The Torsion Pendulum in the Investigation of Polymers

J. HEIJBOER
Division of Technology for Society TNO
2600 AE Delft, The Netherlands

The early history of the use of the torsion pendulum in the

investigation of polymers is described together with the de-
velopment of dynamic mechanical testing at TNO. Examples
are listed of studies of structure-property relationships by
means of the torsion pendulum. Techniques using supported
samples are compared with those using unsupported samples,
particular attention being paid to the advantages and restric-
tions of torsional braid analysis (TBA). The comprehensive
application of TBA by Professor Gillham is reviewed; a few
TBA results are compared with our torsion pendulum mea-
surements. A rheologist’s view on the so-called liquid-liquid
transition ( T l l )in polymer melts, as observed by TBA, is
presented.

EARLY HISTORY OF THE TORSION PENDULUM
AND DYNAMIC MECHANICAL TESTING
s an introduction to the discussion of torsional braid
A a n a l y s i s (TBA), which has been so successfully de-
veloped and applied by Professor Gillham, I will first
present a retrospective view of the use of the torsion
pendulum, including some early uses of other dynamic
mechanical techniques for testing solid polymers.
The oldest reference I found to a torsion pendulum in
the investigation of polymers was a paper by Mooney
and Gerke (1)of the U. S . Rubber Co., who used it in the
testing of rubber. They attached a horizontal circular
disc to the lower end ofa vertical rubber strip clamped at
its upper end, and made the disc oscillate about a verti-
cal axis, measuring the oscillation period by noting the
passage of a mark on the edge of the disc.
The next example found, also concerning rubber, was
the instrument of Kuhn and Kuenzle (2), at the Univer-
sity of Basel, who as early as 1947 counterbalanced the
load on the sample and used different moments of inertia
by applying different discs between the suspension wire
and the sample. The motion was traced by means of a
beam of light reflected by a mirror.
Application of the torsion pendulum to plastics began
in the early fifties. In the USA, Nielsen and Buchdahl
(3-6)of Monsanto were the first to publish an investiga-
tion of plastics with a torsion pendulum. Their first
equipment was built according to Kuhn and Kuenzle’s
principles. As early as 1953 (6), they investigated four
important topics using a torsion pendulum: the effect of
plasticization on the glass transition of PVC; the be-
havior of‘two-phase systems (high-impact polystyrene),
The first major development in Europe was made by
Schmieder and Wolf (8-lo), of BASF, who used the
equipment shown in Fig. 1 . They applied Mooney and
Gerke’s principle by using a sample loaded with an
oscillating disc, but determined the oscillation period by
means of Kuhn’s optical method. In 1953, they pub-
lished curves of t h e t e m p e r a t u r e - d e p e n d e n c e of
modulus and damping (as the logarithmic decrement A
= T tan 6) for about 50 polymers. They also paid atten-
tion to the frequency-dependence of these properties.
As their data were more accurate than those of Nielsen,
et al., they were able to define a secondary maximum
more precisely, e.g., that of poly(methy1 methacrylate)
(9). Later, BASF investigators extended the frequency
range of their mechanical measurements to the ul-
trasonic region (11).In 1957, Thurn, Schmieder, and
Wolf (12) published a spatial representation of the
logarithmic decrement of high and low density polyeth-
ylene from 1 to lo’ Hz and from -150 to +150°C. This
representation was reproduced in a survey paper by
Woodward and Sauer (13). (A representation of Young’s
modulus and damping of a rubber over so broad a fre-
quency range had already been given in 1950 by A. W.
Nolle (14)of the Massachusetts Institute ofTechnology.)
-Specimen
,Thermal
locket

the effect of crystallization on the modulus of polyethyl-

ene, and the minimum in the damping of plastics above
their glass-transition temperature, To. Later, Cox, Isak-
son, and Merz (7) correlated t h e position of this Fig. 1 . Schematic druuing of Schmieder und Wolfs torsion
niiniinum in polystyrene with its molecular weight. pendulum.

