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 THE STRUCTURE AND ELASTICITY OF
RUBBER
BY L. R. G. TRELOAR,
The British Rubber Pfoducers' Research Association
§ 1. I N T R O D U C T I O N

its ability to undergo a very large reversible deformation natural rubber

I
N
must be considered as a member of a large and rapidly increasing family
of substances of widely diverse chemical constitution; a few of which are
shown in table 1. Not all of these show rubber-like elasticity under normal
conditions, polystyrene and polymethyl methacrylate, for example, become
elastic only-on heating, and are hard glass-like solids at ordinary temperatwres-;
gelatin is .elastic only when swollen with water. For all rubbers the range of
-
Table 1. Some rubber-like materials

Natural rubber

Polyisobutylene

Polystyrene

Polycboroprene dCH2-C =CH-CHz-

(" Neoprene")
c1
I
Polyethylene disulphide -CHt-CHz-S-S-
I! I
(I'Thiokol A")
s s

Polymethyl methacrylate

R
I
-NH-CH-CO-NH-CHA+
Gelatin
I
R

Elastic sulphur - -s-s-s-s- _ . .

8
Pspl
 114 L.R.G. TreZoar
temperature over which rubber-lie behaviour is observed is limited. The
lower limit is associated with the transformation to the glassy or crystalline solid
state; the upper Iimit is associated with the transition to the viscous liquid state
. (unless chemical breakdown intervenes). In many cases, such as natural rubber,
the upper l i t may be raised by vulcanization, whilst in others, e.g. methacrylate,
an extension of the range to lower temperatures may be achieved by the incorpor-
ation of a " plasticizer ".
In this Report an attempt will be made to show how both the elastic and
the other states of a rubber are related to the properties of the molecule and the
arrangement of the molecules in the material.
§ 2. E L A S T I C M O L E C U L E S
Most of the theories put forward to explain the elasticity of rubber have
related it directly to the structure of the molecule, the molecule-thus being
regarded as the fundamental elastic unit. But whereas many of the earlier
theories attributed the elasticity to attractive forces between certain atoms or
groups of atoms along the molecular chain, more recent theories explain the
phenomenon in terms of the thermal motion of the chain atoms: This change
inview-point, which represents nothing less than arevolution in thought, revealing
a fundamental distinction between the rubber-like type of elasticity and the
elasticity of " hard solids of a crystalline or glassy character, took place about
))

ten years ago. The kinetic theory of elasticity was first clearly expressed by
Meyer, von Susich 'and Valko (1932), and was developed mathematically by
Kuhn (1934, 36) and by Guth and Mark (1934). At the same time a similar
concept was in process of evolution in the minds of other workers. Griffith
(1934)) for example, worked out a theory according to which the molecules
rotated in " skipping-rope fashion between their points of interconnection,
))

and though Mack (1934) attributed the elasticity to the attractive forces between
hydrogen atoms in an irregularly-kinked molecule, he was aware that the
postulated ability of certain groups of atoms to rotate about the single C-C
bonds as axes would lead to an enormous number of molecular configurations-
a concept not essentially different from that underlying Kuhn's statistical
treatment.
When we look at the molecular formulae listed in table I, we find in all cases
a chain-lie 'structure. This type of structure is characteristic of all rubbers.
The molecular weight of these long-chain molecules is invariably very high.
Natural rubber, for example, has a molecular weight of about 300,000 (Gee, 1940))
corresponding to a chain length of some 20,000 carbon atoms. Moreover, in '
all rubbers the chain contains single valence bonds, permitting relatively free
rotation of the groups of atoms forming the chain. This characteristic-a long
chain-like structure, containing single bonds-is the only common property of
the chemical constitution of rubbers. If this characteristic is present there may
be a wide variation in other features of the molecule. Thus, for example, double
bonds (which do not allow of rotation) may or may not be present, there may or
may not be side groups along the chain, the chain may be formed of carbon
atoms, or it may be formed of other atoms (e.g. sulphur), or of an alternation of
different atoms,
 The structure and elasticity of rubber . 115

The kinetic theory of Kuhn (1934) idealizes the molecule, stripping it, so to
speak, of all chemical.properties, and treating it simply as a chain of freely-
rotating links. This will be made clear from figure 1, representing a para&
chain. If Cl, C2are the first two carbon atoms, the third atom C, lies on the
rim of a cone formed by the rotation of C,C, about C,C2as axis, where CIC$,
is the valence angle (109Q"). T h e fourth atom, C,, lies similarly on the rim
of a cone whose vertex moves round the first cone, and so on. We thus arrive
at a randomly-fluctuating, irregularly-kinked form of the molecule, such that

Figure 1. Rotations about bonds in paraffin molecule.

the average distance between the ends is only a small fraction of its outstretched
length. It follows that if such a molecule is extended and then released, the
thermal motion of the chain atoms will tend to restore it to its statistically most
probable length. The elasticity is, therefore, a function of the statistical form
of the free molecule, and arises from the heat motion of its component atoms,
Some of the recent developments in the mathematical theory of elasticity
will be considered later; at the present stage we are concerned only with the
general picture of the elastic rubber molecule which this theory enables us
to draw.

tj 3. EXPERIMENTAL EVIDENCE F O R T H E K I N E T I C THEORY .

