16-Year Creep of Polyethylene and PVC

WILLIAM NICHOLS FINDLEY

and
J OSEPH FRANCIS TRACY
Diuision of Engineering, Brown University
Prouidence, Rho& Island
Creep tests at constant values of tensile stress, temperature,
and relative humidity for two thermoplastics were conducted
for approximately 132,000 hr. The strains, c, for the first 2000
hr of time, t, were described by an equation of the form
c = eo +r+tn where all other symbols are constants. This
equation was found to predict the creep of poly (vinyl chloride)
for approximately 132,000 hr with reasonable accuracy. The
predicted strains for polyethylene (density 0.924) were some-
what low. Strains during unloading and reloading after 90,000
hr of creep were predicted reasonably well by the Boltzmann
superposition principle.
n 1944 ( 1) it was shown that the first u)oo hr of
I tension creep of several reinforced thermosetting
plastics could be described by the equation
c = co + c+tn
( 1)
where c is the strain, t represents a dimensionless
ratio of time to unit time, cO, c + are constants for con-
stant stress and n is a constant independent of stress.
Some of the experiments reported in ( 1) were con-
tinued to approximately 100,000 hr. In 1958 ( 2) it
was shown that the creep predicted by using Eq I
with the constants reported in ( 1) for 2000 hr was
in good agreement with the extension of the experi-
mental data to about 100,OOO hr.
Since commencing the experiments described be-
low, about 16 years ago, a number of investigators
have reported results of long-duration creep of plas-
tics. Of these only that by Gohn and Cummings on
polyethylene ( 3) approached 100,000 hr duration.
An extensive table of creep data on many plastics ap-
pended to (4) contains data on three materials for
35,000 to 60,OOO hr duration.
Other investigators in addition to ( 2) who have
considered various expressions for describing the time
dependence of creep include Bergen ( 5) .
The present paper reports long-time tension of two
thermoplastics, polyethylene ( glass transition about
-165F) and unplasticized PVC (glass transition
about 188F). The tests were conducted at 75F.
Thus one material was tested above and the other
below its glass transition temperature.
Three of the tension creep experiments reported
in ( 6) for the first 1900 hr were continued for more
than 90,OOO hr. The stresses for these experiments
were 225 psi for polyethylene; 2000 and 4000 psi for
PVC. An additional experiment on the same poly-
ethylene at 450 psi started at the same time as the
others is also described in the present paper.
MATERIALS, APPARATUS, AND
EXPERIMENTAL PROCEDURE
The materials employed in this investigation were
the same as employed in (6, 7) , and three of the
specimens were the same ones used in ( 6) . The ma-
terials were described as follows:
Polyethylene. This material was obtained as a
compression molded sheet 9/16 in. thick from the
Plax Corporation. The molding powder used by Plax
Corporation was Bakelite DE2400, having a melt
index of about 1.2 decigrams/min and an extrapo-
lated number-average molecular weight of about
22,000. There were no additives or anti-oxidants. The
molding powder was preheated for 25 min at 5 psi.
Then the pressure was raised to 30 psi for 4 min,
then left in the press for 30 min with 60F water
running through the platens. The density was deter-
mined to be 0.924 g/cm3.
Poly(viny1 chloride), This PVC (Geon 404) was ob-
tained as a sheet 9/16 in. thick from the Nixon Nitra-
tion Works. The formulation was VX-108 Natural
and contained no plasticizer, 3.3 percent dibutyl-tin-
diborate as a stabilizer and 0.5 percent stearic acid
as a lubricant. It was blended at 280F and calen-
dered into sheets 0.02 in. thick on rolls at 300F.
Twenty-eight of these sheets were laminated together
in a press at 280 psi and 315F for 30 min and then
cooled rapidly in the press. This sheet was later an-
nealed at 275F for i5 min in an electric oven re-
sulting in a shrinkage of 5.7 percent in width and an
expansion of 1.6 percent in length. The density was
found to be 1.357 g/cm2.
The specimens were flat with enlarged ends. The
test sections were 5/32 in. by 9/16 in. cross sections
with a 4 in. gage length.
The apparatus and experimental procedure were
the same as described in detail in ( 8) and shown in
( 2) except that the testing frame for each specimen
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1974, Vol. 14, No. 8 577
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William Nichols Findley and Joseph Francis Tracy
was isolated from all the others and supported di-
rectly on the floor through isolation mounts. The
specimens were loaded by dead weights and levers
and the strain was measured by an averaging-type
extensometer employing a lever and measuring micro-
scope ( 8) . Companion specimens were employed
which carried no load and were used to indicate pos-
sible dimensional changes. The temperature and rela-
tive humidity were maintained constant at 75 1F
and 50 -t 1 percent relative humidity.
