Polymers
B. E. READ
The shear modulus and damping have been measured at a frequency of about
1 c/s and at temperatures down to --190°C [or polyethylene oxide, polypro-
pylene oxide and polyacetaldehyde. Five different samples of polyethylene
oxide have been investigated, ranging in molecular weight from about 4× 103
i~p to 5 × 10 ~. The sample of highest molecular weight exhibits a loss peak at
about --57°C. As the molecular weight decreases the temperature of maximum
loss initially increases, passes through a maximum in the molecular weight
region of 104, and then decreases. After annealing the samples, the loss peaks
move to higher temperatures and broaden slightly and the magnitudes o] the
relaxations show a small reduction. The reverse effect is observed when water
or dioxan is added to the polymer. The relaxations are attributed to the
motions of chain segments in the disordered regions of the polymer, and it
is suggested that these regions may be subjected to strains induced by the
ordered regions of the polymer. Polypropylene oxide and polyacetaldehyde
exhibit loss peaks at about --62°C and --19°C, respectively, both of which
are attributed to relaxation processes related, to the respective glass transitions.
The results are discussed and compared briefly with data on other related
polymers.
EXPERIMENTAL
The logarithmic decrement (&) and the real and imaginary shear moduli,
G' and G" respectively, were determined from -190°C up to room
temperature. For one sample of polyethylene oxide (Polyox FC 118) the
measurements were extended up to the melting point of the polymer (66°C).
The measurements were made with a torsion pendulum operating at a
frequency of about 1 c/s 1.
Five samples of polyethylene oxide have been studied. They were obtained
from the Union Carbide Chemicals Co. (U.S.A.) and are designated, in order
of decreasing molecular weight, Polyox FC 118, Polyox FC 2 075, Polyox
2 464, Carbowax 20M and Carbowax 4000. Strips of each polymer
were moulded under pressure. The moulding temperature for the three
529
B. E. READ
highest molecular weight samples was 90°C. The two samples of lower
molecular weight were moulded at temperatures a few degrees above
their melting points. The densities and estimated molecular weights 2 of the
specimens are listed in Table 1. Samples were annealed by heating to 55°C
Polyethylene oxide
Polyox FC 118 f 5×10 ~
Unannea'ed 1"208 ] 5×10" -56 -59 0"34 34 0'27
Annealed 1-214 5×10 ~ -50 -52 0'75
+ Wa:er (3%) [ 5x10" -59 -61 0"44
Dried 1"278 5×10 ~ -55 -56 f'40
-~ Dioxan (7%1 5x10 ~ -66 -71 0"50 32 0"33
Polyax FC 2075 [ 8x10 ~
Unat~nealed 1,216 [ 8x10 ~ -54 -57 0"44 36 0"35
Ann=aled 1'222 8×10' -39 -50 0'96
Polyox 2 464 2x10'
UnanneaJed 1"223 2 x 105 -41 0"86
Annealed 1"228 2X I(P -38 l'O1
Carbowax 20M 1.5X10 ~
[--.>2'0x 10'
Unann:aled 1"196 -.->2"0 X 104 -2~ 0'68 33 0"22
Annealed 1"216 -->2.0>¢ IO~ 1"29
Carbowax 4 ¢,00 4X103
Unannealed 1"222 4XlO 3 -32 -37
Polypropylene oxide
t 1"7
Amorphous
(sulphur
vulcanizate) 1,045 -62 -65 0'24
Partially
crystalline 1.057 -62 -65 0"32 28 0"50
i:a sealed tubes under nitrogen for periods of about one week and slowly
cooling to room temperature. In order to study the effect of absorbed water,
a moulded specimen of Polyox FC 118 was placed over a beaker of water
in an evacuated desiccator for four days after which 3 per cent by weight of
water had been absorbed. After completing measurements on this sample
below room temperature it was pumped under high vacuum for three days
until its weight remained constant and a further run was then carried out.
Although this drying procedure was not generally adopted it indicated that
the specimen before wetting had contained only about 0"25 per cent of
moisture. In order to investigate the effect of absorbed dioxan, a sample of
Polyox FC 118 was immersed in dioxan at room temperature for 15 h
after which approximately 7 per cent by weight of dioxan had been
absorbed.
The partially crystalline sample was obtained from the polymerization
of propylene oxide in dioxan solution using zinc diethyl and water as
catalyst. For the mechanical measurements a strip was moulded at 90°C
under pressure. The amorphous sample was prepared by a zinc diethyl
-water catalysed polymerization of the monomer containing 10 per cent
530
MECHANICAL RELAXATION IN SOME OXIDE POLYMERS
RESULTS
The variation of G', A and G" V~ith temperature for the five unannealed
samples of polyethylene oxide is shown in Figure 1. For all samples G' is
seen to decrease with increasing temperature over the entire temperature
&-.
