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24 ~ I,V.=0'54 16500
_~ 13 []
22 ............. ,~. . . . . . . & I.V.=O.58 18000
20 e A^~. x I.V.=0.60 18500
.E 16
_a | e
|
I--
~o
z 8 ~G e | |
o6 A x ee
x
~' 4
0
2
r I I I 1 q I t r I
210 l I
-- O 0 --180 --160 --140 --120 --100 --80 --60 --40 --20 0 40 60
TEMPERATURE ~
Figure 4 E f f e c t o f molecular weight on amorphous PET. 1 in rain, - 1 = 2.54 c m rain - 1
*1 in. m i n . - z = 2.45 cm rnin -1.
TENSILE gEHAVIOUR OF PET
24
" X X
. . . . ~ . . . . . . . .
2O
"7-, 16
z
x
'0
~ 4
m t~
F i i i i ~ J I ~ i i i F
-200 -t80 -t60 -140 -120 -100 -80 -60 -40 -20 0 20 40 6O
TEMPERATURE OC
18
16
14
,E
~12
t~
mtO
d
<
z
0 g
z
~•
0
~ 6
i i i 1 i F I I
drawing transition both move to higher tempera- expected to have a higher activation energy than
tures with increasing strain rate. the high temperature yield process. The data
At the higher rates of extension the stress tend to confirm this, although the range of strain
values had to be measured from an oscilloscope rates is not sufficiently great to allow a detailed
response because of the lag on the recorder pen. interpretation.
Three regions of failure were evident, but at the The change in behaviour at ~ -- 60 to -- 40~
highest rate of strain the ductile/cold-drawing could be associated with the ),-relaxation
transition was not very clearly defined. At the transition in this polymer [7].
highest crosshead speed of 40 in. rain -1 the yield
stress values fell below those for 10 in. min -1 3.2. Crystalline P E T
(see fig. 6), which suggests that adiabatic heating The effect of crystallinity on the stress/tempera-
occurs. ture behaviour is shown in fig. 7. It can be seen
The experimental results show that there are that up to 35 % crystallinity there is little influ-
two well defined regions of yield behaviour. As ence on the brittle stress, but the yield stress is
well as differing in the nature of strain hardening much increased. The brittle/ductile and ductile/
i.e. in post-yield behaviour, the regions differ in cold-drawing transitions therefore move to
the nature of the yield process, as revealed by the higher temperatures. Increasing the crystallinity
strain-rate sensitivity. A possible explanation for from 35 to 44% (see fig. 8) has a dramatic effect
this is as follows. At high temperatures, cold- on the brittle stress, reducing it from about
drawing occurs and this has been described [6] as 20000 to 15000 psi.* This could be due either to
the stretching of a molecular network. In this annealing faults or to a change in the morpho-
region it was shown by the effects of cross-linking logical structure. The transition points are still
that the yield process involves freeing the evident, and there is a further increase in the yield
molecular chains between entanglement points. stress in both the ductile and the cold-drawing
At lower temperatures, the polymer ruptures i.e. regions. These results show that both yield
the strain hardening associated with the orienta- mechanisms are affected by crystallinity. This is
tion of the molecular network does not occur. It an acceptable result, in terms of our tentative
is therefore proposed that at these temperatures proposals for these yield mechanisms. The
the yield process involves the pulling out of presence of crystallites is likely to make it more
entanglements. This yield process would be difficult either to disrupt the structure entirely, or
| 35% CRYSTALLINE
24 x. AMORPHOUS
2O
16!
w
~12
Z
o
z8
I I I I I / I I ! I / I I
-200 -t80 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40 60
TEMPERATURE ~
Figure 7 Effect of crystallinity, 1 in. min - I = 2,54 cm min - 1 .
*1 p s i = 6894.76 N m -~.
1092
TENSILE BEHAVIOUR OF PET
'clO e ~
x •
x•
.1
~
Z
I I i I I I I I
- O -60 -40 -20 O 20 40 60 80
TEMPERATURE ~
Figure8 Effect of molecular weight on crystalline PET. 1 in. rain -1 ~ 2.54 cm rain -1
to allow chain sliding which is the essence of the 3.3.1. Preparation of Samples
high temperature yield process. A mould was constructed for producing samples
It is interesting to note a direct effect of that could be effectively notched and the
molecular weight. Fig. 8 shows that decreasing dimensions of this mould are shown in fig. la. A
the molecular weight from 16 500 to 11 000 Charpy 0.010 notching tool was mounted in a
moves the brittle/ductile transition from - - 3 0 specially constructed holder and cutting of the
to -- 10 ~ C. This appears to be due entirely to a notches was carried out on a milling machine.
reduction in the brittle stress. The ductile/cold- Two notch depths were used, 0.075 in. and 0.110
drawing transition does not move significantly. in.
