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JOURNAL OF M A T E R I A L S S C I E N C E 1 (1966) 389-398

On the Tensile Behaviour of Oriented
Polyethylene
A. KELLER
H. H. Wills Physics Laboratory, The University, Bristol, UK

J. G. RIDER
Department of Physics, The University of Surrey, London, SW11, UK

Received 22 July 1966

Tensile tests of oriented, high-density, polyethylene films were carried out in order
to assess how far the intrinsic molecular and textural features of the samples affected
their mechanical behaviour, and to see whether this behaviour bore any resemblance
to that of metals. Brittle fracture, ductile fracture or necking followed by drawing
occurred, depending on the pretreatment used to orient the material, the angle
between the tensile axis and the c axis, and the speed of testing. The feature of the
crystalline texture (common to all the films) which was important in determining the
geometry of deformation was the alignment of the c axis; the additional orientations
present in some of the films did not significantly affect the deformation geometry. The
results suggested that ductile deformation approximated to slip in the direction of th9 c
axis, while brittle fracture was observed to occur on planes parallel to the c axis. There
were some noticeable differences in behaviour between those films which had
received a pre-anneal and those which had not; these differences appeared not to be
due to differences in the crystalline texture. Several striking similarities to the mechanical
behaviour of hexagonal single crystals were observed.

1. I n t r o d u c t i o n macroscopic structural effects have been re-
The tensile behaviour of polymeric materials is ported in the course of yield and fracture, which
clearly of great importance for many applied resemble features long familiar in non-polymeric
problems, particularly at high deformations in substances [I, 2].
the region of yield and fracture. The correspond- The present work, the commencement of a
ing effects in simpler materials, such as metals, longer-term research project, has been under-
are well documented and reasonably well under- taken in order to assess how far yield and frac-
stood both in terms of general plastic behaviour ture phenomena, occurring on tensile testing,
of matter, and in terms of atomic structure. In are attributable to molecular and textural
the case of polymers, the situation is much more features intrinsic to the polymeric nature of the
obscure as regards both these facets. Our out- samples, and how far there is a common de-
look is much influenced by the unique atomistic nominator with simple substances such as metals.
feature of these materials, and there is a tendency For the purpose outlined, we chose samples
to regard all observations as consequences of the which are as well defined as possible, in our
long-chain nature of the molecular constituents. present state of knowledge, as regards molecular
Lately, our microstructural picture has been orientation and crystalline texture. The basis for
greatly extended by the manifold morphological this is provided by recent work on polyethylene
features recognised in crystalline polymers, with which one of us was associated [3, 4]. In
which are now gradually being taken into the course of this, polyethylene was first drawn,
account by current works on macroscopic then rolled along the draw direction and subse-
properties. On the other hand, a number of quently heat treated appropriately. This led to
389
A. K E L L E R , J. G. R I D E R

