Glass Transition of Poly(oxymethy1ene)
Hidematsu Suzuki, Janusz Grebowicz and Bernhard Wunderlich
Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12181, USA
(Manuscript received 22 June I984: accepted 6 Augut 1984)
Heat capacity data of semicrystalline poly(oxymethy1ene) samples, Delrin and Celcon, are analysed in
order to discuss the glass transition behaviour of this polymer. There are two types of non-crystalline
poly(oxymetheylene), the mobile and rigid amorphous parts. The glass transition of the former occurs in a
rather wider range of temperature: it starts at 180 K and could end at 265 K. The latter, under restraint due
to the crystallites, remains frozen up to the melting temperature.
1 INTRODUCTION
The glass transition temperature Tg of poly(oxymethy1ene) is
a longstanding problem.' The Tgs reported in the
literature2-' range from 188 to 270 K, just bridging the y and
p relaxation regions dynamic mechanically and dielectrically
observed. Hojfors et al. state that the p relaxation, at c.
270K, involving motion of long segments, can be considered
to be the glass transition.6 The editors of the Polymer
Handbook assigned 191K to Tg of this polymer2 and
Wrasidlo adopted 200K in his review." Nielsen" gave two
temperatures of 190 and 223 K with the latter in parentheses
in his table of Tg. Van Krevelen" also cited two ex-
perimental Tgs like 188/243K, comparing them with his Tg
of 223 K calculated from the additive contributions of given
structure groups.
The main problem of the discussion above seems to be that
the authors tried to find a specific temperature for Tg. The
assignments were done to highest possible precision, but
often without full explanation of the reasoning for a given
choice. Such efforts are not necessarily adequate, since the
glass transition occurs over a (time-dependent) temperature
range, and Tg the temperature of half-transition is only one
of several characteristics. One must also state the tempera-
ture interval and the overall change in the quantity used for
measurement, C, in our case. Such more detailed descrip-
tion is particularly necessary for semicrystalline polymers
which have often a broad range glass transition.
Recently Boyer' analysed the transition temperature data of
some debatable polymers including poly(oxymethy1ene). His
assignments for this polymer are, in the notation, 225K to
Tg(L) and 313-323K to Tg(U). Here, Tg(L) and Tg(U) are
the lower and upper glass transition temperatures. It is
assumed that Tg(L) arises from purely amorphous material,
while Tg(U) arises from amorphous material which is under
restraint due to the crystallites. Accordingly, Tg(L) corres-
ponds to the normal Tg of amorphous polymers and Tg(U)
often increases with an increase in crystallinity. Since his
assignments are different from those mentioned above to a
large extent and a two-step transition is assumed, it is
necessary to reanalyse the heat capacity data available in the
literature, which were not taken into account in Boyer's
analysis.
As has been demonstrated frequently since 1962,13the heat
capacity at constant pressure C, is a useful quantity which
enables us to discuss quantitatively the glass transition
behaviour. Discussions have already been published for
p ~ l y - ( e t h y l e n e ) , ' ~ ~poly(propylene)15
'~ and poly(tetra-
BRITISH POLYMER JOURNAL,VOL. 17, NO. 1 1985
Keywords
glass transition,
poly(oxymethylene),
heat capacity,
rigid amorphous,
mobile amorphous
fluoroethylene)." Similarly, the heat capacity data of
poly(oxymethy1ene) will be analysed below.
2 HEAT CAPACITY DATA
Heat capacity data, published by 1980, for linear macro-
molecues were critically assessed in nine serial articles." For
(100%) crystalline poly(oxymethylene), the best, selected
data for a temperature range 0-390K are known as the
recommended data." On the other hand, data for (com-
pletely) amorphous poly(oxymethy1ene) for a similar range
of temperature have not been reported so far. Here, the
results obtained recently on the molten and supercooled
poly(oxymethylene) and poly(ethy1ene oxide) will be used
for discussion.'' They can be expressed as
C:(POM)=46.51+0.0372 T (43GS40 K)
q(PEO)=67.85+0.0668 T (33W30 K)
Here, C, is given in the units of joule per mole of the
repeating unit per kelvin, the superscript a refers to the
amorphous state, POM and PEO are the obvious abbrevia-
tions of these polymers, and T is the temperature in K. Data
for the amorphous poly(ethy1ene) are taken from the second
article of ref. 17: C;(PE)=17.919+0.4325 T. Based on those
C, data of the crystalline and amorphous materials, data of
semicrystalline, commercial samples, Delrin and Celcon
measured by Dainton et aL2' and ourselves21 will be analy-
sed.
3 DISCUSSION
Figure 1 shows plots of Cp for the crystalline and semicrys-
talline poly(oxymethy1ene) against the temperature. The
former is the recommended data taken from ref. 18 and the
latter is the data of Dainton et al. for Delrin whose
crystallinity is assumed to be 67%. As has been well
documented, below the glass transition temperature, the
amorphous and crystalline polymers have almost the same
heat capacity. This is confirmed in this figure again. At
180 K, the two curves are seen to start departing. This is the
beginning of the glass transition. This transition looks
complete at 210K. At the mid-point, 195K, the C, jump of
2.4 J mo1-l K-l can be seen from the figure. For a number of
polymeric and non-polymeric organic materials, the C jump
at Tgis known to be 11.3 Jmol-' K-' per mobile unit.2PSince
there are two mobile units of methylene and oxygen in this
polymer, the expected jump for this particular sample is
2x11.3xthe amorphous fraction, i.e. 7.5 Jmol-'K-'. Accor-
1
 I I

