You are on page 1of 14

Mechanical Relaxation in Some Oxide

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.

IN A recent publication we reported on a study of molecular motions in
polymethylene oxide ([----CH2--O--].) by dielectric and dynamic mech-
anical methods 1. The purpose of the present paper is to present and discuss
some low frequency mechanical data on the related oxide polymers
polyethylene oxide ([---CH2----CH~--O--].), polypropylene oxide ([--CH
(CH-~)--CH2--O--].) and polyacetaldehyde ([---CH(CH3)--O--].). The
relaxation behaviour of polyethylene oxide has been found to depend
significantly on the molecular weight of the polymer, its state of annealing
and the presence of absorbed liquids such as water and dioxan. Partially
crystalline and amorphous samples of polypropylene oxide and an
elastomeric sample of polyacetaldehyde have also been studied.

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

Table 1. Summaryof data
Estimated
Density
I
] molecular Fr,q.e
Polymer T , . m~x. Tc, ' ". nl
(g l ml) weight* (*C) (°CI tx. (c/s keal/mole
. . . . ( ~ t av.) _

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

Polyaeetaldehyde -19 -29 I o58 I
*The molecular weights quoted for the polyethylene oxide samples are to be regarded as approximate.
They were suggested to us in a private communication with the Union Carbide Chemicals Company
(U.S.A.)L
"fCalc'flated from intrinsic viscosity measurements using the viscosity/molecular weight relationship of
Bvvey and Wands~L

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

of butadiene monoxide which rendered the product vulcanizable. The
polymer was subsequently vulcanized with 2 per cent sulphur.
The polyacetaldehyde specimen was prepared in this laboratory by bulk
polymerizing acetaldehyde using zinc diethyl as catalyst s. In order to
stabilize the polymer the end groups were esterified by heating at 50°C in a
pyridine-acetic anhydride solution. A small tough fraction of the polymer
(thought to be the crystalline fraction s) was insoluble in the esterification
mixture and was consequently separated. After esterification, the product was
precipitated in water, and twice redissolved in acetone and precipitated
with water. The polymer was then dried in a vacuum desiccator at room
temperature and finally moulded into rubberlike strips at 60°C.

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

U

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

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 \\

x

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

Figure 5--Plots of G' and A against
temperature for amorphous (O) and
partially crystalline (A) polypropylene
oxide
534
MECHANICAL RELAXATION IN SOME OXIDE POLYMERS

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

Figure 6--G', A (Z~) and 2' 0 2"0
G" (Q)) against temperature for
polyacetaldehyde
~1'5 1"5

~'o 1.0 I'0
%
0-5 0"5

-101 -60 -20 20
Temperature oC

535
B. E. R E A D

of G" against 1/T at constant frequency

<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.

Distribution of relaxation times
From the general shape of the loss curves it is clear that an extremely
broad non-symmetrical distribution of relaxation times would be required to
describe the behaviour over the entire temperature range. In the vicinity

1'0 - -

0"8

~0'6

0'4
o

0"2 o o
O~ 0 .)______ ~__

O~ 3'5 4.0 4-5 50 5"5 60
I/T (xlO3)
Figure 7--Theoretical curves of G"/G"max. against 1/T for two
values of the distribution parameter ~: /3= 1 (broken curve),/3=0"35
(full line). Experimental point for Polyox FC 2075 (O)
536
MECHANICAL RELAXATION IN SOME OXIDE POLYMERS