The kinetic approach leads directly to certain important results, which have
been discussed in an earlier Report (Pelzer, 1939). These are:
(i) The reversible extension of rubber, at constant temperature, involves
no change in its internal energy. The work done on the rubber is trans-
formed into heat, and there is a resultant reduction in entropy on extension.
(ii) I n rubber maintained at constant extension, the elastic tension is
proportional to the absolute temperature.
In both these respects rubbers behave in an entirely different manner from
ordhary elastic solids. Investigation of the behaviour in respect of either
(i) or (ii) may therefore be used to test the applicability of the theory. In a
careful study of - the stress-temperature relations in vulcanized rubber, Meyer
8-2
L x_.6 L. R. G.Tre2oar
and-Ferri (1935) found that, provided that irreversible crystallization and plastic
flow effects were avoided, the prediction of the theory was fulfilled. Figure 2,
taken from their work, shows a proportionality between tension and temperature
over a very wide rmge of temperatures. Other workers, also, have found the

Temperature (OK.)
Figure 2. Variation of tension at constant length with absolute temperahue
for vulcanized rubber (Meyer and Feai).
(a) 350 % elongation, experkental curve.
(b) 350 elongation, corrected for thermal expansion.
(c) 170 56 elongation.
(Reproduced2by Kind pmission, from Helvetica Chimica Acta ', 18, 570.)

tension to increase with increasing temperature, but the relationship was not
always a direct proportionality ; the departures from this simple relationship
are indicative of changes in internal energy, superimposed on the simple entropy
effect. The most complete experimental investigation of such changes is

Table 2. Internal energy and entropy changes on stretching.

(From Wiegand and Snyder's curves.)

Extension ' F (a mo, Twiao,

per cent (gm. wt.) (gm. wt.) (gm. a.)

158 70 + 20 - 50
288
376
104
121
+ 24
+ 5
. - 80
-116
462 113 -142 ~ -255
548 131 -240 -371
632 156 -170 -326
718 250 1390 + 140

probably that carried out by Wiegand and .Snyder (1934), who covered the
whole range of extension of vulcanized rubber. Table 2- gives the relative
internal energy and entropy changes (aUjaZ), and T(aSIaZ)T per unit extension
__
ved ,(Treloar,
. 1942) from their data,
 The structure arid eluitcity of rubber :I.r7
egand-and. Snyder recognize three distinct regions in the extension curve.
first, region (07350 yo extension) there is a reduction in entropy, accom-
panied by a relatively small increase in internal energy, in approximate agreement
with the simple theory; in the second region (400-700 % extension) there is a
large reduction in internal energy, whilst in the third region (>.700 yo) the
energy and entropy terms both be3ome positive. It is clear that in the second
region a spurious effect is introduced by crystallization (see $5), the internal
energy changes resulting from this cause being sufficient to obscure the changes
relating directly to the elastic extension. 'In the third.region the rubber has
ceased to behave like a rubber, and has acquired properties comparable with
those of a crystalline solid.
Meyer (1936) has stated that in the inorganic rubber phosphonitrilic chloride
( PNCl8), the tension at constant extension increased with temperature, in %e
same way as-in natural rubber.
In the direct measurement of the heat evolved on extension the experimental
difficulties have been considerable, and quantitative data which might be used
to check t h e theory do not exist. If rubber is stretched isothermally, the heat
evolved shodd equal the work done on the rubber. This reversible evolution
of heat on extension is well known, but here again the heat of crystallization
tends to obscure the primary effect, thus rendering the interpretation of the
data difficult.

$4. THE MOLECULAR S T R U C T U R E O F RUBBERS

So far the elasticity of the molecule has been considered without relation to
the arrangement of molecules, and the forces between molecules, in the actual
material. In passing on to these other considerations we see at once that certain
other conditions have to be satisfied, if the bulk material is to be elastic. We
are thus led to the following statement of the essential conditions for rubber-like
elasticity, based primarily on the work of Busse (1932) and Treloar (1940) :
(i) The presence of long-chain molecules, possessing freely-rotating
links. -
(ii) Weak secondary forces between the molecules.
(iii) An interlocking of the molecules at a few places along their length
to form a 3-dimensional '' network ".
The first of these conditions has already been discussed. The second is
necessary-if the molecules areato have that freedom of movement which the
kinetic theory of elasticity requires. The third arises from the general con.
sideration that if the molecules are to be under tension they must be connected
more or less firmly with each other, so that a continuous structure is €ormed,
but these intereonnections must not be so frequent that the freedom of motion
of the chain atoms is impeded.
The ideal rubber therefore consists of an irregular network of long elastic
molecules, connected together by chemical bonds. The portions of molecules
between points of linkage are completely free to move among their neighbours,
s the molecules of a liquid, subject only to the restrictions
f;irming part of a chain. Well-vulcanized natural rubber
I 18 L. R;G. Treloar
approximates to this ideal at ordinary temperatures. In this case the cross-links
are generally assumed to be chemical bonds resulting from the combination of
the rubber with sulphur. In unvulcanized rubber, on the other hand, the inter-
connections are not thus sharply defined, but are probably cohesions of vitiying
strength formed as a result of complex local entanglements between the hydro-
carbon chains (Treloar, 1940). Unvulcanized rubber, therefore, shows complex
time effects, due to the breaking down and re-formation of entanglements under
strain, and, at higher temperatures, a plastic or irreversible deformation, effects
which are much less noticeable in vulcanized rubber.

$5. CRYSTALLIZATION
Reference has already been made to crystallization in connection with the
phenomenon of elasticity. Much work has been devoted to the elucidation of
the mechanism of the process of crystallization, and information has been
obtained which throws a good deal of light on the molecular states of rubber.
It has been known for many years that unvulcanized rubber becomes hard
and inextensible if kept at 0" c. or a lower temperature for a few days. It is
known also that raw rubber after stretching to its fullest extent will, under
suitable conditions, remain extended for an indefinite time, but that retraction
to the original length will occur if it is subsequently warmed to a certain sharply-
defined temperature. These effects have been shown by x rays to be due to
crystallization. Some, but not all, synthetic rubbers crystallLe on stretching.

(a) Unstretched. (b) Stretched.