structures which were well specified in terms of cular to the draw direction, with a corresponding
macroscopic sample dimensions both with 1 0 ~ increase in length in the draw direction.
respect to molecular structure and crystalline The annealing caused a 30 ~ increase in thick-
texture. Amongst others, macroscopic samples ness and a 10 ~ decrease in width, accompanied
were obtained where the three crystal axes a, c, by a 40 ~ decrease in length in the draw direc-
and b were uniquely defined by the rolling-plane tion. Wide-angle X-ray diffraction then showed
normal (a), rolling and drawing direction (c), and a satisfactory degree of double orientation of the
by the direction in the film (rolling) plane per- crystalline material, with the b and c axes aligned
pendicular to the draw-roll direction (b). In parallel to the plane of the film (the latter in the
these samples, the planes of the crystal lamellae draw direction) and the a axis aligned per-
had a well-defined double texture with the pendicular to it. It is convenient to denote the
lamellar planes parallel to b and inclined by mode of preparation of this film by the code
about 40 ~ with respect to c. This was the basic D - R - A (drawn - rolled - annealed). The
sample type used in this work, together with three control films were then prepared: respec-
three others less uniquely specified in terms of tively, by drawing at room temperature (D), by
macroscopic dimensions serving as controls (see drawing and rolling at room temperature
below). (D - R), and by drawing at room temperature
It ought to be stated at the outset that the and then annealing at 131.1~ (D - A). The
influence of the orientation, both on the level of dimensional changes were similar to those re-
the crystal lattice and that of the crystal lamellae corded above. The crystalline textures as deter-
(with the exception of the c axis position itself), mined by wide-angle X-ray diffraction were as
was not as decisive as originally anticipated, at follows: D had c aligned parallel to the plane of
least under the test conditions in question, and the film with a and b randomly distributed
that there emerged a closer resemblance to around it; D - R had c aligned parallel to the
metals than is normally recognised. On the plane of the film and also (110) and (110)
other hand, there were some differences which aligned parallel to the plane of the film; D - A
may become important for further work to be had c aligned parallel to the plane of the film
discussed in the paper. Having indicated these and in addition a small amount of D - R - A-
facts to begin with, the experimental material type double orientation. The presence of double
will be presented in the order in which it was orientation in D - A was unintentional. The
originally obtained. amount was small compared with the amount in
D - R - A; it was therefore considered reason-
2. Experimental able to regard D - A as a valid control sample.
2.1. Samples
The starting material was a film of high-density 2.2. Tensile-Testing Arrangements
polyethylene (Marlex 50) 4.9 • 10 -2 cm thick. Parallel-sided tensile-test-pieces were cut from
It showed little preferred orientation as judged the prepared films with a razor blade. Most test-
from wide-angle X-ray diffraction photographs. pieces were in the range length 1 to 3 cm, width
Preparation of the doubly oriented, basic, 1 to 3 ram, thickness 0.1 to 0.2 mm. The angle
sample-type material referred to above was between the test-piece axis (i.e. the direction
carried out in the light of the work of Hay and along which the sample was pulled) and the c
Keller [4]. The process consisted of room- axis was measured in a polarising microscope to
temperature drawing of a strip of the material about zk 1 ~ This angle is denoted by the
(draw-ratio about 6, the thickness being reduced symbol )~0 before deformation and by )t after
by a factor of about 3 and the width perpendi- deformation.
cular to the draw direction by a factor of about A conventional tensile-testing machine was
2), followed by room-temperature rolling with used with the crosshead driven at a constant
the direction of advance in the draw direction, speed. Most tests were carried out at a standard
followed by annealing at a suitable temperature speed of 1.6 cm/min; in a few cases, the speed
with the film held between sheets of mica in a was reduced to 1/80 of this. The loads involved
silicone oil bath. The best annealing tempera- were about 1 to 2 lb (1 lb = 454 g) and were
ture was found by experiment to be 131.1 ~ C. measured on a Boulton Paul, 250 lb, load cell,
The rolling resulted in a 1 5 ~ decrease in the output from which was fed to a constant-
thickness and a 5 ~ increase in width perpendi- speed chart recorder via the associated bridge
390
ON THE TENSILE BEHAVIOUR OF ORIENTED POLYETHYLENE