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

is consistent with a mechanism involving segmental motions in the dis-
ordered regions of the polymer. The effects of both water and dioxan in
increasing the relaxation magnitude and moving the relaxations to
lower temperatures support this conclusion. Both liquids may preferentially
enter and plasticize the less dense disordered regions as in the case of
polyoxymethylene1. Also since water and dioxan are each potential solvents
for the polymer they would tend partially -to break down the crystallinity
and plasticize the resulting disordered regions. The possibility that the loss
mechanism arises entirely from small quantities of absorbed moisture has
been considered, but this seems unlikely since the estimated 0.25 per cent of
moisture normally present would probably have a negligible effect when
compared with that produced by the 3 per cent of absorbed water. Unfortu-
nately our present experimental set-up does not allow measurements to be
made in a completely moisture-free atmosphere, and experiments under
these conditions would be desirable. The suggestion that the relaxation
process occurs in the disordered regions has received additional support from
the dilatometric observation of a glass transition temperature at about
- 6 7 ° C for a quenched sample of Polyox FC 1181°. Glass transitions
determined dilatometricaUy usually occur some 10 ° to 15°C below low
frequency mechanical loss peaks. The fairly high activation energies are
also consistent with relaxation processes related to the glass transitions.
If the proposed mechanism is essentially correct, then the increase
of Ta,, .... after annealing shows that the heat treatment has in some way
restricted molecular motions in the disordered regions. It is tentatively
suggested that this restriction results from the existence within the disordered
regions of strains induced by the ordered crystallites and therefore
enhanced by annealing. In discussing the possible nature of the proposed
strains it is convenient to distinguish between orientational strains in which
the volume remains constant, and compressional (or dilatational) strains
which involve volume changes. For example, when orientational strains
are produced in natural rubber by simple extension, the loss peak associa-
ted with the glass-rubber transition broadens but its position remains
unchanged 11. On the other hand, by analogy with dielectric behaviour 12,
the loss peaks would be expected to shift to higher temperatures if the
volume is decreased by an increase in external pressure. Also the peaks have
been seen to move to lower temperatures when the volume is increased by the
addition of liquid plasticizers. In fact much evidence exists to suggest that
mechanical relaxation times are largely determined by the free volume avail-
able to the moving segments. We may thus suggest that the increase in
To,,, .... (and TA. max.)upon annealing may be related to compressional strains
induced in the disordered regions by expansion of the crystalline aggregates,
and that the broadening observed in the case of Polyox 2 464 may be due to
induced orientation.
The shoulders which appear after annealing on the high temperature side
of the loss peaks for Polyox FC 118 and Polyox 2 075 are perhaps
suggestive of a crystalline mechanism similar to the so-called a-mechanism
in polyethylene 1S. Unfortunately there is little evidence for such a hypo-
thesis. However, since the loss peak for Carbowax 20M lies in the
538
MECHANICAL RELAXATION 1N SOME OXIDE POLYMERS

temperature region where this crystalline mechanism might be operative, the
possibility of overlapping mechanisms due to both disordered and crystalline
regions in this polymer cannot be excluded. In this connection it should be
noted that crystalline peaks also move to higher temperatures after anneal-
ing owing to an increase in crystaUite size 13.
The dependence of To,, max (and T ~..... ) on molecular weight appears at
first sight surprising. In the absence of crystallinity To,,,.... would be
expected to increase with molecular weight toward an asymptotic limit in the
molecular weight region of 5 000 > 10 000 (300 > 600 chain atoms).
Such a trend has been observed for the glass transition temperature of
polystyrene and has been attributed to the plasticizing effect of chain ends at
low molecular weights 1". The packing around chain ends is inevitably looser
than along the main chains which leads to an increase in free volume. The
predicted molecular weight dependence of T~,, .... in the absence of
crystallinity is represented qualitatively by the full line in Figure 2. The point
shown at a molecular weight of 194 was derived from the dielectric data of
Koizumi and Hanai 1~ on supercooled (amorphous) tetraethylene glycol. The
maxima of ~" (dielectric loss factor) versus T curves determined in the
frequency range 10a c/s to 5 × 10S c/s were extrapolated to a frequency of
0-5 c/s. This comparison with dielectric data assumes a correlation with
mechanical data at low molecular weights which is in fact found in the
higher molecular weight range. The high values of TG,,,.... in the intermediate
molecular weight region are most likely due to crystallinity. As the mole-
cular weight decreases from a value of 5 × l0 s the chains are able to pack
more easily together, the proportion of disordered material decreases, and
the strains induced in the disordered regions increase. Hence the magnitude
of the loss decreases, the loss peaks broaden slightly and shift to higher
temperatures. Below molecular weights of about 104 the additional chain
end effect c a u s e s TG,,, . . . . to decrease with a further reduction in molecular
weight. The fact that TG- .... for Carbowax 20M (-33°C) derived from
McCrum's data 4 is 9°C lower than our value could perhaps be due to
differences in molecular weight between different batches of this material
or to different moulding conditions (for example, a faster rate of cooling).
Acording to the above discussion TG,,,.... should depend on annealing and
molecular weight largely through its dependence on density. Although a
general trend with density is found, the density of Carbowax 20M appears
low. Density measurements in this material are probably unreliable on
account of small holes which were often visible in moulded samples,
although care was taken to select an apparently homogeneous sample. It
should be emphasized that the interpretation suggested for the effect of
molecular weight is somewhat tentative, particularly in view of the possi-
bility, mentioned above, of the existence of a crystalline mechanism in the
samples of lower molecular weight.
In comparing the loss peak temperature of polyethylene oxide with that
of related polymers, it is preferable to consider the T~ ..... value for the
very high molecular weight Polyox FC 118. At high molecular weights the
effects of crystallinity and chain ends are probably at a minimum and
possibly negligible. McCrum ~ has compared the T~ ..... value of - 2 7 ° C
539
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.