11'0
E
c
]3
•--q10.0
_3
°
90 I I J I I i I I I P I "
03
" /\ • .t"
0-2
01
- ' 7 i i I L I I I I ~ I i
C
-~ 10
%
x
.~ 0-5
= i L i ~ i = t t I I I
-180 -140 -100 -60 -20 20 60
Temperature oc
Figure l~Variation of G', G" and the logarithmic decrement
(A) with temperature for Polyox FC 118 (O), Polyox FC 2075 (rq),
Polyox 2464 (&), Carbowax 20M (®) and Carbowax 4000 (A)
531
B. E. READ
range investigated, but shows the largest changes in the relaxation regions
where loss peaks are also observed. The A versus T curves are broad but
exhibit well defined maxima at temperatures denoted by T a ..... in Table 1.
The corresponding maxima in the G " curves, shown as TG-..... in Table 1,
occur at somewhat lower temperatures than T~ ..... and coincide with the
inflection points of the G" curves. Between Ta ..... and room temperature the
A values are fairly high on account of the low magnitude of G" in this region
(A ~ x G " / G ' ) . The G " peaks, which in all cases are more symmetrical than
the corresponding A loss peaks, are slightly broadened in this high
temperature region. As the molecular weight decreases, the G" peaks
-10
-20
s
-30 / \
,~ -4o
.~E
" %
-5o
-60
-70
-80 I I
2 3 4 5 6 7
Log/~w
Figure 2--Plot of TG,,' max. versus log M w for unannealed (O) and
annealed ([[]) polyethylene oxide. M~ is the estimated weight average
molecular weight• Filled circle (0) derived from McCrum's data 4
on Carbowax 20M. The triangle (A) represents T,,,, max. estimated
from the dielectric data of Koizumi and Hanai '5. The solid line
represents schematically the predicted dependence of TG,,' ra~x. on
molecular weight in the absence of crystaUinity
broaden slightly and decrease in height, this effect being most marked with
the three samples of lower molecular weight.
The variation of the loss peak temperature with molecular weight is
illustrated in Figure 2 where T G",.... is plotted against log Mw. At the highest
molecular weight (Polyox FC 118) To-.~,z. has an apparently limiting low
value of - 5 9 ° C . As the molecular weight decreases To-~,x. increases,
appears to reach a m a x i m u m value of about - 2 4 ° C in the molecular weight
region of 104 and subsequently decreases. The filled circle shown in
Figure 2 is the value of T o , .... calculated from the data of MeCrum 4 on
Carbowax 20M. It is seen to lie some 9°C below our own value.
After annealing, an increase in density was observed for all samples (see
532
11C
E
"ID
.c_ 10"C
E~
o
9C t I I I i I I I¸ I I
1"5 - - /k
q.,
~0
k 1.c /
a:;--
'o
× 05
L I I L t I I I I I I
-10( -80 -60 -/.,£) -20 0 20-100-80 -60 -40 -20 0 20
(a) Temperature (b) °C
11'0
&-....
E
c 10.0
0
_J
9.0 I 1 I I I I I I I I , I
15
/
E
>-s
~ 1.0 k-
£
0.5
0 I 1 I I I I I I I I I
-100 -80 -60 -40 -20 0 20-80 -60 -40 -20 0 20
(c) Temperature (d) oC
Figure 3--Plots of G' and G" versus temperature for annealed polyethylene
oxide (Q): (a) Polyox FC 118, (b) Polyox FC2075, (c) Polyox 2464, (d)
Carbowax 20M. Broken lines show the data for the unannealed samples for
comparison
533
._. 11.0
E
E
>.,
x~lO.0
r~
9"0 • I 1 I I t I t I t_ ~ i,
2"0
ul.5
¢-
"0
.--,I.0
T \\
I
OI I I I f I ] I J J J ~ /
•,-100 -80 -60 -40 -20 0 20-100 -80 -60 -gO -20 0 20
Temperature °C
(a) (b)
Figure 4--(a) G' and G" versus temperature for Polyox FC 118 containing 3 per
cent water (0) and after drying (C)); (b) Data for Polyox FC 118 before (broken
curve) and after full line adding 7 per cent dioxan
/
7'0
8~
.,~ 1.C~
0.5 ' ~
-+ ...