664 POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, Vol. 19, NO. 10
 The Torsion Pendulum in the Investigation of Polymers
At TNO we have from the outset been interested in
measurements over a broad frequency range. For this
purpose, Dekking (15) developed two pieces of equip-
ment, shown schematically in Fig. 2. For the torsion
pendulum we took a counterbalanced system. The
movement of the arm was recorded by means of an
electric spark striking on a thin strip of paper attached to
a rotating drum. By using dfierent moments of inertia,
we covered the frequency range from about 0.3 to 3 Hz.
For the frequencies from 200 to 3000 Hz we used the
same specimen that was tested with the torsion pen-
dulum, but now suspended horizontally by two loops of
rayon threads at its nodes. Small fragments of a razor
blade were glued to the end of the specimen; one end
was excited electromagnetically, and the movement of
the other end recorded. The frequency was varied by
means of an audiofrequency oscillator. We thus ob-
tained Young‘s modulus from the resonance frequency
of the sample, and the losses from the width of the
resonance peak. As a rule, we measured four or five
modes of vibrational harmonics. Using this equipment,
we studied the effect of chemical modifications on the
secondary loss peak of poly(methy1 methacrylate) (15-
17), and were able to show that this loss peak is due to
the rotational motion of the methoxycarbonyl side group
being hindered by adjacent methyl groups on the main
chain.
In an early stage, the thermostat of our flexural vibra-
tion equipment could only be heated and not cooled. At
that time, J. Seffelaar of our Institute observed that, at
room temperature, the losses of a copolymer of methyl
methacrylate and cyclohexyl methacrylate showed a
tendency to increase at the upper extreme of the
measuring range then available. This finding prompted
us to repeat the experiment in the cold (2OC) outside,
and in fact we found that the losses at high frequencies
had increased considerably. This experiment was the
beginning of a long line of research into the motion of
saturated rings incorporated as side groups into amor-
phous polymers (16-22). One result of this research was
our determination of the energy barrier opposing the
chair-chair transition of the cyclohexyl group (16), about
four years before it was determined by NMR (23). Our
result for the energy of activation, 11.5kcal/mole, is in
good agreement with what is probably the best experi-
mental value available for cyclohexane, and obtained by
NMR, viz., 11.2 kcal/mole (24).
A further development at TNO was the extension by
Waterman (25, 26) of the measuring range to higher
frequencies, viz., the kHz and the MHz range.
-.
I
T
i I
rorsiond free v b r o i m Flexura/ forced wbrohon
Fig. 2. Schematic drawing of the originul apparatus for vibra-
tion measurements at TNO.
POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, Vol. 19, NO. 10
In the course of many years, our torsion pendulum
was improved considerably by Drent, Nederveen,
Schwippert and van der Wal(27). With some modifica-
tion, the same equipment can also be used for torsional
creep measurements, which extend the lower limit of
the effective frequency range to Hz (28). The
equipment is provided with a special thermostat whose
temperature can be rapidly and accurately adjusted (29).
Our fully automated version of the torsional creep in-
strument became available and proved to be very useful
in the investigation of physical aging (30).
The standard specimens we use are 7 mm wide and
3.5 mm thick. Fortuitously, at this ratio of width-to-
thickness the clamping correction is a minimum (31).
Some results of our torsional pendulum mea-
surements on commercial polymers are presented in a
review paper (32). A recent paper (33) on the charac-
teristics of secondary maxima contains a survey of our
dynamic mechanical measuring methods. A more de-
tailed description of our present measuring techniques
is given by Struik (30).
Apart from Monsanto, BASF and TNO, some other
laboratories have as early as the fifties published about
the dynamic mechanical properties of polymers below
the glass transition. The torsion pendulum was applied.
at the Technische Hochschule, Aachen, by Jenckel and
Illers (34-39), and at DuPont by McCrum and Sinnott
(40-43). At Princeton University, Maxwell used a rotat-
ing bar to measure the mechanical losses of poly(methy1
methacrylate) (44). At an early stage, the vibrating reed
technique was extensively applied at the Plastics Re-
search Laboratory of ICI by Willbourn, Deutsch, Hoff,
Reddish and Robinson (45-48).
At the Technisch-Physikalische Bundesanstalt in
Braunschweig (Germany), Oberst, Becker and Kop-
pelmann made very important contributions to the
study of the dynamic mechanical properties of hard
plastics over a broad frequency range (49-52). At
Pennsylvania State University, Kline, Sauer, and
Woodward (53-55) studied semicrystalline polymers by
flexural resonance vibration of a rod (56).At the Univer-
sity of Pisa, Baccaredda and Butta (57)also studied semi-
crystalline polymers, but by longitudinal vibration of a
bar.
To conclude our survey of papers on the dynamic
mechanical studies of hard polymers, already published
in the fifties, we should mention also the early contri-
butions of Fukada (58) and of Iwayanagi and Hideshima
(59, 60) on poly(methy1 methacrylate) and poly(methy1
acrylate).
It has been our intention to mention only those labo-
ratories which made early contributions to the determi-
nation of the dynamic mechanical properties of hard
polymers. We have therefore omitted the very impor-
tant work by Ferry and coworkers at Madison (61), since
this is especially concerned with the glass transition.
A complete survey of the further investigations of
polymers by torsion penduIum would be far outside the
scope of this paper. Instead, we present a list of subjects
(Tuble 1 ) investigated by torsion pendulum and illustrat-
665
 J. Heijboer
Table 1. Subjects of Torsion Pendulum Research shape of a V, is fixed at the outer ends of its legs, and
Reference coated by a thin layer of the material to be investigated.
The coated filament is placed in a vacuum and made to
1. Plasticizers (5, 9, 38) vibrate. The method of attaching the V-shaped filament
2. Crystallinity, annealing (41, 62-68)
has the advantage that its apex is constrained to vibrate
3. Crosslinking (10, 69-71)
4. Polymer blends (72-82) in a single plane, and so cannot describe Lissajous
5. High-impact homopolymers (83-87) figures. The amplitude of vibration of the apex decays to
6. Block copolymers (88-92) half its initial value in a certain time. This “half time” is
7. Interpenetrating networks (93)
measured, and is inversely proportional to the loss
8. Side groups (19-22, 43,94-97)
9. Low-molecular weight additives (86, 98-103) modulus (in extension) of the coating. Thurn presents
10. Antiplasticization (104-107) data for, among others, PVC and PE.
11. Physical aging (30) A rather complicated method for dealing with tor-
sional vibrations of a coated strip is described by Inoue
ing its versatility. The references listed are intended as and Kobatake (121).
examples and are not exhaustive. The most successful technique for measuring sup-
The extension of the measurements down to liquid ported samples is no doubt that which is now called
helium temperatures (42, 96, 108) has essentially torsional braid analysis (TBA). The first TBA instrument
broadened the scope of the torsion pendulum. A device was developed at American Cyanamid, Stamford,
has been developed to perform torsion pendulum mea- Conn., by Lewis and Gillham (122-125). Later, when
surements at pressures up to 1500bar (109). The torsion Gillham was at Princeton University, he and his co-
pendulum can also be used to measure fatigue proper- workers developed the device into a highly sophisti-
ties (110). cated instrument (126-132). An extensive review paper
In addition, the instrument is suitable for studying (127)dating from 1972, gives as many as 49 references to
other materials: a recent paper (111)describes a ver- torsional braid analysis, and since then the rate of ap-
satile apparatus for measurements on metals. pearance of papers referring to the technique has still
Roller and Gillham (112) give a survey of equipment increased. In many applications TBA has superseded
for dynamic mechanical testing, including equipment the conventional torsion pendulum.
that is commercially available. An older, more detailed, The apparatus is shown schematically in Fig. 3. Its
survey ofautomated equipment for the determination of basic principle is the use of a loose glass braid made from
mechanical relaxation has been given by Becker (113). three or six yarns containing a total of about 3600 fila-
In comparison with other dynamic mechanical ments, each about 7 pm thick. The braid is either soaked
equipment, the conventional torsion pendulum is un-
surpassed in accuracy and reliability: if the test bars are 1- D R ! V E G E A R T R A I N