circuitry. The load-cell displacement at 250 lb ing parallel to it in the most highly extended
was 0.02 in. (1.0 in. = 25.4 mm), and was pro- portions. The ratio of the width of an unextended
portionally smaller at smaller loads. Tests were test-piece to that of the same test-piece when
carried out with the specimen either in air at fully extended was very much greater than the
r o o m temperature or in water cooled with ice to corresponding thickness ratio. Width ratios
4 ~2~ increased with A0 from about 4 at A0 = 15 ~ to
about 10 at A0 = 90 ~ whereas thickness ratios
2.3. R e s u l t s were all between 1.1 and 1.3 and appeared not to
2.3.1. Tensile Tests at Room Temperature and vary systematically with A0.
Standard Speed During the load drop, the deformation be-
The behaviour of all four types of prepared film came clearly inhomogeneous along the length of
could be classified under three headings: the test-piece. In certain circumstances, the
(a) Drawing The load, after rising to a maxi- inhomogeneity was rather striking: one or more
m u m (upper yield point), fell to a lower value deformation bands were formed, across which
(lower yield point), and thereafter remained con- there was high local shear (shear angles of tan -1
stant or rose slowly. Inhomogeneous yielding 10 were often seen) accompanied by abrupt
took place during the load drop, and the region steps on the edge or edges of the test-piece
of greatest elongation then propagated along (bands did not always pass right across the test-
the test-piece at constant or slowly rising load. piece). A deformation band is illustrated in fig. 1.
(b) Ductile fracture The load rose to a maxi- It appears to be like some of the bands reported
m u m and then fell gradually to zero. At some by K u r o k a w a and Ban [1] (see their fig. lb and
stage during the load drop, the specimen began fig. 2b, upper diagram). The boundaries of the
to break by a tearing process which could be band were approximately plane, and intersected
arrested by stopping the tensile-testing machine. the wide surface of the test-piece approximately
(c) Brittle fracture The test-piece broke in two at right-angles. Close examination of several of
after inappreciable plastic extension, the break- these bands showed that the wide surface of the
ing being too quick to be arrested by stopping test-piece was grooved where the band inter-
the tensile-testing machine. sected it. This indicates that the deformation in
The circumstances in which these types of the band was not just a simple shear parallel to
behaviour occurred are shown in table I. (D - A the boundaries of the band. The sum of the
tested at )to = 0 ~ was unusual in breaking sud- depths of the grooves on the two sides was some
denly rather than gradually after appreciable 5 to 1 0 ~ of the test-piece thickness. Often the
deformation.) As seen, the major difference be- band was observed to be not quite straight, but
tween the four samples is the increased angular to have slight curvature in the opposite sense at
range of brittle fracture in the D - R - A and the two ends. The boundaries appeared to be
D - A (i.e. the annealed) materials. smooth when seen at magnifications up to 320.
In test-pieces which exhibited drawing, it was When A0 was less than about 40 ~ the bands were
observed that with increasing elongation the c parallel to the c axis in the adjacent material,
axis swung round towards the tensile axis (i.e. within the uncertainty of measurement: for
)t decreased from its initial value of A0), becom- larger values of A0, there were increasing devia-

T A B L E I Behaviour at room temperature and standard speed as a function of )t0.

Material Behaviour

Ductile fracture Drawing Brittle fracture

A0
D 0~ 15 to 90~ Did not occur
D-R 0~ 15 to 85~ Only occurred at g0~
D-R-A 0 to 15~ 30 to 70~ 75 to 90 ~
D-A 0* to 15~ 30 to 73 ~ 75 to 90~
*At Ao = 0 ~ broke suddenly after appreciable deformation.
391
A. KELLER, J. G. RIDER

it was not known at precisely what moment the
band was formed, it was thought that at the
m o m e n t of formation this angle was closer in
value to 2` than to 2`o. F o r this reason, ~ was
also plotted against 2`, as in fig. 3. The effect has
been to reduce the scatter; within experimental
error all points for D - R - A and D - A, except
two, lie on the same smooth curve, which
diverges from ~ = 0 ~ as 2, rises above 20 ~
20 i i I i I i I i

n D-R-A rl$

Figure I D - A test-piece, ,~o= 60 ~ showing the large O D-A O/
shear across a deformation band. A n g l e between band A D oO o
and c axis is 8 ~ ( • 12). 8 o ~,o;
n~n ~ 0 ~'~"~
tions, up to a m a x i m u m of 17 ~ between the
o
deformation boundary and the direction of the
O IO 20 30 40 50 60 70 80 90
c axis, always in the sense that the acute angle
;k Degrees
between the deformation boundary and the
test-piece axis was less than that between the c Figure 3 c~, the angle between deformation band and c
axis, plotted against A, the angle between c axis and
axis and the test-piece axis. Denoting the angle
tensile axis measured after formation of band, for D - R -
between the c axis and the deformation band by A and D - A tested at room temperature and for D
~, then ~ varied with Ao as shown in fig. 2. It will tested at 4 ~ C.
20 i i i i i i i
0 D-R-A 0 All test-pieces which draw with continued
0 D-A extension necked, whether or not deformation
L AD o bands were formed. In some cases, the transition
~1o 13 o region between the highly and slightly deformed
s
regions had long gently-tapering sides; in other
cases, the change in width occurred abruptly and
o . . in a characteristically asymmetrical way, which
O IO 20 30 40 50 60 70 80 90 suggested that shear had taken place in a direc-
~o Degrees
tion approximately parallel to the c axis. An
Figure 2 06 the angle between deformation band and c example of the abrupt type of transition region
axis, plotted against Ao, the initial angle between c axis in a D - R test-piece with ;~o = 75~ is shown in
and tensile axis, for D - R - A and D - A tested at room fig. 4. The set of fine, parallel lines, which origin-
temperature and for D tested at 4 ~ C.