Figure 3. Molecular structure of crystalline rubber (diagrammatic).
The parallel bundles represent crystallites.

At 90" c. vulcanized rubber shows crystallization only when stretched beyond

500 % extension (Field, 1941a). Hence crystallization, though important, must
be regarded as a secondary effect, connected only indirectly with the phenomenon
of elasticity.
The molecular structure of ( a ) unstretched and (b) stretched rubber is
shown diagrammatically in figure 3. A rather similar picture to 3 (b) has been
put forward by Mark (1940) to represent the structure of partially crystalline
cellulosic fibres, with which rubber possesses many common features. In
unstretched crystalline rubber the crystallites are oriented at random. These
crystallites do not occupy the whole of the volume ; there must necessarily be
an appreciable proportion of amorphous rubber, due to the presence of complex
entanglements and portions of molecules which cannot be fitted into the available
 The structure and elasticity of rub6er 1 '9

lattices. In stretched crystalline rubber the forcible extension of the molecules

assists the crystallization ; the crystallites are all nearly parallel, and the amount
of amorphous rubber present is smaller than in unstretched crystalline rubber.
From the breadth of the spots in the x-ray diffraction photographs the length
of the crystallites has been estimated to be 300-600~.(Meyer and Mark, 1928);
since the average chain length is 20,000~.,it follows that an average molecule
must pass alternately through many crystalline and amorphous regions.
The process of crystallization' in unstretched rubber is very slow compared
with that in a low-molecular compound. According to Bekkedahl (1934) it is
most rapid at temperatures between -35" and - 15" c., within which limits of
temperature the crystallization of raw rubber is completed in a few hours.
At -50" c. no crystallization at all was observable Similar observations have

0
W
M
9
- 0.5
3
- 1.0
- 1-5
-2-5
-2 -5
0 50 1U0 150 200
Time (days)
Figure 4. Dependence of rate of crystallization (measured by change of density) of vulcanized
rubber on amount of combined sulphur. Temp. 2' C. (Bekkedahl and Wood.)
1. 0'0 and 0'1 % s. 5. 040:/,s. -
2. 0'20 % s. 6. 0-43% S.
3. 0'30% S. .7. 0'46% S.
4. 0 3 5 % s. 8. 0'50% S.
(Reproduced,hy kind permission, from ' Indushial and Engineering Chemistry '.)

been reported by Meyer and Ferri (1935) and others. The effect of vulcanization
is to reduce the rate of crystallization, as shown by the accompanying curves
(figure 4) obtained by Bekkedahl and Wood (1941), who made use of the
accompanying change in density to study the changes in crystallization.
Apparently cross-linking affects the mobility of the molecules sufficiently to
impede their " shaking down " into a crystalline lattice, but it affects only slightly
the amount of crystallization ultimately arrived at. Furthermore, the tem-
perature of melting of the crystals (-14" c.) appeared to be independent of the
vulcanization. Thiessen and Wittstadt (1938) followed the changes in crystal-
ization in stretched vulcanized rubber by observing the double refraction,
which was shown to be closely related to the amount of crystallization. This
.method, as we€l as the measurement of density, has been used (Treloar, 1941)
 ‘r-
f 20 L. R.G. Treloar
1low the growth of crystallization in raw rubber maintained at 0”c. at
extensions ranging from 34-% to 870 yo. The optical data, shown in figure 5,
reveal a continuous gradation in rate of crystallization from the slightly stretched
to the fully stretched rubber, and leave no doubt that the slow crystallization of
unstretched rubber and the very rapid crystallization of highly extended rubber
are essentially the same process.
The density was found to vary in a very similar manner to the birefringence,
the firial increase of density ranging from 2.24 yo for the unstretched rubber to
3.06 % for rubber stretched to 700 % elongation before freezing. For extensions
from 100 yo upwards the maximum change in density was approximately pro-
portional to the birefringence ; below 100 % extension the birefringence was
relatively lower, due to the imperfect orientation of the crystallites at low
. extensions. The conclusion drawn from these experiments (which seemed to

4
Time (hours)
Figure 5 . Rate of Crystallization of unvulcanized rubber at various exqensions, as shown by
changes in birefringence. Temp. 0” C. (Treloar.)
(Repodwed, by kind permission, from the ‘ Transactions of the Favadcy Society’.)

be confirmed by Gehmari and Field’s (1939) x-ray experiments) was that a

comparatively small egongation leads to a relatively high degree of orientation
of the crystallites in stretched rubber. By extrapolation of the density data
it was inferred (Treloar, 1941) that the change in density corresponding to the
maximum extension used in the optical experiments was 3.75 %. The density
-of the rubber crystal must therefore exceed that of the amorphous rubber by
about 4.0 %.
Crystal growth curves of the type depicted in figures 4 and 5 are consistent
with the view that the growth proceeds from nuclei, “which may consist merely
of an approximate parallelism of neighbouring portions of long-chain molecules ”
(Gehman and Field, 1939).

Relative amounts of crystalline rubber

From x-ray photographs Field (1941 a) has estimated the relative amounts
of the crystalline and amorphous components present in stretched rubber. His
data, some of which are reproduced in figure 6, show a maximum of about 80 %
crystalline’ material, for both raw and vulcanized”rubber at -room temperature.
 The structure arid elmlEi'ccity of rubber t2i

Tlhis -doesnotrepresent the highest degree of crystallizatien obtainable, - a ~-it d

seems probable, from a comparison of the birefringence data at 0"c:and 2S9C.
(Treloar, 1941): that. at the fullest extension at 0" c. at least 90 % of the rubber is
crystalline.
100
1

200 300 400 500 600 700

Percentage elongation

Figure 6 . X-ray determination of proportion of crystalline materid in (a) unvulcanized and

(b) vulcanized rubber (Field).
(Reroduced, by kind permission, from the ' &urnal of Applied PhysiW '.)