large enough, the absolute modulus values can be ob-

tained with an accuracy of at least 2 percent. Other
dynamic mechanical equipment may yield absolute
modulus values which can be in error by 50 percent
(114).
The classical, accurate, version of the torsion pen- SUPPORTING ROD

dulum with free vibration has the disadvantage, how-

ever, that its operation is rather laborious and time- TEMPERATURE
CONTROLLED
consuming, particularly when several moments of iner- I
i ENCLOSURF
tia are successively applied to obtain data at a number of
frequencies.

MEASURING TECHNIQUES USING SUPPORTED

SAMPLES
L SPECIMEN

When the amount of material available is small, or

when it cannot support a load, the conventional torsion
pendulum cannot be used. It is, therefore, not surpris- POLARIZER

ing that techniques for measuring supported samples

ATMOSPHERE
have been developed from the outset. PORT VACUUM
The easiest method, from a practical point of view, PHOTOTUBE

uses flexural vibrations of thin metal strips, coated on

one side with the material to be investigated. The
AND DATA
method and theories have been described (115-118).
They are more suitable for determining the damping
than the modulus and are of practical importance for
noise-abatement systems (119).
Thurn (120) has described an interesting variation of Fig.3. Schemutic drawing of Gillham’s automated torsion pen-
the method in which a quartz filament, bent into the dulum. Insert: part uf the braid and its attuchment to the eyelet.