be observed that the room-temperature data in
this figure are confined to D - R - A and D - A.
This is because deformation bands of this kind
were not found in D and D - R in room-tem-
perature tests, although they were found at 4 ~ C,
as described in section 2.3.3. The data go only
up to 2`o= 73~ because, above this angle,
D - R - A and D - A suffered brittle fracture
without developing deformation bands. In the
tests in which ~ was measured, the testing
machine was stopped as soon as it was appre-
ciated that a deformation band had formed. The Figure 4 Shoulders of neck in a D - R test-piece, Ao = 75 ~
angle 2` between test-piece axis and c axis in the after drawing in the tensile test. The closely-spaced
material adjacent to the band was less than its parallel lines run everywhere parallel to the direction of
initial value 2`0because of deformation. Although the c axis; a sharp kink boundary is clearly visible (• 6).
392
ON THE TENSILE BEHAVIOUR OF ORIENTED POLYETHYLENE

ated naturally in the preparative drawing process The kink boundaries enclose the darker len-
and survived the subsequent rolling, are parallel ticular region, darker because of its different
to the c axis. (The abrupt change of orientation orientation, which makes an angle of about 30 ~
across a straight boundary, which these lines with the edge of the test-piece. It appears that the
reveal, is referred to in the next paragraph.) specimen attempted to yield here but could not
Abrupt transition regions were associated with avoid brittle fracture. It was not necessarily the
high values of A0 and often also with proximity case that kinks formed early and persisted
to a grip, either because the neck formed near a throughout the test. One ductile test-piece was
grip or because the transition region approached observed at intervals throughout a test. A kink
a grip during the test. boundary developed before necking occurred
As was mentioned above, Z decreased with but disappeared as a gently tapered neck was
increasing deformation. Thus A changed along formed. Later, one of the transition regions
the length of the transition region. The change moved towards a grip, became more abruptly
was sometimes abrupt across a straight bound- tapered, and a second kink appeared.
ary, here named a "kink" boundary. An example The upper and lower nominal yield stresses of
of a kink boundary can be seen in fig. 4, running the four materials have been plotted against )to
obliquely across the test-piece; the change in over the drawing range in figs. 6, 7, 82 and 9. T h e
orientation across the boundary is revealed by nominal stress is the load divided by the initial
the change in direction of the fine lines which area of cross-section of the test-piece. The varia-
run everywhere parallel to the c axis. It can be tion of the yield stresses with A0 is qualitatively
seen that the kink boundary did n o t bisect the the same in all four materials; the scatter in the
angle between the c axes on either side of the case of D - R - A is rather higher than would be
boundary; this was typical, the angle between expected from the estimated measurement errors.
the kink and the bisector ranging from 4 to 18 ~ The curves for upper and lower yield stresses are
in the cases examined. Kink boundaries were plots of the functions A(sin Ao cos Ao + k sin s
commonly seen in the abrupt transition regions A0)-1 and B cosec Ao respectively, where k, A,
in D - R and D test-pieces, not so often in and B are constants whose values, given in table
D - R - A and D - A test-pieces. Kink bound- II, have been chosen to give the best fit with the
aries were sometimes seen in the neighbourhood experimental points. The reason for using these
of the curved parts of deformation bands. In a functions is discussed in section 3; at this point,
few cases, such boundaries were seen at the very A and B may be regarded simply as convenient
start of yielding, before substantial deformation parameters with which to compare the upper
had occurred. They were also seen in the D - R and lower yield stresses of the different materials.
test-pieces at Ao 90 ~ which suffered brittle
= As regards the room-temperature tests, the
fracture. One such test-piece is pictured in fig. 5. materials fall into two groups, the annealed and
the unannealed; the former had yield stresses
about twice those of the latter. In each group,
the rolled had slightly higher yield stresses than
the unrolled, but these differences were distinctly
smaller than those between the two groups.
There is little to report at this stage of the
work about the ductile and brittle fracture
behaviour. The former was a tearing process
usually initiated at the grips. The test-pieces
which suffered brittle fracture broke along planes
parallel to the e direction and perpendicular to
the wide face of the test-piece, after inappreci-
able plastic extension. An example of such a
break in a D - R specimen with A0 = 90 ~ has
Figure 5 D - R test-piece, Ao = 90 ~ Brittle fracture has already been given in fig. 5. The nominal tensile
occurred parallel to the c axis. T h e lenticular region fracture stresses for brittle fracture are plotted
running in from the edge of the test-piece at a b o u t 30 ~ in figs. 7, 8, and 9; the values may not be very
is dark because its orientation differs significantly from reliable, as breaks often occurred near the
that of the remainder of the material (• 6). grips.
393
A. K E L L E R , J. G. R I D E R