-180 -140 -100 -60 -20 20
Temperat u re oC
Table 1). Plots of G' and G" versus temperature for the annealed specimens
are compared with those for the unannealed samples in Figure 3. In all cases
annealing is seen to shift the loss maxima to higher temperatures, as shown
also in Table 1 and Figure 2. Generally the magnitude of the relaxation,
determined by the incremental change in G' and the height of the loss peak,
is decreased slightly. The loss peak for Polyox 2 464 is considerably
broadened, whilst the G" curves for Polyox FC 118 and FC 2 075 exhibit
shoulders between the main loss peak and room temperature.
The effects due to absorbed water and dioxan are shown in Figure 4 and
Table 1. Both liquids cause the loss peaks to move to lower temperatures
and cause a slight increase in the magnitude of the relaxation.
The data for both the partially crystalline and amorphous polypropylene
oxide are shown in Figure 5 and Table 1. Both samples exhibit a single
relaxation below room temperature and, within experimental error, the loss
peak temperature is the same for both samples. The magnitude of the
relaxation is much larger, however, for the amorphous polymer.
The results for polyacetaldehyde are illustrated in Figure 6 and Table 1.
This polymer also shows a single relaxation region below room
temperature.
Activation energies
In a recent paper ~ it was shown that an average activation energy
(<Q-1)~v.-1) for relaxation may be estimated from the area beneath a plot
~
~'qOO
E
f~9-0
"0
e"
~8-0
0
~7"0 o
I I
535
B. E. R E A D
<Q- *>=,.-* = 1 /
f:f o
• (r o, Q) Q - ' dr o dQ
= (G L - G;) R II
(1)
2
fo'~ 0 " dO/T)
where G'~, and G'0 are the infinite frequency and zero frequency moduli,
respectively, determined from a frequency dispersion at constant tempera-
ture. Both G ~ and G'0 are assumed to be independent of temperature.
(r 0, Q) is a normalized distribution function giving the fraction of relaxa-
tion processes have activation energies between Q and Q+dQ and, in
addition, relaxation times between ro and ro + d% at infinite temperature.
In the present application we may, to a good approximation, replace
(G'~-G'o) by the total modulus drop from - 1 9 0 ° C to 20°C (at constant
frequency) and graphically integrate the loss curves between the same
temperature limits. Activation energies deduced in this way for several of
the unannealed samples are presented in Table 1.
1'0 - -
0"8
~0'6
0'4
o
0"2 o o
O~ 0 .)______ ~__
of the loss maxima, however, the loss peaks are relatively sharp and
symmetrical and we may attempt to analyse them by the empirical Fuoss-
Kirkwood equation ~
G"/G"m~. = sech/3 In tot (2)
where/3 is a parameter which is equal to unity for a single relaxation time
and for a distribution lies betwee~ zero and unity, to is the experimental
frequency and the relaxation time r = r 0 exp (Q/RT). /3 may be obtained
from the following equation relating the width of a G" versus 1/T curve
to Q~
fl=2"63 / Q (T2 - 1 - T -~ .... ) (3)
where T2 is the temperature at which G"=½G"ma~. and Q is given in cal/
mole. Values of/3, calculated from equation (3) using Q values determined
as above, are given in Table 1. Plots of equation (3) for fl-- 1 and/3 =0.35
respectively are shown in Figure 7 together with the experimental points for
Polyox FC 2 075. It is observed that the experimental curve is much broader
than would be obtained for a single relaxation time. The curve for/3=0"35
fits the data reasonably well in the vicinity of the maximum but does not
provide a good overall fit.
DISCUSSION
Polyethylene oxide
Polyethylene oxide is a highly crystalline polymer in which the
fundamental unit cell is monoclinic and consists of two polymer chain
segments probably present in the form of parallel helicesL The unit cells
form crystalline aggregates which make up the radial arms of polymer
spherulitesL The measured densities of the samples (Table 1) are con-
siderably lowek than the value of 1"33 g/ml estimated from the unit cell
dimensions for a completely crystalline material. Although the low densities
may partly be due to the presence of voids 7, it is probable that the polymer
contains 'disordered' regions which may be regarded either as a separate
amorphous phase or as crystalline lattice defects8. When considering high
degrees of crystallinity, the lattice defect hypothesis seems more appropriate
and, furthermore, it is unlikely that a normal amorphous phase could exist
unaffected by the large amount of crystallinity. However, in the absence of a
precise knowledge of the physical structure of the polymer we refer generally
to the existence within the material of disordered regions, the fraction of
which is indicated by the density.
The loss peak temperatures of the four higher molecular weight
unannealed polyethylene oxide samples (Table 1) correlate with the tem-
peratures of dielectric loss maxima observed at higher frequencies in this
laboratory 9. In addition, the activation energies of about 30 to 35 kcal/mole
compare well with values obtained from the temperature dependence of the
average dielectric relaxation time. Thus similar mechanisms probably give
rise to both the mechanical and the dielectric relaxations.