666 POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, YO/. 19, NO. 10
 The Torsion Pendulum i n the lnvestigation of Polymers
in a polymer solution, or dipped in a polymer melt, or
dipped in a liquid that reacts to form a crosslinked
polymer. The braid soaks up the liquid by capillary
action. The impregnated braid is used as a specimen to
be tested in a sensitive torsion pendulum. To this end it
is provided with eyelets, by the upper one of which it is
clamped to a supporting rod and by the lower one to an
extender rod, the two rods protruding from the oven of
the torsion pendulum. As the braid has a small cross-
section (diameter about 0 . 5 mm), only a small moment of
inertia can be applied. The braid is kept in a vertical
position by a magnetic stabilizer at the lower end of the
extender rod. The torsional motion is recorded electro-
optically by the rotation of a horizontal polarizer disc,
whose transmission is a linear function of the position
angle. By virtue of this ingenious system, the specimen
can make well-defined undisturbed motions in spite of
the low moment of inertia. Moreover, this motion can be
recorded electronically and is amenable to processing by
a computer. The logarithmic decrement, A = m tan 6,
and the period P of the vibration are calculated. P-’ is
proportional to the rigidity G, of the system polymer-
braid. Both A and G, can be plotted on logarithmic
scales as a function of temperature or time.
One might wonder why torsional braid analysis has
taken such a wide scope. First, the method has a number
of inherent advantages over unsupported techniques.
There is no doubt, however, that the inventiveness and
perseverance of Professor Gillham and coworkers have
greatly contributed to the success of the technique.
Particularly their early success in fully automating the
instrument has promoted its practical application.
The advantages ofTBA are listed, together with a few
restrictions, in Table 2 and will be discussed below.
First of all, the measurement requires only a small
amount of material: a few mg. This is, of course, an
advantage in investigations of exotic materials. The clas-
sical torsion pendulum requires an amount of material in
the order of 1 g.
A second advantage is the simple way in which the
polymer can be converted into a suitable specimen from
a solution, melt or suspension. No compression molding
or machining is required.
By TBA, measurements through transition ranges can
be made in a simple fashion. In the glass transition range
Table 2. Torsional Braid Analysis
Advantages
-The amount of material needed is small
-The material can be applied from a solution, melt, or suspen-
sion
-Measurements can be made through majortransition ranges,
even into the melt
-In situ monitoring of chemical reactions is possible
-The sample rapidly approaches equilibrium with the sur-
rounding atmosphere
-The supporting system has a favorable geometry
Restrictions
-The physical quantities obtained are not absolute
-“Modulus curves are squashed non-linearly”
-It is difficult to apply different moments of inertia
POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 7979, Vol. 19, No. 70
the conventional torsion pendulum needs additional
stiffnesses, owing to the high damping. Crystalline
polymers cannot be measured through their entire melt-
ing range by the conventional torsion pendulum, be-
cause in that range they will not support sufficient loads.
In my opinion, the most important feature of TBA is
the possibility it affords of following chemical reactions
in situ. Examples are the gelation of a crosslinking sys-
tem starting from the liquid, and the degradation of a
high-temperature polymer until it completely disinte-
grates.
In this connection it is worth mentioning that the
small size of the sample used in TBA allows for ready
removal of volatiles and for rapid thermostating. The
sample approaches thermal, physical and thermal
equilibrium in a shorter time than does the larger sam-
ple of the conventional torsion pendulum.
One point remains to be discussed: the favorable
geometry of the special supporting system used in TBA.
The frequency of flexural vibration of a coated quartz
filament is only slightly influenced by the modulus of the
thin coating and, hence, this vibration method is unsuit-
able for the determination of the storage modulus of the
coating. By contrast, the shear deformation of a loosely
woven impregnated braid depends much more on the
polymer than on the glass, so that the total stiffness in
shear is determined mainly by the polymer. This situa-
tion changes only when the polymer has a very low
stiffness, as, e.g., a liquid polymer.
As far as the determination of the modulus is con-
cerned, the torsional braid also has .a more favorable
geometry than the impregnated strip of blotting paper,
which has been applied by Koleske and Faucher (133-
135). This does.not detract from the suitability of the
latter method for the determination of the glass transi-
tion temperature of low molecular weight compounds,
because the glass transition is accompanied by a very
large decrease in modulus.
The supported technique used by Fava and Chaney
(136), in which the polymer is encapsulated in a rigid
matrix of a phenolic resin, is suitable only for the location
of loss peaks and does not permit the determination of
the storage modulus.
We conclude that, among the supported techniques,
TBA is particularly suited to the observation of changes
in modulus with temperature. Nevertheless, it should
be borne in mind that the method gives only relative
values and that the ratio of the relative to the real shear
modulus is not a constant. As Gillham puts it (Ref. 127,
p. 165) “the relative rigidity curves are not quantita-
tively relative and are squashed non-linearly”. This is
particularly evident in the glass transition of amorphous
polymers: going from the glassy to the rubberlike state,
the modulus decreases by a factor of the order of 1000,
whereas TBA yields only a factor of about 10 (compare,
e.g., the curves for the poly(methacry1ates) in Ref. (137)
and Ref. (138) with those in Ref. (17) or Ref. (32); see
also, Figs. 6a and 6b).Therefore, considerable caution
should be exercised in drawing quantitative conclusions
from TBA data on G’ or the loss modulus G” = G’ tan 6
(138, 139). As we will see in the section on the liquid-
667