Melting of the crystals

In unstretched rubber the crystals melt, not at a sharply defined temperature,
but over a range of about 10"c. (Bekkedahl and Wood, 1941b). The tem-
perature of melting depends on the temperature of crystallization and increases
with the time of storing of the rubber over a period of several years. This is
another respect in which crystalline rubber differs from crystalline substances
of low molecular weight. Similarly the temperature of melting of the crystals
in stretched raw rubber depends on the temperature of stretching (Treloar,
1940). In explanation of effects of this kind, Alfrey and Mark (1942) point out .
that if we consider successive segments of a randomly-kinked molecule attaching
themselves to a crystallite, the free energy of the crystallite will increase by a
constant amount with each segment added, but the decrease in free energy of
the "amorphous ') or statistically-kinked portion of the molecule will b e h e
progressiveIy less (as the statistical theory shows) with each segment 'srtb-
tracted from its length. The crystallization will proceed to the sedge at which
the increase in free energy of the crystalline component is balanced by the
decrease in free energy of the amorphous component. An increase -in -tem-
perature will, therefore, not melt the whole crystal but will merely shift-the
point of equilibrium, causing a greater length of molecule to detach itsel€ from
the lattice. A cruder, but perhaps more tangible, way of expressing this con-
Cepi5on would be to say that there is always a tendency for-the uncrysfallized
I22 L.R. G.Treloav
portions of molecules, being under tension, to pull the crystallized portions
away from the lattice. As crystallization proceeds the amorphous portions
become more extended, and a point is eventually reached at which the resultant
molecular tension balances the molecular attractive forces in the lattice. One
imagines that with the lapse of time some of the molecular entanglements are
slowly broken down, and the molecular tensions are relaxed, enabling further
crystallization to occur. T o produce a state of crystallization corresponding
with the initial state it would therefore be necessary to raise the temperature.

Mechanical efects of Crystallization

It is probable that the high tensile strength of vulcanized rubber is connected
with the crystallization produced on stretching, just as the strength of textile
fibres is related to the degree of crystallization of their molecules (Harris, Mizell
and Fourt, 1942). Mark (19401, in a discussion of the structure and properties
of fibrous materials, suggests that the crystalline elements provide strength
whilst the amorphous elements give flexibility, or extensibility.
The effect of crystallization in reducing plastic flow in raw rubber is very
noticeable, as is shown by figure 7 (Treloar, 1940). One sees from this that

0 100 200 300 400 SC4 600 700

Original percentage extension

Figure 7. The plastic deformation in raw rubber held for 1 hour at the
extensions indicated (Treloar).

(Reproduced, by kind pe?mission, from the Transactions of the Faraday Society '.)

the flow increases rapidly until crystallization sets in, when it reaches a maximum
and subsequently falls. The entanglement-cohesions postulated as linking the
molecules together ($4)evidently-would not by themselves be sufficiently strong
to prevent considerable flow at high extensions; they are just strong enough,
however, to maintain the structure until the onset of crystallization, which
results in the formation of new and stronger intermolecular linkages.
The converse effect-the increase in toughness of a crystalline body due to
the presence of an amorphous high-molecular component-is apparent in a
material like polyethylene. Polyethylene crystallizes almost immediately on
 The structure and elasticity of rubber 123

cooling, and has comparatively little extensibility. But it contains -enough

amorphous material linking together the crystallites to make it flexible and
tough, in contrast to the chemically similar paraffin wax, which is- inflexible
and brittle.
Gutta-percha and balata
A brief reference may be made here to gutta-percha and balata. It is
generally supposed that the molecules of these two rubbers differ from that of
natural rubber only in that in the former the arrangement of the single bonds
about the double bond is trans, whilst in rubber it is cis. This apparently favours
crystallization, for both gutta and balata crystallize quickly at room.temperature,
the crystals melting in the neighbourhood of 60" c.

The P-anomaly in the specific-heat curve

It is satisfactory to note that the so-called /3-anomaly in the specific-heat
curve of rubber (Ruhemann and Simon, 1928), which showed considerable
variation and lack of reproducibility, has recently been shown to be a spurious
effect due 'to crystals formed in the. temperature range - 10" to -20" c.
(Wood, 1942). -

$6. THE T R A N S I T I O N T O T H E G L A S S Y S T A T E
Our knowledge of the transition from the elastic to the glassy state
rests largely on the work of Bekkedahl and his collaborators. From figure 8:
taken from his publications (Bekkedahl, 1934), it is seen that the transition,
which is associated with a change in expansion coefficient by a factor of nearly 3 ,

Temperature (" c.)

Figure 8. Volume-temperature relationship for purified rubber, showing '' second order "
transition at -72" c. and melting,of crystals at 11" c. (Bekkedahl).
(Reproduced, by kind permission,from the 'Journal of Research, National Bureau of Standards '.)