Since the proportion of disordered polymer generally decreases with
annealing, the small decrease in the relaxation magnitudes after annealing
537
B. E. READ
(I c/s) which he observed for Carbowax 20M with loss peaks exhibited by
polytrimethylene oxide 1~ ([--CH~---CH~--CH2---O--]~) at - 4 5 ° C (100 c/s),
polytetramethylene oxide xB ([--CH~---CH2--CH2---CH~--O--]n) at - 5 5 ° C
(100 c/s), and a very small peak (labelled /3) in polymethylene oxide
([--CH~--O--]~) at about - 1 3 ° C (I c/s),. Though tentative, this compari-
son would indicate that the loss peak temperature increases as the pro-
portion of oxygen in the main chain increases. However, in view of the large
variation of T~ ..... with molecular weight for polyethylene oxide this
conclusion is not necessarily valid. For example, from the data on the high
molecular weight Polyox FC 118 sample we estimate, in conjunction with
the dielectric data, a T~ ...... value of - 5 0 ° C at 100 c/s which is intermediate
between the values for polytrimethylene oxide and polytetramethylene
oxide*. Also we consider that the predominant peak shown by polymethy-
lene oxide at - 6 0 ° C (100 c/s), which McCrum labels the 3' P eak4, should
be involved in the comparison rather than the small fl peak which we were
unable to detect a. Both polytrimethylene oxide and polytetramethylene
oxide exhibit additional peaks at - l l 0 ° C (100 c/s) which have been
attributed by Willbourn 1~ to [--CH2--]r, segments containing a minimum
of three - - C H 2 - - units. The fact that polyethylene oxide and polymethy-
lene oxide do not show peaks in this temperature region lends support to
this view.
Polypropylene oxide and polyacetaldehyde
Stereoregular polypropylene oxide crystallizes with an orthorhombic
unit cell lz. Two planar zig-zag molecules lie parallel to the c axis. From
the unit cell dimensions we estimate a theoretical crystalline density of
1-154 g/ml. From the densities of amorphous polypropylene oxide (1"002
g/ml) TM and the partially crystalline sample used in this study the latter
sample is estimated to contain 39 per cent by weight of crystalline material.
Since the loss maximum temperatures for both the amorphous and crystalline
samples coincide, the loss peaks for both samples are undoubtedl3/related
to the glass transition in this polymer. Also the disordered regions of the
partially crystalline sample, at this relatively low degree of crystallinity,
probably resemble a normal amorphous phase.
The close proximity of the loss peaks for the high molecular weight
polyethylene oxide ( - 5 7 ° C , 0-34 c/s) and polypropylene oxide ( - 6 2 ° C ,
0"3 c/s) suggests that the methyl substituents in the latter polymer do not
have much influence on molecular mobility. This may be partly due to the
effect of oxygen atoms in spacing apart the methyl substituents. For example,
in the planar chain configuration, successive CH3 groups occur on opposite
sides of the chain axis. A similar conclusion results from a comparison of the
position of the loss peak in polypropylene oxide with that shown by its
isomer polytrimethylene oxide 1~ ( - 4 5 ° C , 100 c/s).
The large modulus change accompanying the relaxation in poly-
acetaldehyde is also in,dicative of processes related to the glass transition
in this material. The value of Tzx..... ( - 19°C, 0-58 c/s) compares well with
*Since TA, m~x. for polytrimcthylene oxide and polytetramethylene oxide could also depend or. molecular
weight~ this comparison is tentative.
540
MECHANICAL RELAXATION IN SOME OXIDE POLYMERS
a value of approximately + 10°C (100 c/s) very recently reported for this
polymer by Weissermel and Schmieder 18. F r o m the position of our low
frequency loss peak we would estimate a glass-transition temperature of
about - 3 0 ° C . Comparison of T:~...... in this polymer with that shown by
polymethylene oxide ( - 7 6 ° C , 0-43 c/s) and also with that of its isomer
polyethylene oxide ( - 57 °C, 0"34 c/s) indicates that the occurrence of methyl
substituents on alternate carbon atoms sterically hinders molecular motions.
It is interesting to note that the polyacetaldehyde loss m a x i m u m lies fairly
close to that observed for polypropylene x9 ( - 4 " 7 ° C , 1 c/s) which also has
----CH~ substituents on alternate carbon atoms.
The positions of the loss peaks in polypropylene oxide and poly-
acetaldehyde could, of course, depend on molecular weight. However,
amorphous samples of both polymers were studied, the polypropylene oxide
being an infinitely crosslinked network, and the polyacetaldehyde having
a molecular weight (Table 1) much higher than the usually critical value
of about 10 4.
541
B. E. R E A D
542