of
either the couple k, per unit change of angle, or the force k~ acting at the
extremities of the associated bonds, per unit linear displacement. As
shown in Part I, kp=kJP.
285
L. R. G. TRELOAR

Table 1. Values of force constants
k x (stretching) k~,(bending) k~ = 1112kp
Bond (dyn/crn) Re/. Angle Re/. (dyn cm rad. -1)
(dyn/em)
-T --F-
C---C 4"36 x l0 s C---C--O 0'524 x 105 1.105x 10-ix
(paraffin)
C---O 4'54 x 105 C--O~ 0"432 x 105 0"883 x10-11
C--C 7"620 x 105 4 C---C----C 0"661 x 105 4 1"29~x 10-I1
(arom.) (arom.)
@-; 1'064 × 103 2"523 x 10-Ix

The C---O stretching constant and the C--O----C bending constant were
calculated from data for ether quoted by Herzberg 5, using his equations
(II 190, 191). The C - - C - - O bending constant was derived from the data
of Cross and van Vleck 5 for ethyl alcohol, their value being slightly modified
to correspond with the definition used in the present paper (approximately,
k~ = 2k3 in Cross and van Vleck's notation). The last constant in the table
is equivalent to the constant kv defined by equation (1). This was calculated
from the frequency of vibrations (347 cm-1) for the CH3 group in toluene
recorded by PlylerL
NUMERICAL C A L C U L A T I O N S
The chain axis passes through the centre of the ring and the mid-points of
the CH2--CH2 bonds (Figure 1). Since the repeating unit has a centre
of symmetry at the centre of the ring, it is sufficient to calculate the
deformation of one half of the unit only. This will include one half of
the ring and one half of the terminal CHs--CH2 bond. The contributions
to the total deformation due to (a) bond stretching (excluding the benzene
ring), (b) the benzene ring (bond stretching and valence angle deformation)
and (c) valence angle deformation (excluding the benzene rin D will be
calculated separately.

Bond stretching (excluding benzene ring)
As in the treatment of nylon in Part I, the deformation due to bond
stretching is calculated from the formula

8LI=F/_,
S'cos2
~
0,
(32)

where 0~ is the inclination of a particular bond to the chain axis. With
the values of bond length given in Figure 1, and assuming tetrahedral valence
angles, the bond inclinations have two values only, namely,
0x=21°34 ', cos281=0"8650, for bonds (1,2), (3,4) and (4,5)
02=48 ° 58", cos202=0"4310, for bonds (0,1) and (2,3)
For half the C---C bond (0,1) we have
1058L/F = ½(0"4310/4.36)= 0-04948 c m / d y n
For the C---O bond (1,2)
1038L/F = 0"8650/4.54 = 0" 19053 cm [dyn
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C A L C U L A T I O N S OF ELASTIC M O D U L I OF P O L Y M E R CRYSTALS: I1

For the O---C bond (2,3)

1053L/F=0.4310/4"54 =0"0949, c m / d y n
For the C----C bond (3,4)

1053L/F = 0"8650/4"36 = 0"19839 c m / d y n
The total deformation due to bond stretching (excluding the benzene
ring) is therefore
1053L1/F = 0"5333 c m / d y n (33)
Benzene ring
The formula (31a) gives directly the contribution of the ring (arising
from both bond stretching and angular deformation) to the extension of
the chain due to a force F acting along the chain axis. For the half-ring
we have 3L2 = 3s/2, and therefore (since l~/4k, = kp/4),

F°25 0-75q
1053L2/F=½ L0.-~61 + 7.620-1 =0.2383 c m / d y n (34)

Valence angle deformation (excluding benzene ring)
The general method of handling the deformation of valence angles was
discussed fully in Part I, with particular reference to the nylon chain. The
same method is applied here to the deformation of the angles ~ , ~ , ~3, and
7 (Figure 1). If d~ is the distance of the vertex i from the chain axis, the
couple acting on the angle ~ is F x d , and the angular deformation is
F×ddk~, where k~ is the angular deformation constant. The changes
b0~ in bond inclination are calculated assuming one particular bond to be
fixed, and superimposing the effects of the successive changes 3~. In the
present case the bond (0,1) is arbitrarily fixed. We have then

30o~= 0

(35)

30,5 = + ~;03~- 37

The values of dr and the corresponding values of 3ff~calculated on the basis
of the angular deformation constants listed in Table 1 are shown in Table 2.
Knowing the changes in bond inclination, the contribution to the axial