is common to both amorphous and crystalline rubber. The transition tem-

perature ( - 70" c.) is accompanied by changes in - other physical properties,
such as dielectric constant (Bekkedahl, 1934), specific heat (Ruhemann and
Simon, 1928 ; Bekkedahl and Matheson, 1935), and thermal conductivity
(Schallamach, 1941).
 ...
fS4 . L.R; G. Treloar
- This low-temperature transition, which is of the type known as second-order
transitions, .presumably corresponds with the onset of some form of molecular
vibration. The temperature of the transition is in the same region as the change
in amorphous rubber from the rubber-like to the glass-hard state. There -can
be little doubt that, in general terms, the change in mechanical properties is
associated with the loss in freedom of molecular movement; the property of
relative freedom of rotation about valence bonds is lost, the atoms becoming
relatively fixed in position, as in a glass. It is not possible to say exactly how
this loss-of molecular freedom of motion is related to the change in other physical
erties, such as expansion coefficient. In this connection, the occurrence
of the transition in the crystalline rubber presents difficulties. Alfrey and
Mark (1941) consider the theory that the transition is due to molecular rotation
to be supported by x-ray evidence on the rotation of molecules in paraffin crystals
(Muller, 1940), but it should be pointed out that Muller’s observations referred
to transitions occurring near the melting point. It must be remembered that
the crystalline rubber contains a considerable proportion (-30 %) of amorphous
rubber, but if the transition effects were due simply to the residual amorphous
component, they would be considerably smaller in the “crystalline” than in
the amorphous material. Actually, the volume changes are almost identical,
and though the discontinuity in the specific-heat curve is sharper in the
amorphous than in the “crystalline” rubber (Bekkedahl and Matheson, 1935))
the difFemces are not great. A further difficulty is raised by the observation
t h a t the transition in thermal conductivity, when the temperature is falling,
may not -take place until a temperature 50” c. below the equilibrium transition
temperature (Schalfamach; 1941). The glassy state is usually regarded as a .
non-equilibrium state, in which the liquid structure has become “ fixed ” ;
it is difficult to believe that the transition to the supercooled liquid state can itself
be subject to supercooling effects. The point merits further experimental
investigation.
If the hypothesis that the transition to the glassy state is due to the cessation
of rotation about single bonds in the molecule is accepted, there are two sets of
forces which would be expected to play a part in producing the effect, namely :
(i) forces between groups of atoms in the molecule itself, and (ii) forces between a
given molecule and its neighbours. It must be assumed that in the case of
rubbers which readily crystallize (polyethylene, polyisoprene), the effect of
intermolecular or “lattice” forces is predominant, but in the case of more
complex molecules, like polymethyl methacrylate, the energy barriers to internal
rotation may be comparatively high, and it may be that it is to this internal
“ stiffening)) rather than to the intermolecular forces that the low-temperature
transition should, in such cases, be ascribed. It is to this factor that the difference
between polymethyl acrylate, which is elastic at room temperature, and poly-
methyl methacrylate, which becomes rubber-like at about 90” c., has been
attributed (Tuckett, 1942). On the other hand, the transition temperature of many
polymers which are normally glass-like may be reduced by many tens of degrees
by the incorporation of a “ plasticizer (or, more correctly, ‘‘ elastifier ”). This
))

is true, for example, of methyl methac$ate (Tuckett, 1942), and seems to throw
doubt on the adequacy of the hypothesis of internal stiffening. The “ elastifier”
 The structure and elmticity of rubber 125

reduces the forces between molecules, but clearly cannot affect the .forces
restiicting rotation in the individual molecule.
In other cases the transition temperature may be raised by the introduction.
of foreign molecules. This happens when divinyl benzene is incorporated
into polystyrene, and has been attributed to its well-known cross-linking effw,
which leads to reduced molecular mobility (Ueberreiter, 1940). The increase
in transition temperature on vulcanization of rubber by sulphur has been
similarly explained (Ueberreiter, 1940). In the latter case it is doubtful whether
the cross-linking is the only, or even the most important, cause of the change;
the mere addhion of sulphur to the molecule, without cross-linking, would
increase the inter-molecular forces and hence affect the transition temperature
(Gee, 1942).
The transition temperature and relaxation phenomena
Whatever the view taken as to the relative importance of the various factors
discussed above in determining the transition from the glassy to the elastic
state, there seems to be general agreement with the theory that at this tem-
perature the atoms of the molecular chain cease to be fixed, as in a solid, and
aquire a degree of mobility comparable with that of. the molecules of a liquid,
but limited, of course, by their being joined together as members of a single
chain. As in the case of a liquid, the chain atom may be thought of,as.normally
occupying a potential “hole” from which it escapes from time to time on
receiving the requisite thermal energy.

Tempemture (” c.)
Figure 9. The relation between amplitude of deformation of vulcanized rubber (3% S)
and temperature. Parameter :-frequency in cycles per minute.
(Aleksandrov and Lazurkin, 1939.)
(Reproduced,by kind pm@ssion,frm the ‘Journal of Technical Physics, U S S R . ’ )

Whether, or not, a substance is highly elastic will depend on whether the atoms
“nave, or have not, sufficient energy to escape from their potential “holes” in the
time during which the observation is made. I t follows that-a substance may
be rubber-like when the deformation takes place slowly, but not rubber-like
under rapid deformation. This aspect has been studied by Aleksandrov and
Lazurkin (1939)) who investigated the relation between amplitude of vibration
and temperature Wbbers subjected” . to
- an alternating compressive force
 I 26 L. R. G. Treloar
varying in fre.quency from 1 to 1000 cycles per minute. Figure 9, which is
typical of their results, shows that the transition temperature for vulcanized
rubber was raised by about 20"c. when the frequency of vibration was raised
from 1 to 1000 cycles per minute. Their curves could be interpreted on the
basis of the following equation :
D=D,(l -e+),
relating the deformation D with the time of application t of a constant force,
D, being the deformation when t = 00. In this equation T appears as a time of
relaxation, or "time of orientation", of the molecules, which was related to the
potential barrier U restricting the change of form of the molecule by the usual
formula,
r =Aeulm.

This relation adequately represented the experimental data. It is to be hoped

that the evaluation of U for d8erent materials will help in the understanding
of the processes involved in molecular orientation and viscous flow in polymers.