35

-
Y
-
I

{ 30
-cp
3

25

)O 300 400
Temperature ( K )
160 200 240 I
Temperature (Kl Fig. 3 Heat capacity of the amorphous poly(oxymethy1ene) as pre-
dicted by the addition scheme of liquid heat capacity. POM3: poly(oxy-
Fig. 1 Plots of C,, for a semicrystalline (wc=67%) sample, Delrin,'" and, trimethylene); PEO: poly(ethyiene oxide); PE: poly(cthy1cnc); whose
crystalline poly(oxymcthylcne)" against temperature. Broken line: for a repeating unit is taken as methylene.
hypothetical sample having the amorphous fraction of 33%.

dingly, the heat capacity curve for Delrin should be like the
broken line drawn in the figure. However, the actual C, jump
is clearly too small for a full glass transition. This means that
only one-third of the amorphous materials in Delrin gets full
mobility at 195 K, while two-thirds remain frozen.
In Fig. 2 the heat capacity of liquid poly(oxymethy1ene) is
depicted. When the line is extrapolated to lower tempera-
ture, as is shown in a broken line, the proper heat capacity
deviation from that of the crystalline poly(oxymethy1ene)
can be seen at 26SK. This could be the end of the glass
transition. Since that is a rather long extrapolation, two
other estimates are presented in the succeeding figure in
support of the long straight-line extrapolation.
Poly(ethy1ene oxide) and poly(oxytrimethy1ene) are polyox-
ides which have lower melting temperatures. This character
eliminates a longer extrapolation. According to the additiv-
ity nature of the liquid heat capacity,18,l9 the heat capacity
of poly(oxymethy1ene) may be calculated by the simple
subtraction of the contribution of the methylene group, as is
shown in Fig. 3. Again, the end of the glass transition
temperature seems to be around 26SK. Hojfors et aL6
looked upon this temperature as Tg, although they under-
stood that the y1 relaxation at c. 205K involved motion of
short segments in disordered regions.
Next, the heat capacity at 26SK of Delrin and Celcon with
the different thermal treatments will be considered. In Fig.
4,those data are plotted against the crystallinity wc.Usually,
the linear crystallinity extrapolation allows us to estimate the
60
I I I
Mobile amorphous

70 0 Celcon
50 - Y
- -
I

.
0 Delrin
0
Y
E
-
I

-.
0 7
60 E
?
-
3 -
-
Y
f-- /-
3
-
I
0 40
5 50
-
3

2
Rigid amorphous \

40

3c
0 25 50 75
3c w c (%I

Fig. 4 Crystallinity extrapolation of heat capacity for semicrystalline

Temperature t K I
Fig. 2 Heat capacity of the amorphous poly(oxymethylene), C,; as
derived in ref. 19, and of the crystalline one, Ci. Broken line: linear
extrapolation of C.:
samples with various thermal treatments.2' Open circle: Celcon; closed
circle: Delrin, closed circle with pip; from ref. 20. Datum at w"=lOO%,
from ref. 18; upper datum at wc=O%, extrapolated from of
amorphous polyfoxymethylene).