The author wishes to thank Dr F. E. Bailey of Union Carbide Chemicals
Co. [or supplying the polyethylene oxide samples and Dr G. Allen of
Manchester University for the polypropylene oxide specimens. Thanks are
also due to Mr G. O'Neill for preparing the polyacetaldehyde and to Mrs J.
Hawkins for help with the experimental work. The work described above has
been carried out as part of the research programme of the National Physical
Laboratory and is published by permission of the Director of the Laboratory.

Basic Physics Division,
National Physical Laboratory,
Teddington, Middlesex
(Received December 1961)
REFERENCES
1 READ,B. E. and WmLIAMS,G. Polymer, Lond. 1961, 2, 239
2 BAILEY,F. E. Private communication
Ftmt~AWA, J., SAE~USA,T. and Fum, H. Makromol. Chem. 1961, 44-46, 398
4 McCRuM, N. G. J. Polym. Sci. 1961, 54, 561
READ, B. E. and WILLIAMS,G. Trans. Faraday Soc. 1961, 57, 1979
Fvoss, R. M. and KmKWOOD,J. G. J. Amer. chem. Soc. 1941, 63, 378 and 385;
J. chem. Phys. 1941, 9, 327
SMITH,K. L. and CLEVE,R. V. lndustr. Engng Chem. (Industr.), 1958, 50, 12
8 STUART,H. A. Ann. N.Y. Acad. Sci. 1959, 83, 23
9 WmLIAMS,G. To be published
10 ALLEN,G. Private communication
11 MASON, P, 'The physical properties of polymers', p 262. S.C.I. Monograph No. 5,
London, 1959
12 O'REmLY, J. M. Abstracts of IUPAC Conference on Macromolecular Chemistry,
Montreal, Canada, 1961
13 NIELSEN, L. E. J. Polym. Sci. 1960, 42, 357
~Fox, T. G and FLORY, P. J. J. appl. Phys. 1950, 21, 581; J. Polym. Sci. 1954,
14, 315
a5 KOIZUMI,N. and HANAI,T. J. phys. Chem. 1956, 60, 1496
16 WILLBOURN, A. H. Trans. Faraday Soc. 1958, 54, 717

541
B. E. R E A D

17 STANLEY,E. and Liar, M. J. Polym. Sci. 1960, 43, 453
18 WEISSERMEL, K. and SCHMIEDER,W. Makromol. Chem. 1962, 51, 39
19 NEWMAN,S. and Cox, W. P. J. Polym. Sci. 1960, 46, 29
eo BOVEY, F. and WANDS, R. C. J. Polym. Sci. 1954, 14, 113

542