$ 7 . K I N E T I C THEORY APPLIED T O A MOLECULAR NETWORK

We return now to the development of the kinetic theory of elasticity, already
briefly considered in $2. The distribution formula derived by Guth and
Mark (1934) and by Kuhn (1934) to represent the length distribution of a
paraffin chain is
s3
p ( x , Y , z ) d x . d y . d ~= ~ ~ e - B ' ( z ' + d i z ' , d , . d y . d z , . . . . . .(ij
where p ( x , y , z ) is the probability of the chain having components of length
y and z respectivdy along each of three coordinate axes. In this equation
x,

......( l a )

1, being the C-C bond distance, 2 the number of links in the chain, and
180" - 0 the valence angle. In order to visualize the distribution function
represented by (l), one may imagine one end A of each molecule fixed at the
origin of coordinates 0, and consider the distribution of the coordinates of the
'other ends B. According to equation (l), the most probable position of B is
given by x =y = z = 0, i.e. the most probable position of the end B is at the origin.
The probability density falls off on moving outwards from 0, in the way shown
in figure 10 (a), representing the function

This does not mean that the most probable length of the chain, when all
directions are considered, is zero. T o find this we write r ( =(x2+y2+zz)*)for
the length of the chain and determine the number of molecules for which the
end B lies within a kolume bounded by spheres of radii r and r + dr respectively.
From equation (1) this is (Kuhn, 1934)
P8 .k
i(,r)dr= - 2 e+'+ dr, .
.I.. * (2)
7P'B
i
 The structure and elasticity of rubber 127

which is zero when r=O and reaches a maximum when r = 1//3(figure lo@)).
Equations (1) and (2) correspond to those met with in the kinetic theory of gases,

?--

Figure 10. Theoretical distribution of molecular lengths.

(a)Length component in fixed direction p ( x ) = --eB -Bs’.
7d

(b) Total length in any direction p(7) = 4 P rze-’?.

representing (1) the distribution of components of velocity in a given direction.

and (2) the distribution of total velocities (when all directions are included)
respectively (Roberts, 1940, p. 66).

$8. KUHN’S T R E A T M E N T O F T H E NETWORK

In order to simplify the problem of the elasticity of a network of molecules,
Kuhn (1936) made the following assumptions :
(i) All the molecules have the same chain-length.
(ii) The distribution of length components of the molecules is that
represented by equation (1).
(iii) On extension the components of length of each molecule change in
the same ratio as the components of length of the macroscopic rubber.
(iv) The volume of the rubber remains unchanged during”peformatbn,
 I 28 L,R. G. Treloar
The fallowing is a summary of Kuhn's treatment, An expression is first
derived for the entropy s of a single molecule in terms of its length components.
This is obtained from Boltzmann's reIation S = k I n p , so that, from equation (1).
we have for this entropy
s = ~ 1 kP2(x'
- ,C.Y~+Z~), . .. .. (3) I

where cl is a constant. Multiplying this entropy by the number of molecules

having the components of length (x,y , z) (equation (l)),and integrating, leads
to an expression for the total entropy S of the network of N molecules per C.C. in
the unstretched state. If the specimen is extended in the x-direction by the
fractional amount y, the distribution of molecular lengths in the stretched state
(making use of assumptions (3) and (4) above) is

The total entropy9 corresponding to the stretched state is obtained by using (4)
in place of (1). Evaluation of the integrals, neglecting powers of y higher than
the second, leads to the following approximate expression for the entropy change
due to the extension :
s'-s= - 3-j-fky2.
2
. .
* .. ( 5 )
I

This, according to Kuhn, is not the whole of the entropy change on extension.
It represents only the partial entropy change due t o what he calls the rl values,
where rl is the distance between the ends of the molecule. Since the molecule
not only has a " length ' 9 , given by rl, but also a " breadth " r2 and a " thickness )'
r,, it is argued that the contribution to the total entropy due to these r2 and
r3 values should be added to the expression ( 5 ) . Distribution functions
analogous to (1) are worked out for the r2 and r3 values, r2 being defined as
the distance of the mid8 le link of the chain from the line joining its ends, and
r3 as the distance of links one quarter of the way from each end of the chain
(measured along the chain) frbm the plane containing rl and r2. The result is
an additional entropy change on extension amounting -Nky2 for each of the
r2 and r, values, so that (5) becomes
.:,
.
.__
.'. 65 a)
.- ., -. ,
which, on application of the thermodynamic relation between tension F and
entropy (cf. Treloar, 1942)) i.e.,

. ...(6)
i

gives the linear stress-strain relation

F = 7NkTy. ......(7)
$9. AMENDMENT O F KUHN'S T R E A T M E N T
.
As- it stands, Kuhn's treatment is open to' criticism. From a study of Wall's
. work (to be considered later) the author (Treloar, 1943) has been led to argue
of &e r2 and' r8-vaIues'b the expression 6 r the entropy
 The structure and elasticity of rubber 129

change on extension is incorrect. For, in considering the extension of the

molecule, one has to consider one end fixed, whilst the other is confined to the
.
element of volume dx .dy dz. The entropy is related to the probability that
the end of the molecule shall be in this element of volume, which in turn is
determined by the number of possible configurations of the molecular chain
consistent with the given values of x, y and x. In computing these configura-
tions all values of y2 and y3 are automatically included. Hence, to attribute to
them a separate contribution to the total entropy would appear to be un-
warranted. The approximate expression for the entropy change should there-
fore be ( 5 ) and not (5 a).
It has been shown further (Treloar, 1943) that if the approximation made
by Kuhn in omitting powers of y higher than y2 in the evaluation of the entropy
change on extension is avoided, the resulting accurate form of the stress-strain
relation is not linear, but is given by .

.. . .. (8)
where x ( = 1s y ) is written for the ratio of the lengths in the x-direction after
and before extension.
This amended treatment thus leads to a result which agrees with that
derived by Wall by a different method. Wall’s method will now be considered.