The experimental procedure was as follows. On
September 2, 1957, four specimens each of polyethy-
lene and PVC were subjected to a constant tensile
load. After about 2000 hr, tests of two specimens of
each material were discontinued. The remaining
specimens, the polyethylene at 225 and 450 psi and
PVC at 2000 and 4000 psi, were continued under
constant load and constant temperature and relative
humidity for more than 90,000 hr.
After about 90,000 hr it became necessary to re-
locate the laboratory, so all specimens were unloaded
and recovery strains were recorded. Then one speci-
men of each material plus a control specimen were
placed in a box to shield them from temperature
changes and moved quickly to a new laboratory (9)
at the same temperature and humidity but having
closer control. The original loads were reapplied to
the two specimens at about 300 hr after unloading
and the tests were continued to 132,000 hr.
scale. Figures 3 and 4 show to an expanded time
scale the recovery following unloading at about
90,000 hr. Also shown in Figs. 3 and 4 are the data
after reloading of one specimen of each material.
0 20 4 0 60 80 100 120 140
Ti me, IO'hr.
Fi g. 2. Creep curves for PVC at 75"F, 50 percent R. H.
RESULTS AND INTERPRETATION
OF CREEP DATA
The experimental data are shown by circles in
Figs. 1 and 2 for polyethylene and PVC, respectively.
Note the changes in the time scale. The data for the
first lo00 hr are shown to an expanded scale followed
by the data for 132,000 hr shown to a compressed
- Theory
0.4
0
0 20 40 60 80 100 120 140
Ti me, 103hr .
Fig. 1. Creep curues f or polyethylene at 75"F, 50 percent R. H.
N
4
Time, hr .
Fig. 3. Recovery and reloading of polyethylene following
creep for about 90,000 hr.
578
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1974, Vol . 14, No. 8
1 &Year Creep of Polyethylene and PVC
2.4
2.2
2.0
I . 8
1.6
.I-
C
Q)
1.4
Q)
a
.- Ii- 1.2
?
+
m
- 1.0
0
t
2
0.8
0.6
0.4
0.2
C
Theory
1, =90589.4
' 0 0
I I I I I I I
' 0 o q o o o o
t W m
0
N
+
N
+
N
c
+N +N
4 4
+-
d m 4
4
I1
4
N
Time, hr .
Fig. 4. Recovery and reloading of PVC following creep for
about 90,000 hr.
Note that the curves for the first 1000 hr and the
curves for 132,000 hr, drawn to a different scale,
have very similar shapes. Also note that the data
from about 500 to 1000 hr suggest a nearly constant
rate of creep. That this is incorrect is proven by the
long-time results.
The test data from approximately one-half hr to
2000 hr were fitted to the same power law ( E q 1 )
employed in earlier work (1, 2, 6-8) and found sub-
sequently to be applicable to combined stresses and
various temperatures, see for example (10, 11).
Values of eO, c +, and n were determined graphi-
cally from the data from one-half hr to 2000 hr by
methods described in previous papers and are shown
in Table 1. The values shown in Table 1 as re-evalu-
ated for this paper differ somewhat from those re-
ported in (6) for PVC and differ considerably from
those reported in ( 6) for polyethylene. Apparently
there was an error in the previous analysis for poly-
ethylene.
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1974, Vol . 14, No. 8
The data shown in Figs. 1 and 2 indicate that the
PVC is somewhat nonlinear and the polyethylene
strongly so for the stresses employed. Table 1 shows
that the nonlinearity occurs mainly in the coefficient
of the time-dependent term B+.
Long-Time Creep
Using the constants shown in Table 1, which were
obtained from the data from about one-half hr to
2000 hr, and substituting them in E q 1, the creep for
132,000 hr was computed and is shown in Figs. 1 and
2. The actual creep for polyethylene was somewhat
greater than predicted by E q 1 as shown in Fig. I ,
whereas the actual creep of PVC was slightly less
as shown in Fig. 2.
Recovery and Reloading
The Boltzmann superposition principle may be em-
ployed for complete unloading and reloading to the
same stress even when the stress is in the nonlinear
range. The modified superposition principle ( 12)
which has been shown to be useful for nonlinear be-
havior gives the same result under these circum-
stances. According to the superposition principle the
strain during recovery at zero stress is given by, see
( 2) for example:
or
where tl is the time at which the stress was removed.