z BRITISH POLYMER JOURNAL,VOL. 17, NO. 1 1985

 I I I 1
I Liq.POM . 1
Temperoture ( K 1
Fig. 5 Comparison of experimental and calculated heat capacities.
Thick line: data of Delrin by Dainton er al." Dotted line: C,, guessed for
0% crystallin sample. Dash-dotted line: C , calculated for samples with
w'=67% (33% mobile amorphous) and 80% (20% mobile and 13% rigid
amorphous).
heat capacity of the amorphous p ~ l y m e r . ' ~However,
,'~ the
value extrapolated here is much lower than that extrapolated
from the molten heat capacity.
This means that the crystallinity is not a structure parameter
adequate enough to describe the variation of the heat
capacity of poly(oxymethy1ene). Another structure para-
meter is necessary, which may be interpreted as the 'rigid
amorphous' part of the amorphous fraction. The other part
of the amorphous fraction can be renamed as the 'mobile
amorphous' part. The former, under heavy restraint due to
the crystallites, is supposed to have the same heat capacity
as the crystalline fraction, while the latter is nothing but the
normal amorphous material. It can be said from Fig. 4 that
at 265K, 43% of the amorphous fraction of these samples
corresponds to the mobile amorphous part, That is, roughly
speaking, the normal amorphous fraction of these samples is
only 20%.
In Fig. 5 the calculated and measured heat capacity curves
are compared with each other. The calculated curve for the
sample having the original crystallinity of 67% does not fit to
the experimental curve at all. However, when the mobile
amorphous part is set to be 20%, a reasonable fit can be
obtained up to the beginning of melting. This means that the
rigid amorphous part does not get any mobility up to the
temperature of melting of crystallites. Similar results are
obtained for samples having different crystallinities. This
view is supported by the fact that no obvious transition can
be seen on the experiment Cp- T curve between 250 K and
the premelting temperature.
BRITISH POLYMER JOURNAL,VOL. 17, NO. 1 1985
4 CONCLUSIONS
The glass transition of
methylene) starts at 180K.
semicrystalline poly(oxy-
There are two types of non-crystalline poly(oxy-
methylene), which are distinguishable between 180 K
and the melting temperature. They may be called the
mobile and rigid amorphous parts.
The mobile amorphous part of this polymer shows the
glass transition in a rather wider range of temperature.
A fractional, but noticeable glass transition occurs at
195K, which is in accord with the result of
d i l a t ~ m e t r y The
. ~ ~ full transition might be complete at
265 K, which is close to the p-transition temperature
dynamic mechanically observed.
The rigid amorphous part remains unchanged up to the
melting temperature. The two-step nature of the glass
transition, as observed on poly(ethylene), is not obvious
for poly(oxymethy1ene).
5 ACKNOWLEDGEMENTS
This work has been supported by the National Science
Foundation, Polymers Program, Grant No. DMR 8317097.
References
1 See, for example, Boyer, R.F., in Encyclopedia of Polym. Sci. and
Technol., Ed. Bikales, N.M., Suppl. Vol. 2, p. 746. New York:
Wiley and Sons.
2 Lee, W.A. & Rutherford, R.A., in Polymer Handbook, Eds
Brandrup, J. & Immergut, E.H., 2nd edn, 1975,111-139. New York:
Wiley-Interscience.
3 Kumler, P.L. & Boyer, R.F., Macromolecues, 1976, 6 , 903.
4 Privalko, V.P., Polym. Scz. USSR, 1976, 18, 1392.
5 Enns, J.B. & Simha, R., J . Macromol. Sci., Phys., 1977, B13, 25.
6 Hojfors, R.J., Baer, E. & Geil, P.H., J . Macromol. Sci. Phys., 1977,
813, 323.
7 Brew, B., Clements, J., Davies, G.R., Jakeways, R. & Ward, J.M.,
J . Polym. Sci., Polym. Phys. E d . , 1979, 17, 351. 8.
8 Blumberg, A.V. & Niemira, E.R., J . Polym. Sci., Polym. Phys. Ed.,
1979, 17, 1891.
9 Boyer, R.F., Br. Polym. J . , 1982, 14, 163.
10 Wrasidlo, W., Adv. Polym. Sci., 1974, 13, 1.
11 Nielsen, L.E., Mechanical Properties of Polymers and Composites,
1974, New York: Marcel Dekker.
12 Van Krevelen, D.W., with the collaboration of Hoftyzer, P.J.,
Properties of Polymers, 2nd edn, 1976. Amsterdam: Elsevier.
13 Wunderlich, B., J . Chem. Phys., 1962, 37, 1203. See also, J . Polym.
Sci., 1963, C1, 41.
14 Gaur, U. & Wunderlich, B., Macromolecules, 1980, 13, 445.
15 Grebowicz, J., Lau, S.-F. & Wunderlich, B., J . Polym. Sci. 1984, C71,
19.
16 Lau, S.-F., Suzuki, H. & Wunderlich, B., J . Polym. Sct., Polym.
Phys. Ed., 1984, 22, 379.
17 Wunderlich, B. etal., J . Phys. Chem. Ref. Data, 1981,10,89,119,1001,
1051; 1982,11,313,1065; 1983, 12,29,65,91.
18 The third article of ref. 17.
19 Suzuki, H. & Wunderlich, B., Makromol. Chem., in press.
20 Dainton, F.S., Evans, D.M., Hoare, F.E. & Melia, T.P., Polymer,
1962, 3, 263.
21 Suzuki, H., Grebowicz, J. & Wunderlich, B., J . Polym. SCL, Polym.
Phys. Ed., in press.
22 Wunderlich, B., J . Phys. Chem., 1960, 64, 1052.
23 Stehling, F.S. & Mandelkern, L., J . Polym. Sci., 1969, B7, 255.
3