9 I 11 S ~ .... , ' ~ ' Ii L 9 .... I ' ' ,' ' .I JI " j ~ I

8 B
Upper yield [] Upperyield []

7
Loweryield 0 7 Loweryield 0
E
~6 6' Brittle fracture A
%
c, |
~s ~JS
oJ

.~ 4
o~
Z
3 z 3 O

L I ~
I

0 t .... t t , I ! , i J 0 t , , f , ,,,I,,, I ! ,, J
0 tO gO :30 40 SO 60 70 80 90 0 iO 20 30 40 50 60 70 BO 90
~'0 Degrees X9 Degrees
9 ~ ~ ,,~
J J J I # 9 1 'J J I J' i'm i" , j

I Upper yield []
n
B B Lower yield 0
Upp%r yield I'I Brittle fracture A

7 Lower yield 0 7

E
"~6 Brittle fracture ~/~ E
"Z6

,o5

~4 ~4

z Z~ z
A

0 I | I' .... I I . . . . ! I I I I I I 9
0 I0 20 30 40 SO 60 70 80 90 00 I0 20 30 4I0 50 I
60 70 I
80 90
•o Degrees X o Degrees

Figures 6, 7, 8, and g Upper and lower nominal yield stresses and brittle fracture stress at room temperature
plotted against ,~o, the initial angle between the tensile axis and the c axis for D (fig. 6), D - R (fig. 7), D - R - A
(fig. 8) and D - A (fig. 9). (Fig. 6, top left; 7, top right; 8, bottom left.)
394
ON THE TENSILE BEHAVIOUR OF ORIENTED POLYETHYLENE

TABLE II Values of the parameters k, A, and B in the expressions A (sin/~ o cos,~ o @ ksin 2 ,~o)-1 and B cosec '~o,
which were used to fit the upper and lower nominal yield-stress data respectively.
Material Room temperature 4~C

k A B k A B
(10Sdyn/cm2) (108dyn/cm 2) (108dyn/cm ~) (10Sdyn/cm~)
D 0.45 0.87 0.70 0.45 1.4
D- R 0.40 1.10 0.80 0.40* 1.5
D- R- A 0.40 2.31 1.80 0.40* 2.8
D- A 0.45 2.17 1.50 -- -- m

*Assumed value.