This confirms that crystallinity is more important
than molecular weight in determining the yield 3.3.2. Amorphous P E r
behaviour, a result to be deduced from the data Experimental results for P E T show that notching
of figs. 4 and 7. The data for the crystalline can drastically alter the pattern of the character-
material is summarised in table I. istic behaviour for a given polymer. In fig. 9 the
notched and unnotched stress/temperature curves
3.3. E f f e c t o f N o t c h i n g and Notch Sensitivity for amorphous P E T at a cross-head speed of 0.1
Notched samples were examined for stress/strain in. rain -1 are shown. The notched sample has
behaviour at various temperatures. two notches diammetrically opposed, cut to a
TABLE I Summary of results from the stress-strain temperature exp3rimants carried out on crystalhne PET.
t6
w
rr
I-
mt2
...1
z
O 8
z
x
?
o
4
-200 -180 -160 -140 -120 -1OO -80 -60 -40 -20 O 20 40 60
TEMPERATURE~
depth of 0.110 in. In the cold-drawing region the temperature of the brittle/ductile transition very
average yield stress has been raised by notching appreciably so that notched PET shows brittle
by a constraint factor, but not to the extent that behaviour at room temperature. The brittle
the calculations for such notch dimensions strength is temperature dependent, rising with
predict (see appendix). decreasing temperature to a value close to the
Notching also affects the brittle stress, reduc-
unnotched brittle strength. The fracture surfaces
ing this so that when the stresses are calculated
on the basis of the remaining cross-sectional area indicated brittle behaviour over this temperature
the notched brittle stress curve undercuts that for range.
the unnotched sample. The notched brittle strengths are molecular
These effects taken together increase the weight dependent, as shown in fig. 10.
24f
22
EXTENSION RATE O'1 in.rain-1 |
•
I.V,=O,84
I,V.= 0 ' 5 4
2O A I.V, = 0 " 4 0
T *
.~ 18
m 1 6 -~, •
if)
uJ
w 14
j12 A | X X
0
z 8
O" i I I I I -- 810 I I I I I I
-200 -180 --160 -140 --120 -IOO --60 --40 -20 0 20 40 60
TEMPERATURE ~
1094
TENSILE BEHAVIOUR OF P E T
20
• UNNOTCHED
| NOTCHED
u)
u.112
M
Z 8
O
Z
)
I
-100 -80 - 6 0' - 4 0' - 2 0' 0' 2o 4o 6o 80
' l e' o
TEM PERATU RE ~
24
Z ~ ~ O _ _ 9 ".% 9
Z
x
b
4
/ I I I I I I I I
-100 -80 -60 -40 -20 O 20 40 60 80
TEMPERATURE ~
Figure 12 Effect of crystallinity on notched P E T .
1095
J. M. STEARNE, I. M. WARD
crystallinity and this can lead to brittle behaviour (i) For a 0.075 in. notch and r = 0.010 in. the
if this yield stress exceeds the fracture stress, constraint factor is 2.09.
which is reduced by crystallisation. (ii) If r is 0.005 in. then the constraint factor is
(iii) The brittle stress is comparatively insensitive 2.12.
to molecular weight at high molecular weights (iii) For a 0.110 notch and r = 0.010 in. the
but falls rapidly at low molecular weights. The constraint factor is 2.04.
brittle/ductile transition therefore moves to
higher temperatures as the molecular weight of Acknowledgement
the polymer falls and can even lead to brittle The authors would like to thank Mr T. A.
behaviour at room temperature for a very low Roberts who carried out much of the experi-
molecular weight. mental work and Mr P. I. Vincent for helpful
comments on the draft manuscript.
Appendix
Constraint Factor for Deep Wedge-Shaped References
Notches with Circular Roots [8] 1. P. I. VINCENT, Polymer 1 (1960) 425.
From the longitudinal tensile stress distribution 2. J. B. J A C K S O N a n d E. R. D I X O N , J. Materials Sci. 3
across the minimum section of a long notched (1968) 464.
bar, use of Hencky's theorem leads to a yield 3. D. A. S. RAVENS and I. M. WARD, Trans. Faraday
Soc. 57 (1961) 150.
point load (L) per unit thickness of,
4. P . I . VINCENT, Encyclopedia of Polymer Science and
L=4ka
[ (1 + a ) - - a ( er~ - - i --a)
] Technology Vol. 7 (1967) p. 292.
5. P. R. PINNOCK and I. M. WARD, Trans. FaradaySoc.
62 (1966) 1308.
if a/r /> e ~ -- 1. Here r is the radius of the circu- 6. s. w . ALLISON and I. M. WARD, Brit. J. Appl. Phys.
lar root, of angular span 2a. 2a is the width of the 18 (1967) 1151.
minimum section of the bar and 2k is the tensile 7. A. B. THOMPSON and D. W. WOODS, Trans. Faraday
yield stress. Soc. 52 (1956) 1383.
The constraint factor is the ratio of the yield 8. R. HILt, "Plasticity" (Clarendon Press, Oxford,
point load to the yield point load for tensile yield 1950) p. 250.
of the same thickness of width 2a and equals
L/4ka .
~ ' ~ ~ / / 2 0=45~
ct=t35 ~
\
\ / 2(a "38in
\ /
\ /
v
A1
1096