liquid transition, the situation for polymer melts is not
yet settled. In the glassy region the relative modulus-
temperature curve is much less distorted. Hartmann
and Lee (140)maintain that in this region the multiplica-
tion factor between the relative and the absolute
modulus is a constant. However, a closer examination of
their Fig. 6 reveals that this conclusion is a rather op-
timistic one: in the temperature range from -160 to
+20°C, where the absolute modulus decreases by 45
percent, the multiplication factor already increases by
about 8 percent.
Another restriction of the torsional braid method is
due to the fact that the frequency changes with tempera-
ture, owing to the changing stiffness. This, however,
applies to most conventional torsion pendulums. To
obtain data at a constant frequency, one has to apply
different moments of inertia and to interpolate the re-
sults to a constant frequency. TBA usually gives data
near 1 Hz.
For a further comparison of TBA with the torsion
pendulum and with the Rheovibron, we refer to Boyer
(141). In this connection it should be mentioned that, in
spite of considerable effort (142-144), absolute modulus
values obtained by Rheovibron are less reliable than
those obtained by the conventional torsion pendulum
(114). The Rheovibron and the torsional braid instru-
ment are very suitable for finding the exact values of
transition temperatures.
EXAMPLES OF THE APPLICATION OF
TORSIONAL BRAID ANALYSIS
In the foregoing, I have stressed the great versatility of
TBA. The number of papers describing the technique
and its results has already exceeded 100.
I shall now proceed to present a general survey of the
topics tackled by Professor Gillham and coworkers by
means of TBA, and to compare a few of their results with
our own torsion pendulum measurements.
To start with epoxy-crosslinking systems: Gillham and
coworkers (127, 145-151) have increased the under-
standing of these systems by showing that in isothermal
curing two characteristic temperatures can be observed:
an upper temperature, above which the material only
gelates and does not vitrify, and a lower temperature,
below which the material only vitrifies. Between these
temperatures the two processes, gelation and vitrifica-
tion, are seen as separate loss peaks in the time-loss
curve during curing.
The influence of catalyst content on phase separation
in rubber-epoxy systems can also be understood from
results of TBA. At this symposium, the subject of
crosslinking systems will be introduced by Professor
Gillham himself (151).
TBA has proved to be particularly useful in the study
of the high-temperature polymers. The classical exam-
ple is polybenzimidazole (127, 152). Extensive investi-
gations have been made into the effect ofchemical struc-
ture on the properties of polyimides (127, 153-155).
The formation of the tough poly(chromium I11
triphosphinate) from the brittle poly(chromium I1
biphosphinate) could also be followed by TBA (156). The
668
J. Heijboer
effect of various fluorinated side groups R on the melt-
ing, the glass transitions and the subglass transitions of
polyphosphazenes, [NPR2],, have been studied on
homopolymers, copolymers, and polymer mixtures
(157, 158).
Roller and Gillham (127, 159-162) have made a very
extensive study of silicon-based high-temperature elas-
tomers, containing carborane cages (CB5H5C and/or
CBIoHIoC)in their polymer chain. They studied glass
temperatures, crystallization and thermal stability in
nitrogen and air. This investigation neatly illustrates the
wealth of information that- can be obtained on small
amounts of exotic polymers by TBA. These high-
temperature elastomers, and also the polyimides, often
crosslink at high temperatures. This crosslinking is
unambiguously revealed by TBA. So the technique is
particularly suitable for selecting systems having op-
timum high-temperature properties.
TBA has demonstrated an unexpected relationship
between glass temperature and structure in two series of
polyolefins, viz.
CH3
+(cH~)nJ-~rn
I
R
with n = 1, 2, and 3, and R = CH3 or C2H5 (127, 163).
Figure 4 assigns the T , values obtained by Martin and
Gillham to the polymers in question.
It is very surprising that in both series an increase i n n
from 1 to 2 is accompanied by an increase in T,; one
would, by contrast, expect a greater flexibility of the
main chain for n = 2. However, when the number of
interceding methylene groups is increased from two to
three, T , decreases as expected. To explain t h e
maximum in T , for n = 2, Martin and Gillham intro-
duced the concept of intermolecular interlocking. In the
first member of each series, the side groups shield the
main chain from the approach of neighboring chains; for
n = 2, there is just space enough for two main chains to
T IKI OF POLYOLEFINS
253 I2681 2 78 258
I296 I
Fig.4 . Glasr temperatures T,, (in K ) of polyolejins, determined
by TBA and by the torsion pendulum ( i n parentheses).
POLYMER ENGINEERING AND SCKNCE, MID-AUGUST, 1979, Vol. 19, No. 70
 The Torsion Pendulum in the Investigation of Polymers
fit nicely together at contact points between the side
groups, whereas for n = 3, there is more space left,
resulting in a higher mobility. Martin and Gillham argue
that intermolecular interlocking can also manifest itself
in a lower density.
The rise of T , (for n = 1 and n = 2) found when R =
methyl is exchanged for R = ethyl is also unexpected.
However, it does fit the concept of interlocking: the
lower symmetry of the chain favors interlocking.
At TNO we measured by torsion pendulum the first
number of the second series: poly(2-methylbutene-1),
and also the corresponding polymer with an n-propyl side
group: poly(2-methylpentene-1) (164). Our T , values are
included (in parentheses) in Fig. 4 . The storage and loss
moduli are given, as functions of temperature, in Fig. 5 .
Considering the greater flexibility and length of
n-propyl, we were quite surprised to find an increase in
T , when it was substituted for ethyl. This curious finding
may perhaps be explained by the interlocking concept:
n-propyl groups protrude farther from the main chain,
which therefore interact more strongly with neighbor-
ing chains. The puzzling fact that the polymer with the
lower modulus in the glassy state has a higher T , points
in the same direction: interlocking reduces the density
and, hence, the modulus in the glassy state.
Closely related to the concept of interlocking is that of
the sweeping volume (32), i.e., the volume required for
the motion of the main chain parts at the glass transition.
X G'
0 G"
7.7 Hz
los
10'
10'
lo6
I - 700
- 0
e,"c
100
Fig. 5 . Storuge niodulus in sheur, G', and modulus, G", ut
Loss
about I H z as a f u n c t i o n of temperature, 8, of poly(2-
methylbutene-1) und pol!y(2-methylpentene-l).
POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, Vol. 19, No. 10
This concept explains why bulky stiff side groups will
cause an increase of T,, whereas long flexible side
groups, which can easily accommodate themselves in
the available space, will cause a decrease of T,. The loss
curves in Fig. 5 show no appreciable increase in the
damping in the region of -180°C when R = ethyl is
substituted by R = n-propyl. This indicates that the
n-propyl group has a rather low mobility. When the side
group is further lengthened, the effect of flexibility will
dominate, and T , will decrease.
Returning to Gillham and Martin we note that these
investigators, in cooperation with Hiltner and Baer of
Case Western Reserve University (165), have measured
the two series of polyolefins mentioned above down to
liquid-helium temperatures to study their secondary
loss peaks. They attributed the loss peaks observed at
about - 110°C for n = 2 and 3 to local main chain motion,
and the one observed near - 160°C to the motion of the
ethyl side group.
Other polyhydrocarbons studied by TBA are 1,5-
polypentamers (166), -(C HZCHzCH2CH=C H-)n.
These have low T,'s, viz., - 109 and -95"C, depending
on ratios of cis- to trans-isomer, which are 98 to 2 and 18
to 82 respectively. The polymer with the higher trans
content t e n d e d to crystallization. Poly(2,5-
norbornadiene) (167)has a very high T,, viz., 320°C and
a broad low-temperature loss region, with peaks at about
-150°C and about -60°C.
Poly(ethy1ene carbonate),
--(CHZ--CHz--0<--0-),,
II
0
has a T , of 22"C, poly(propy1ene carbonate),
-(CHz--CH-0-C-0-),, of 41°C (168). The glass
I
CH3
II
0
temperature is raised by the introduction of the methyl
side group. This is in contrast with poly(ethy1ene oxide)
(T, = -57"C), compared with poly(propy1ene oxide) (T,
= -62°C) (169), but agrees with the T,'s of polyethylene
and polypropylene. Poly(ethy1ene carbonate) and
poly(propy1ene carbonate) both have a pronounced sec-
ondary maximum near -85"C, which for the former
polymer is about twice as high as for the latter.
Polymethacrylates of various tacticities have been ex-
tensively investigated by TBA (127, 137, 138). Isotactic
poly(methy1 methacrylate) (PMMA) has a much lower T ,
than the syndiotactic polymer, the difference being
about 70 K. For poly(t-butyl methacrylate (PtBuMA)
this difference is very small, viz., only a few degrees.
The secondary loss peak of PtBuMA lies at the same
temperature as that of atactic PMMA, but is much
lower. The secondary loss peak of isotactic PMMA is
much lower than that of atactic PMMA.
To explain this difference in T , of the PMMA's, Gill-
ham again invokes the interlocking concept: in fact of
the two polymers isotactic PMMA has the higher den-
sity and the higher modulus in the glassy state (17), and
the lower To.
Figure 6 compares results of torsion pendulum (17)
and torsional braid measurements (138)on atactic and
isotactic PMMA. The curves ofFig. 6b are derived from
669
 3. Hegboer
TP 1Hz
Figure 6 shows that the p-maximum measured by
___ o t o c t PMMA TBA is about 25 percent lower than that measured by
- r s o t a c t PMMA
the torsion pendulum; the difference is due to the glass
content of the torsional braid. This relative lowering of
the damping is fairly constant below the &maximum,
but strongly increases in the region of the glass transi-
tion, where it amounts to a factor of 3 or more. In
addition, the relative modulus curve obtained by TBA is
distorted considerably in the glass transition region; the
modulus decreases by only about one decade rather than
3 decades.
Another interesting structure-property relationship
that has been studied by TBA (170-171) is the effect of
fluorocarbon groups R , and Rz in bibenzoxazole poly-
mers of the formula
r 1