5 10. WALL’S T R E A T M E N T O F T H E N E T W O R K
In its amended form Wall’s theory (Wall, 1942) makes use of the same four
fundamental assumptions that formed the basis of Kuhn’s analysis. The
distribution of lengths (i.e. distances between ends) of a system of No equal
molecules, in the undeformed state, is assumed to be that given by Kuhn’s
distribution formula (1). The effect of an elongation (or compression) in
which the length is changed in the ratio a : 1 is assumed to be to alter the com-
ponents of length of all the molecules in the same ratio as the x-, y- and x-dimensions
of the bulk rubber, so that the distribution of molecular lengths corresponding
to the deformed state is described by equation (4),when a is substituted for
1+ y . Wall’s method consists in calculating the probability P that the dis-
tribution represented by (4)should arise spontaneously, given that (1) represents
the probability that a particular molecule has components of length (x, y, z).
In the same way he determines the probability Po of the most probable
(equilibrium) distribution. He thus obtains the relative probabilities of the
stretched and unstretched state, i.e.,

lnP/P,= *o
2
--(E 2
+2/a-3).

The entropy change accompanying the deformation is readily obtained from

this relation by writing S = k l n P. The final stress-strain relationship thus
becomes (for a specimen of original cross-sectional area 1 cm2)

PSPR 9
130 L.R, G. Treloar
In this equation, which is identical with the. amended expression derived by
Kuhn’s method, F is the force per cm?, referred to the unstrained section,
p the density and M the molecular weight. The molecular weight which this
represents is considered to be the weight between junction points of the network.
It is pointed out that the formula (9) applies equally to extension and to unidirec-
tional compression. The stress-strain curve represented by this equation is
shown in figure 11.
The shear deformation has also been dealt with by Wall (1942) by a method
differing only in detail from that just described. If o is the amount of the shear,
the result obtained for the strain energy W is
W = +NkTo2=iGu2, : ....,.(10)

Figure 11. The theoretical stress-strain relationship for a molecular network

~ M=15,000, T=29S0K.

where G is the modulus of rigidity. Under shear, therefore, the stress-strain

relation is linear, whereas under elongation or unilateral compression it is
non-linear. The expression (10) may also be derived by application of Kuhn’s
original method (Treloar, 1943).
Wall’s method of approach is superior to Kuhn’s in that it does not involve
the somewhat unsatisfactory assumption that an entropy value may be associated
with the individual molecule * (cf. equation (3)).
. It is noteworthy that equations (9) and (10) contain only one molecular
constant, namely M, the molecular weight between junction points. The
formula should therefore apply not only to a paraffin chain network, but also
to any rubber in which the distribution of molecular lengths is represented
t y a formula of the Kuhn type, e.g. to natural rubber, in which not all the
carbon-carbon bonds permit of rotation. But it is important to remember the
* Reference will be made to this difliculty in a later paragraph,
 The structure and elasticity of rubber 131

limitations involved in the initial assumptions. In the first place, Kuhnk

probability relation (1) applies only so long as the molecule is not extended
nearly to its outstretched length. The equations (9) and (lo), based on this
relation, cannot be expected to hold if the deformation (elongation, compression
or shear) is so large that an important proportion of the molecules is fully, or
nearly fully, extended. Secondly, the assumption that all the molecules have
the same chain length is obviously not even approximately fulfilled. If there
is a distribution of chain lengths, the shorter chains will become fully extended
at comparatively low extensions. This will limit still further the range of
applicability of Wall's equations. In spite of these difficulties, however,
equation (9) does give a reasonably satisfactory description of the stress-stain
relations in vulcanized rubber (see below).

$11. O T H E R A T T E M P T S T O SOLVE T H E N E T W O R K PROBLEM

The methods of Kuhn and Wall are not the only ones which have been
applied to the problem of the elastic network. They have been given first,
and in some detail, because they exemplify in the clearest manner the general
principles involved and the type of difficulty encountered.
Pelzer (1938) points out that, if one takes the entropy of the sinsle molecule
\
as a function of the x-coordinate only (corresponding to an extension in the
x-direction), by application of the formula S = k l n p to equation (l), one may
derive a corresponding tension f,given by the formula
f = 2kTf12x,
which shows that the tension vanishes only when x=O. This clearly cannot
be applied directly to bulk rubber. Telzer therefore assumes that the proper
basis for calculating the tension is the distribution function for the r-values
(equation (2)). This gives, for the tension f in the molecule,
d
f = -&T;i;(lnp(r))=KT(2/32r-2/r).
The tension therefore vanishes at a value of Y given by r,= lip. Writing
the stress-strain relation foy the individual nzolecule then becomes
Y/Y,, = r,,