Table 2
Angle 10s di 10-2 3~t/F 10 -2 80~/F - 10a I sin 01(80JF)
Bond
(Fig. I) (cm) (rad./dyn) (rad./dyn) (cm/dyn)
0"5620 +5"084 0"00 o 0"00 o
~2 --0"032 s --0'37 t (1, 2) - 5'086 + 2"691
¢3 1"0436 +9"444 (2, 3) + 5"45r -5-514
T 0"4961 + 1"960 (3,4) - 14.901 +8-15 s
½(4, 5) - 16"86~ +8"36~
287
L.R.G. TRELOAR

extension of the chain due to valence angle deformation is obtained by
summation of the individual contributions from each bond, according to
the formula,
~Ls = - ~ I sin 0~~0~ (36)

The calculated values of - l sin 0 ~ , are given in Table 2. The resultant
total deformation due to the distortion of valence angles, obtained by
summation of the figures in the last column, is
IOSSL3/F= 1-3700 cm/dyn (37)
Calculation of modulus
The longitudinal modulus E is given by the formula
E _ F/A
- 8L/L (38)
where ~L is the total increase of length in the chain direction associated
with the tensileforce F, A is the effectivecross-sectionalarea of the chain
and L the axiallength considered.
Combining the separate increments of length due to bond stretching,
ring deformation and valence angle distortion given by (33), (34) and (37)
above, we obtain,
~L/F =0"5333 + 0-2383 + 1"370o=2"141e x I0-s cm/dyn
The half-lengthof the repeating unit (L) for the planar molecule, with the
bond lengths shown in Figure I, is 5"35 A. The cross-sectionalarea A is
equal to the volume of the unit cell divided by the length of the c-axis,
which from the data of Daubeny, Bunn and Brown is 219/I0-70=20'5 A ~.
Insertion of these figures into (38) yields the value of modulus,
E = 1"219 x I0 '2dyn/cm ~ (39)

DISCUSSION
The only previous calculation of the modulus of the Terylene crystal
available in the literature is that of Lyonss, which yielded the not very
different figure of 1.46× 101~dyn/cmL This close agreement, however,
is purely coincidental, since the two treatments differ quantitatively in
important respects, some of which have been discussed in detail in Part I.
In the present problem there is the additional complication of the defor-
mation of the benzene ring, which is here subjected to a more exact analysis
than in the treatment of Lyons.
In considering the significance of calculations of this kind it must again
be emphasized that the effect of forces other than primary valence forces
is ignored, and that in the absence of any estimate of the effect of such
forces it is not possible to assess the reliability of the calculations. Also,
in the present problem, the assumption of a planar configuration of the
chain will tend to give too high a value of modulus.
Apart from these theoretical defects, the uncertainty of the experimental
data for the force constants must be borne in mind.
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CALCULATIONS OF ELASTIC MODULI OF POLYMER CRYSTALS: II

It has been pointed out by Lyons that his calculated value of modulus
is higher than typical experimental values of modulus for Terylene fibres
by a factor of at least 10. This difference is attributed to the presence of a
non-crystalline component, and to the imperfect orientation of the crystallites
in the fibre. H e also refers to the close agreement between his calculated
modulus and the crystal modulus derived experimentally from X - r a y
measurements of the change of lattice spacing with stress by Dulmage and
Contois 9, namely 1 "37 x 1012 d y n / c m 2. These comparisons remain valid for
the calculated value derived in the present paper.

The author wishes to make acknowledgments to Dr I. Mann for valuable
discussions in the preparation of this paper. The work forms part of a
programme of research undertaken by the British Rayon Research
Association.

British Rayon Research Association,
Heald Green Laboratories,
W yt hens hawe ,
Manchester
(Received 3rd January, 1960)

REFERENCES

I TRELOAR, L. R. G. Polymer, 1960, 1, (1), 95
2 D^UB~rY, R. DE P., BUNN, C. W. and BROWN,C. J. Proc. roy. Soc. A, 1954, 226,
531
3 RASMUSSEN,R. S. I. chem. Phys. 1948, 16, 712
WHIFFEN,D. H. Phil. Trans. roy. Soc. 1956, 248, 131
5 HERZaERG,G. In/tared and Rttman Spectra, Van Nostrand, New York, 1945, p. 354
e CROSS, P. C. and VANVLECK,J. H. J. chem. Phys. 1933, 1, 350
7 PLYLER,E. K. Disc. Faraday Soc. 1950, 9, 100
s LYONS,W. J. J. appl. Phys. 1958, 29, 1429
9 DULMAGE, W. J. and Cotcrols, L. E. J. Polym. Sci. 1958, 28, 275

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