In the glassy region, these polymers show two sec-

ondary loss peaks, which were assigned to a specific
group: in the R , position -(CF&- gives rise to a
T/KI
maximum at about -35°C and -(CF2)20(CFz)sO-
TOO 200 300 LOO 5 00 (CF&- to one at about -8O"C, in the Rz position
-(CF&- gives a maximum at about -130"C, and
(0)
-(CFJIor 40(CF2)20CFz- one at about - 150°C.
TEA Ether oxygen enhances the flexibility of a -(CFZ)n-
- _ _ a t a c t . PMMA
group, and the motion of groups in the R1 position is
__ i s o t a c t PMMA
I more restricted than that in the Rz position. It is remark-
able that a group as long as 11 chain atoms should still
experience such a strong influence of the linkages at its
ends on its mobility: the two positions R , and Rz cause a
difference of about 60 K in the temperature of the loss
peak. In their mobility, the fluorinated side groups in
the polyphosphazenes (158)are more like the groups in
position R z than like those in position R1, their loss peaks
lying in the region of -150°C to -180°C.
We now conclude this survey of structure-property
relationships studied by Professor Gillham and cowork-
ers by means of TBA, by mentioning that the equip-
l o 7 - - 01 ment is also suitable for measuring the effect of other
atmospheric environments, e. g., humid air, on the
dynamic mechanical properties of polymers. Examples
are the study of the effect of water on polyimides (127,
154, 172), PMMA (131) and polypeptides (173). The
effect of water on polypeptides is particularly strong, as
is shown by the interesting paper by Hiltner and Baer
(174), presented at this symposium.