2.3.2. Tensile Tests at Room Temperature and s e p a r a t e d f r o m the D - R - A and D-A
Slow Speed materials.
A few tests were carried o u t at a speed 1/80 o f A few tests with D - R - A a n d D - A test-
s t a n d a r d , in o r d e r to find o u t w h e t h e r this pieces showed t h a t d e f o r m a t i o n b a n d s also
caused the b e h a v i o u r to change f r o m brittle to o c c u r r e d in these m a t e r i a l s at 4 ~ C; indeed, at
ductile. T h e change o f speed did indeed have this l o w e r values of/~0, they were m o r e p r o m i n e n t
effect on D - R test-pieces with 2'o = 90~ a n d on t h a n in r o o m - t e m p e r a t u r e tests at the same
D - A test-pieces with t0 = 77~ these n e c k e d angles. A t 4 ~ C, they were observed in D - R - A
a n d d r e w at c o n s t a n t l o a d in the usual ductile m a t e r i a l d o w n to A0 - 2 2 ~ whereas at r o o m
m a n n e r . H o w e v e r , D - A a n d D - R - A test- t e m p e r a t u r e they c o u l d n o t be o b s e r v e d in
pieces with ,~o = 90o were still brittle, b r e a k i n g D-R-A b e l o w A o = 4 5 ~9
at the same stresses as w o u l d have been expected I n the range A0 = 72 to 90 ~ which is a p p r o x i -
in a s t a n d a r d - s p e e d test. It will be n o t e d t h a t the m a t e l y the range in which D - R - A a n d D - A
test-pieces which did b e c o m e ductile at the slow were brittle at r o o m t e m p e r a t u r e , D was n o t
speed h a d values o f A0 only slightly greater t h a n brittle at 4 ~ C, b u t it d i d n o t show b a n d s o f the
those m a r k i n g the u p p e r end o f the ductile k i n d described above. Instead, at A0 = 72 a n d
o r i e n t a t i o n ranges at s t a n d a r d speed (90 ~ c o m - 80 ~ the test-pieces yielded b y kinking. A p h o t o -
p a r e d with 85 ~ for D - R, a n d 77 ~ c o m p a r e d g r a p h o f a A0 = 72~ test-piece is r e p r o d u c e d in
with 73 ~ for D - A ) . fig. 10. T h e b o u n d a r i e s between d a r k a n d light

2.3.3. Tensile Tests at 4 ~ and Standard Speed
It has a l r e a d y been n o t e d a b o v e t h a t d e f o r m a -
t i o n b a n d s o f the k i n d illustrated in fig. 1 were
n o t observed in D a n d D - R test-pieces tested at
r o o m t e m p e r a t u r e a n d s t a n d a r d speed. One test
was carried o u t at r o o m t e m p e r a t u r e a n d at 10
times the s t a n d a r d speed, a n d this d i d p r o d u c e a
small d e f o r m a t i o n b a n d in a D test-piece. A s
testing at this a n d higher speeds presented s o m e
difficulties, it was decided i n s t e a d to retain the
s t a n d a r d testing speed a n d to see w h e t h e r de-
f o r m a t i o n b a n d s w o u l d be f o r m e d at a testing
t e m p e r a t u r e o f 4 ~ C. It was f o u n d t h a t b a n d s Figure 10 D test-piece, ,~o = 72 ~ tested at 4 ~ C, showing
were i n d e e d f o r m e d u n d e r these c o n d i t i o n s in D two, well-defined, parallel, kink boundaries set up at the
a n d D - R test-pieces, a n d were similar in all start of yielding. The rather poorly-defined parallel lines
respects to those described in section 2.3.2. The run everywhere parallel to the c axis (• 18).
D m a t e r i a l was e x a m i n e d m o r e extensively t h a n
the D - R, a n d in it b a n d s were seen in the r a n g e regions are the k i n k b o u n d a r i e s , a n d the fine
A0----- 15 to 60~ the values o f ~ are p l o t t e d lines are everywhere p a r a l l e l to the c axis a n d
a g a i n s t A0 a n d ,~ in figs. 2 a n d 3 respectively. reveal the difference in o r i e n t a t i o n across the k i n k
I n the latter plot, the D m a t e r i a l is clearly b o u n d a r i e s . Several test-pieces with ~0 = 90~
395
A. K E L L E R , J. G . R I D E R