The strain after reloading to the same stress at
t = tz is as follows according to the same principle:
+ c + ( t - t 2 I n , t > t 2 > tl (3)
r = c O + c + t " - [ E O + + ( t - - t l ) " ] , t > tl
= e + t n - + ( t - t l ) "
( 2)
c = "+ r + t n - +( t - tl)"
Equations 2 and 3 were employed together with
the constants in Table 1 to predict the strain during
recovery and during reloading with the results shown
in Figs. 3 and 4. Only polyethylene at 225 psi and
PVC at 4000 psi were reloaded, As shown the pre-
dicted strains agree reasonably well with the data.
Aging
During the entire period of the long-time creep
experiments the strains of one specimen (the control
specimen) of each material were observed under no
load as a check on dimensional changes occurring as
a result of aging alone. The strain aging caused a
Tabl e 1. Constants for Creep, Eq. 1
EO, ET1
Stress,
Mat eri al psi percent percent n
Polyethylene 225 1.07 0.236 0.154
Polyethylene 450 2.30 0.710 0.154
PVC 2000 0.37 0.0124 0.305
PVC 4000 0.81 0.046 0.305
579
William Nichols Findley and Joseph Francis Tracy
gradual expansion of 0.08 percent in 85,OOO hr for
polyethylene and a gradual shrinkage of 0.01 percent
in 85,000 hr for PVC. No correction was made for
aging in the creep curves shown. However, correct-
ing for strain aging would improve the correlation
between data and prediction by Eq 1 for long times,
especially for polyethylene at 225 psi. For this test
strain aging accounts for more than half the devia-
tion between the data and E q 1.
After about 132,000 hr following loading of the
stressed specimens the control specimens were loaded
as creep tests to determine the effect of aging on
creep. The stresses were: polyethylene, 225 psi; PVC,
4000 psi. These results are also shown in Figs. 1 and
2 in the left-hand portion of the figure. It was found
that no significant change in the creep behavior had
occurred in the polyethylene. The PVC, however,
had become stiffer and more creep resistant.
CONCLUSIONS
The data presented on long-time creep of poly-
ethylene and PVC show that Eq 1 can be used to
predict the creep behavior of these two thermoplas-
tics over long times with reasonable results. The ac-
curacy of the prediction for long-time creep of these
thermoplastics is as good as found earlier for thermo-
setting plastic laminates. It was also shown that the
Boltzmann superposition principle is suitable for
describing creep following unloading and reloading
after long-duration creep. Results of creep tests per-
formed 16 years apart on the same material showed
no effect of aging of polyethylene, but PVC became
stiffer and more creep resistant.
ACKNOWLEDGMENT
This work was sponsored by Picatinny Arsenal,
Ordnance Corps, Department of the Army, and the
Advanced Research Projects Agency of the Depart-
ment of Defense [ Materials Sciences Program
( DAHC 15-67-C-0217) 1. The gift of an air-condition-
ing unit by the Carrier Corporation, the gift of the
polyethylene by the Plax Corporation and the co-
operation of the B. F. Goodrich Chemical Company
and Nixon Nitration Works in preparing the poly
(vinyl chloride) are greatly appreciated. The assist-
ance of D. G. OConnor, R. M. Reed, and R. Mark
is gratefully acknowledged.
NOMENCLATURE
c = strain
co = time independent strain
c + = coefficient of time dependent term
t = time
tl, t2 = time at which stress is changed
n
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
= time exponent
REFERENCES
W. N. Findley, Symposium on Plastics, p. 118, ASTM,
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W. N. Findley and D. B. Peterson, Proc. ASTM, 58, 841
( 1958).
G. R. Gohn and 1. D. Cummings, ASTM Bull., 247, 64
(1960).
-
J . L. OToole, Modern Plastics Encyclopedia, ( 1968-
1969 ).
R. L.Bergen, Jr., SPE J., 23, 57 (1967).
D. G. OConnor and W. N. Findley, J. Eng. Ind., 84, 237
(1962).
W. N. Findley and G. Khosla, SPE J., 12, 20 ( 1956).
W. N. Findley and W. J. Worley, NACA Tech. Note
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W. N. Findley and R. M. Reed, ASHRAE Heating, Re-
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K. G. Nolte and W. N. Findley, ASME J. Basic Eng., 92,
105 ( 1970).
J. S. Y. Lai and W. N. Findley, Trans. SOC. Rheol., 17,
1, 63 (1973).
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580 POLYMER ENGINEERING AND SCIENCE, AUGUST, 1974, Vol . 14, No. 8