I
100 200 300
__j

LOO
TlKl

500
(6)
Fig. 6. Modulus, G', and damping, tan 8, as a function of tem-
perature, T , of atactic and isotactic polyimethyl methacylate).
a. A t 1 H z , as determined b y the torsion pendulum. b. As deter-
mined b y torsional braid analysis (relative ualues).
Figs. 1 and 3 of Ref. (138). The modulus values are only
relative ones. The values of tan 6 have been obtained by
dividing the absolute logarithmic decrement by T.
For literature on TBA before 1972, we refer to the
extensive survey paper by Gillham (127). The examples
given above clearly show how successfully Professor
Gillham and coworkers have applied their technique to a
variety of subjects.
THE LIQUID-LIQUID TRANSITION
As early as 1963, Boyer (175) drew attention to evi-
dence of a transition in melts of polymers at a tempera-
ture above their glass transition. This he called the
liquid-liquid transition, T I [ . An example observed in

670 POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, Vol. 19, NO. 10
 The Torsion Pendulum in the Investigation of Polymers

torsion pendulum measurements was the separate loss P5 , M n - 20,200

peak in styrene-butadiene rubber near 280 K .

TBA clearly showed a loss peak in melts of mono-
disperse polystyrenes, and this observation prompted a
series of papers by Gillham, Boyer and coworkers on
studies of Ttt by means of TBA (176-183). They investi- melt
gated monodisperse polystyrenes (176), mixtures of
monodisperse polystyrenes (177), polystyrenes with
plasticizer (178, 179) and block-copolymers of styrene
(180, 182)with other monomers. A linear correlation has
t
been found between T t l and M;’, the inverse of the
number average molecular weight. Evidence for a
liquid-liquid transition has also been found in other
ways, e. g., by DSC, by rheological measurements and
measurements of solubility and diffusion (181, 183-186).
In addition to polystyrene, many other polymers show
evidence of a Ttt-transition (181). Gillham and Boyer
(181) give a general review.
In this paper, I will restrict myself to the rheological
aspects of Tu. I will show how data obtained by TBA
compare with those obtained with a concentric-cylinder
viscometer, which measures physically well-defined
magnitudes. Den Otter (187) of TNO has developed a
T. K
very sensitive concentric-cylinder viscometer, which
enabled us to measure even the loss modulus ofcetane at 350 LOO L 50 5

25°C with an accuracy of 5 percent. By means of this F i g . 7 . Loss modulus in shear, G“,as a function of temperature,
instrument we hoped to obtain interesting information T , at three frequencies f o r monodisperse P S M , = 20,200, de-
termined by a concentric-cylinder uiscometer, compared w i t h
on the liquid-liquid transition. Den Otter (188) and the relative modulus, G‘lrvl,obtained b y torsional braid analysis
Wales (189) have published data on polystyrene (PS) and of the same polymer.
polyethylene melts, obtained with the instrument.
We would have preferred to compare tan 6 values of
To enable a good comparison to be made with data
the torsional braid with tan 6 values of the polymer melt,
obtained by TBA we investigated an atactic
but the latter values were not available. However, a
“monodisperse” PS of Pressure Chemical Co., M , =
comparison could be made for two polymers with an M ,
20,200, which had also been measured by Stadnicki,
of about 200,000, viz., polystyrene S 111 of Dow Chemi-
Gillham and Boyer (176). Mr. J. L. B. d e Groot at TNO
cal Co., M , = 214 x lo3,M J M , = 1.04, which has been
kindly performed the measurements. He immediately
ran into serious dimculties. As a rule, we fill our vis- measured by den Otter (188), and the very similar PS of
Pressure Chemical Co,, with M , = 193 x 103, which has
cometer by machining a cylindrical sample into a tube,
which exactly fits the gap of the viscometer. However, been measured by Stadnicki, et al. (176). From our
this polystyrene sample proved to be too brittle to original data on G“ and G ‘, we calculated the tan 8 values
machine. On the other hand its melt was too viscous to of PS S111; these are shown in Fig. 8. Figure 9 shows
fill the viscometer perfectly and tenaciously retained that the data could be reduced surprisingly well to a
some bubbles of air. We were therefore able to obtain master curve by horizontal shifts.
accurate data only for the loss modulus in shear, G”, but Figure 10 shows the shift factor, log uT,(with respect
not for the storage modulus, G’. G” was measured at 9 to 413 K) plotted as a function of the inverse of the
temperatures and 3 frequencies. The reproducibility of
O S S l l l , M n .2 1 L x l o 3
the results was checked by repeating a measurement at
an intermediate temperature after completion of the A
series of measurements at increasing temperatures. The
results are given in Fig. 7 , together with data on the
relative loss modulus, calculated from curves of the
relative rigidity and the logarithmic decrement in Fig.
12 of Ref. (176). The loss modulus of the polymer melt
can be seen to decrease sharply with temperature with-
out showing any clear-cut indication of a plateau or a
maximum. By contrast, the loss modulus of the combi-
nation of support and polymer shows a Tll maximum at
420 K, 0 .3 Hz; at higher temperatures it levels off. From
this it follows that the G&l obtained by TBA dfiers Fig. 8 . Tan 6 as a function of circular frequency w at three
completely from the true G” of the polymer melt. temperatures, f o r P S S111.