formed two intersecting bands - one pro- tudes of the upper yield stresses (A in table II)
minent band running right across the test-piece of D and D - R were brought closer to the room-
and a second, short one at approximately 90 ~ temperature values of D - R - A and D - A.
to it and running from the edge of the test-piece (c) By lowering the testing speed, the value of
into the prominent band but no further. the angle ~0 at which behaviour changed from
The upper yield stress of the D material was ductile to brittle was raised. It seems likely that
measured between ~0 --~ 15 and 90~ the values raising the testing temperature would have had
could be fitted by the same function used for the the same effect, and that at a higher temperature
room-temperature results for the same material, D - R - A and D - A would have been ductile
with the same value of k but a higher value of up to h0 ~ 90 ~ as D was at r o o m temperature.
A, as shown in table II. As regards D - R and Certainly K u r o k a w a and Ban found that their
D - R - A, measurements were made at only one polyethylene, which had first been drawn in
and two values of Ao respectively. Assuming the boiling water and was then tested at A0 -----90 ~
same value of k as at r o o m temperature, values was brittle below 60 ~ C and ductile above 60 ~ C.
of A were calculated for these two materials also To summarise, it is as if, when one has the four
and are given in table II. Again, lowering the materials at one temperature, one is, to a first
testing temperature raised the value of A in each approximation, dealing with the same material
case. at two different effective temperatures; D - R - A
and D - A being at a common effective tempera-
3. Discussion ture which is lower than than of D and D - R
The first point to consider is to what extent the (more precisely, D - R is at a slightly lower
behaviour of the four materials, D, D - R, effective temperature than D).
D - R - A, and D - A, differed. In general, their It seems unlikely that the effect of annealing
behaviour was rather similar. However, three can be ascribed to those changes it caused in
points of difference can be distinguished in the crystalline texture which were observed by wide-
room-temperature standard-speed tests. angle X-ray diffraction, in view of the marked
(a) The occurrence of deformation bands (fig. 1) similarity in behaviour between D - R - A and
in D - R - A and D - A materials but not in D D - A despite a considerable difference between
and D - R materials. the amounts of doubly oriented material in
(b) The magnitudes of the yield stresses in the them. However, the annealing also caused a con-
drawing range: as described in section 2.3.2, traction in the c direction of about 40 ~ both in
these are comparable by means of parameters D - R - A and D - A material. This contraction
A and B, whose values are given in table II. was presumably accompanied by structural
(c) The angular range of occurrence or non- changes which did not show in the X-ray pic-
occurrence of brittle fracture, as shown in table I. tures, e.g. increase in crystallinity, increase in
In each case, the distinction is between the crystal size, molecular refolding. It is suggested
two materials which had been annealed on the that these, rather than crystalline orientation
one hand, and the two which had not on the effects, were the factors which were important
other, It is interesting to note that the same three in determining the effect of annealing on the
points of difference can be observed in the mechanical behaviour.
results reported by K u r o k a w a and Ban [1] for On the other hand, the similarities in the
high-density polyethylene. They used two pre- general behaviour of the four materials seem
treatments, drawing in boiling water and draw- likely to have been due to the crystalline orienta-
ing at 30 ~ C. The former differed from the latter tion feature which all had in common, namely,
in the way that the annealed differed from the the alignment of the c axis. Specific observations
unannealed in our experiments. which indicate the importance of the c alignment
The differences between annealed and un- are:
annealed material can be bridged by altering the (a) With increasing extension, the c axis swung
testing conditions. Referring to the three points round towards the tensile axis, whether or not
of difference listed in the previous paragraph: kink boundaries were formed.
(a) Deformation bands did occur in D and (b) The change in width of test-pieces which
D - R material when the test temperature was drew down in tensile tests was much greater than
lowered to 4 ~ C. the change in thickness.
(b) By lowering the test temperature, the magni- (c) The direction of deformation bands varied
396
ON THE TENSILE BEHAVIOUR OF ORIENTED POLYETHYLENE