POLYMER ENGINEERING AND SCIENCE, MID-AUGUST, 1979, Vol. 19, NO. 10 67 1


Fig. 9. Tun 6us u function of reduced frequency waT,ut 413 K f o r
PS s111.
+ PS M n = 211.000 “f,xed fluid
PS M, =20.200
0
logo, I 173KI
/ Fig. 11. Tun 6 und G” of PS M , = 214,000, determined by a
/ coticentric-cylinderviscometer, compared with tan Sof PS M , =
“/+
,o
/ 194,000, obtained by torsional braid analysis.
22 23 24 25
Fig. 10. Shiftfuctora,asu function ofli?’fortan SofPS S111,
M , = 214,000, and f o r G” of PS M , = 20,200.
absolute temperature, T . The figure also shows the shift
factor for G” vs o for the PS with M , = 20,200. Interest-
ingly, the two shift factors practically coincide. The
slope of the curve is a measure of the activation energy of
deformation. According to Gillham and Boyer, in the
whole temperature range shown, the PS with M,, =
214,000 is expected to be what they call a “fixed fluid.”
On the other hand, the PS with M , = 20,200 would be a
“fixed fluid’ at low temperatures, and a “true liquid” at
high temperatures; the expected transition temperature
is indicated by a dashed vertical line. If this were true,
one would expect a change in the activation energy at
the transition temperature. However, our data reveal no
such change.
As the measurements on PS S l l l had been taken at
large temperature intervals, it was impossible to draw a
detailed curve of tan 6 (at a single frequency) as a func-
tion of temperature. However, with the aid of the mas-
ter curve (Fig. 9) and the shift factor (Fig. 10) we could
construct a reliable tan 6 vs T curve for a given fre-
quency. The curve for 0.3 Hz is given inFig. 11 together
with that oftan 6 for PS M , = 194,000 obtained by TBA.
(The latter data have been calculated from Fig. 14 of Ref.
(176)).Once more it is seen that the torsional braid gives
no reliable picture of the dependence of the losses of a
polymer melt on temperature: tan 6 (TBA) increases by
only about half a decade over a temperature range of 50
K, whereas the real increase is more than 1% decades.
672
J. Heijboer
PS M , z 200,000
G“IPol
ton 6
10
1
ton 6
t
7
-
\-
\
~ ( K I \
\
07
350 LOO L50 500
Our data are in agreement with Nielsen’s ideas (190)and
with the old measurements of Cox, Isaksen and Merz
(7).
Figure 11 also shows the GI’ vs T curve of PS S l l l at
0.3 Hz. This curve has been obtained from the reduced
loss modulus G! together with the pertinent shift factors
(188). G! vs log w shows a flat maximum, as is usual for
monodisperse polystyrenes with a molecular weight
higher than a critical value, M,. This maximum indeed
produces a corresponding maximum in the G” vs T
curve, which is shown in Fig. 11. However, it is difficult
to assume acorrelation between the latter maximum and
that obtained by TBA, because there is a difference of at
least 40 K between their temperatures. Moreover, the
plateau in G! vs o is not seen in polymers of lower
molecular weight, e.g., 37,000 (see Marin and Graessley
(191)), which do, however, clearly show a T , (compare
also Fig. 7; no plateau in G“ is seen).
We conclude that the torsional braid measures
neither G” nor the logarithmic decrement of the poly-
mer melt. What it does measure is not yet clear.
Nevertheless, there can be no doubt about the existence
of a systematic correlation of T I [with M,. The puzzle
remains which physical quantities of the melt govern
this correlation.
As the activation energies below and above Tl1 are
practically the same, I do not think it is semantically
justified to call Tll the transition between a fixed fluid
and a true liquid.
CONCLUSIONS
In the hands of Professor Gillham and coworkers,
torsional braid analysis has proved to be a powerful
method, which has opened up new areas for the success-
ful application of the torsion pendulum. However, care
has to be taken in the quantitative interpretation of the
rigidity data obtained by TBA, especially in the region of
the glass transition. In addition, the technique goes
POLYMER ENGINEERING A N D SCIENCE, MID-AUGUST, 1979, Vol. 19, NO. 10
 The Torsion Pendulum in the Investigation of Polymers
wrong if one attempts to use it for measuring the relative
shear modulus or relative losses of a polymer melt.
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