in a regular way with the direction of the e axis. In fact, the upper yield stress data were fitted,
(d) The asymmetry of abrupt transition regions as mentioned in section 2.3.1, by the expression
in necked test-pieces was always related in the
cru = A(sin Ao cos A0 + k sin 2 A0)-1
same sense to the direction of the c axis (fig. 4).
(e) The upper and lower yield stresses varied in rather than by equation 1. This we can interpret
a regular way with A0. by supposing that the resolved normal stress was
(f) The planes of brittle fracture were parallel also involved in the yield criterion: that is, by
to e. postulating that yield occurred when the sum of
Deformation features qualitatively similar to the resolved shear stress and k times the resolved
the six just listed have all been observed in single normal stress reached a critical value A. As
crystals of hexagonal metals, as also have kink regards the lower yield stress, the data were well
boundaries and a ductile-brittle transition. These fitted by equation 2. There is a discrepancy here,
similarities suggest, as a hypothesis, that, when too, however, for on the basis of equations 1 and
the oriented polyethylene was ductile, the 2 we should have A = B = ~c, whereas in fact B
crystalline parts were deforming by shear in the was found to be somewhat smaller than A in
direction of the c axis and on the plane per- every case.
pendicular to the plane of the film and contain- In metal single crystals, the critical value of
ing the c axis. (This hypothesis was also put the resolved shear stress is regarded as independ-
forward by Kurokawa and Ban [1].) This is ent of normal stress. The introduction of a
certainly an approximation because, as already normal stress term in the present case is clearly
described, the deformation bands were not in all a formal necessity in order to account for yield-
cases exactly parallel to c, and because the thick- ing when Ao ___ 90 ~ Its significance, however,
ness changes in the deformation bands cannot be may welt be more than a formal one, as the same
ignored. If the hypothesis is examined more constant in the term ensures a fit along the
closely, discrepancies appear: curves to comparatively low values of A0. Conse-
(a) The deformation bands were not always quently, the normal stress term may be a genuine
parallel to c, but showed a monotonically in- physical characteristic. An evaluation, however,
creasing divergence from c with increasing A0. would require a more detailed mapping of the
(b) The kink boundaries did not bisect the angle deformation geometry (taking into account
between the directions of the c axis on either side. thickness changes, the exact orientation of the
(c) The yield stress results were not strictly in deformation band, etc.) and must accordingly be
conformity with a critical resolved shear stress deferred.
criterion for slip on the plane and in the direction As regards the brittle fracture stress, the
specified above. If such a criterion is obeyed for results suggest that this might obey a critical,
both the onset and the continuation of deforma- normal, stress law, though the observations were
tion, and if this slip is the only mode of deforma- made over too narrow a range of )to to be sure of
tion, the relationship between the nominal this. The change from ductile to brittle behaviour
tensile stress ~ and the length of the specimen with orientation at a given test temperature and
l, which arises from the change of orientation test speed would then take place at the value of
brought about by slip is: ho at which both criteria were reached with the
same tensile stress. The expected effect on this
~rr = crc cosec Ao ( 1
Io2 sin
zl9 A~ -89 value of A0 of altering the test speed would be
the same as was actually observed, namely, that
where ~rc is the critical value of the resolved a reduction in speed raised the angle of the
shear stress on the slip plane (assumed per- ductile-brittle transition.
pendicular to the plane of the test-piece) and in
the slip direction (assumed parallel to the e
4. Conclusions
axis). This expression ignores any change of The results provide evidence that the ductile
length before yielding. The nominal upper and deformation of oriented polyethylene in the
lower yield stresses ~u and ~L are given by conditions described approximated to slip in the
e direction within the crystalline regions. The
cry = ac (sin ~o cos Ao)-1 (1) general resemblance to hexagonal, metal, single
aL = ere cosec Ao (2) crystals is remarkable in spite of certain notable
where at, is obtained by putting l = oo. differences. Not only is the crystalline part of
397
A. K E L L E R , J. G. R I D E R

the polyethylene a more complex organisation One of us (J.G.R.) wishes to thank the
than a metal crystal, there is the additional factor Governors of Battersea College of Technology
of the presence of uncharacterised amorphous for the grant of a year's leave spent at the H. H.
material in the polyethylene. Some of the Wills Physics Laboratory, University of Bristol,
peculiarities noted in the present work, in par- where the work was carried out. He is also
ticular the deviation of the deformation bands grateful to Professor F. C. Frank and to Dr N.
from c, may perhaps be due to such factors, Thompson for making his stay there possible.
notably to the presence of amorphous, rubber- Published with permission of the Director
like material. Nevertheless, it is important to of the Explosives Research and Development
recognise how much of the observed behaviour, Establishment, Ministry of Aviation.
particularly under conditions normally encoun-
tered in every-day applications, is similar to that References
of the familiar, simple substances, before specific 1. M. KUROKAWAand T. BAN, J. Appl. Polymer Sci. 8
deductions based on the specifically polymeric (1964) 971.
nature of the material are attempted. 2. D. A. Z A U K E L I E S , J. AppL Phys. 33 (1962) 2797.
3. T. K A W A I , I. L. HAY, a n d A. KELLER, J. Polymer Sci.,
Acknowledgements in the press.
4. L L. HAY and A. KELLER,Jr. Matls. Sci. 1 (1966) 41.
We are indebted to Professor F. C. Frank for his
interest in the work and for his helpful comments
on the manuscript prior to publication.

398