f=2pkT(~- :).
It is assumed that the stress-strain relation for the bulk rubber is simply Nf,
where N is the number of molecules.
The stress-strain curve thus derived does not differ greatly in shape from
Wall's (equation (9) ), but the treatment is clearly unsatisfactory and arbitrary.
It leads to the erroneous conception that the molecule, when held at a length r less
than its most probable length (lip), exerts a conzpresa*ve force in the direction
of its length, the magnitude of which becomes infinite when r=O. Since,
according to equation (l), if the end A of the molecule is placed at the origin,
the probability density for the other end B is a maximum when B coincides
with A, it is clear that the only force which may legitimately be pastulated
between the ends of a single'molecule is a tensile force, vanishing when T = O .
 L.R. G. Treloar
If at a given instant B happens to be at a distance r less than the most probable
distance ro, then at a later time, though it will most probably be at a greater
distance from the origin, it will not be in any preferred direction, and hence
cannot be regarded as having moved radially outwards, as if acted on by a
repulsive force from the centre. Equation (2), therefore, does not appear to
provide a basis for the calculation of the entropy of a single molecule. Indeed,
the conception of the entropy of a single molecule seems to involve so many
difficulties that it is safer to avoid it altogether.
Guth and James (1941) also considered the problem of the network of
molecular chains, making use of the assumption that the volume remains
unchanged on extension. Writing L;,Ly and La for the lengths of the sides of a
specimen originally in the form of a 1-cm. cube, this assumption means that
L, = L, = dm3.
It is then stated that the probability that the piece of rubber has the dimensions
L,, L, and La is (in a slightly modified notation)
p ,dL, .dL, .dL, =Ae-p(L*a+48+@)dLz. dL, ,dL,, . . . ...( 11)
which, on substitution of the above relation between L,, L, and L,, and
multiplication by the number of molecules N , leads to the stress-strain relation
F = 2NkTj2(L , - 1/LZ2). . . . * . * (12)
Guth and James thus anticipate the general form of Wall's equation (9).
Their method is, however, unsatisfactory in that equation (11) represents the
probability of the molecule having length components L,, L, and L,, and the
justification for using it to represent the probability of the bulk rubber having
these lengths is not explained.

$12. COMPARISON O F THEORY W I T H E X P E R I M E K T

It has been shown (Guth and James, 1941) that the theoretical equation (9)
is in reasonably good agreement with the experimental data of Meyer and
Ferri (1935) for the elongatiqn, and of Sheppard and Clapson (1932) for the
uni-dir ectional compression of rubber, but it is pointed out that the extension
and compression branches of the curve thus derived require ditferent values
of M . This is to be expected with rubbers differently processed. However,
Sheppard and Clapson have also given data for the elongation of rubbers from
the same batch as-those used in their compression tests, and it would seem
preferable to use both their extension and their compression data for the com-
parison with the theoretical stress-strain relation. The relevant data for such a
comparison are represented in figure 12, in which log F (compressive or tensile
force in kg. per cm? of original section) is plotted against log cr (a logarithmic
plot is necessary on account of the very large range of F). For large extensions
or compressions equation (9) approximates to the respective forms F = '9 ci and

pRT 1
-F = -. - represented in figure 12 by straight lines of slope 1 and - 2. The
x2'

-
intercepts A, A' of these lines on the log F axis give the values of pRT
M '
It is
 The structure and elasticity of rubber 133
seen that Wall's equation gives a very fair approximation to the experimental
data, especially for the compression branch, but it is still necessary to use different
values of M, i.e. 13,000 and 8,400, to represent the respective branches. The
actual values of M are of the expected order of magnitude, but it is difficult to
suggest why the effective molecular weight in extension should be 50 o/n higher
than in compression. Nevertheless, to obtain even this extent of agreement
over a range in which r varies by a factor of 300 is not unsatisfactory, in view of
the very general character of the theoretical assumptions.
It should be observed that the compression data of Sheppard and Clapson
were obtained, not by directly compressing the rubber, but by a two-dimensional
extension obtained by the inflation of balloons. An indirect method of this
kind is necessitated by the fact that it is only possible to compress a rubber block
by a small amount (e.g. 50%) before serious trouble arises from the bulging

I , I I
** -1.8 -16 -1.4 -1.2 -10 -0.8 -06 -0.4' -02 0.0 02 34 0.6 0'8 -

Figure 12. Comparison of theoretical stress-strain relationship with Sheppard and Chpson's
experimental data for vulcanized rubber in elongation and compression.

of the block into a barrel-like form as a result of end friction. Provided that
the volume remains unchanged by the deformation, however, the two-dimensional
extension in the yz-plane may be considered to be equivalent to a unilateral
compression in the x-direction, and a very much greater reduction of the
x-dimension (to 1/40th of its original value) is thus obtainable.
The significant rise in F above the theoretical curve at elongations or com-
pressions near the breaking point is to b e attributed to the pulling-out of the
molecules nearly to their fullest extent, an effect not taken into account in the
theoretical treatment. From the very high crystallization observed in rubber
stretched in one direction it is to be inferred that in the fully extended condition
the molecules lie almost wholly in the direction of extension. Likewise, in the
compression, or two-dimensional extension of rubber, it is reasonable to suppose
that at'the point of breaking nearly a3 the molecules are fully extended in the
 ..
I34 L. R. G. Tyehar
plane of the extension. Thus, if breaking did not intervene, each of the two
branches of the stress-strain curve would become asymptotic to a vertical line,
representing the limit of extension of the network. Although this condition is
not reached, it is clearly being approached, and it is possible, assuming as an
appraximation that the breaking points represent the full extensions of the
network, to compare these extensions with the theoretical maximum extensions.

4 13. M & X I M U M EXTEKSIBILITY O F MOLE'CULAR NETVVORK

(I) One-dintensional extension

Assuming that in the fully-stretched network each molecule has its greatest
possible length ,I the extensibility may readily be calculated. For if xl,x, x3 .. .
are the numerical values of the x-components of length of individual molecules in-
the unstretched network, it is seen that, on stretching, x1 becomes Z, x2 becomes
I, etc. The maximum extension in the x-direction may therefore be taken
to be Z7,J5, where f is the mean value of x I , x 2 . . .) etc. From equation (l),
X=1//3d. For a chain of 2 links of length 1, joined universally (i.e. without
the restriction imposed by a valence angle), the value of ,I is ZZ,, and we have
the relation (Kuhn, 1936)
lip2= ;l22,
wkence
maximum extension = (&z)*=
2.1724.

Figure 13. Segment of polyisoprene chain

The value to be assigned to 2,the effective number of freely rotating links in

the rubber chain, has now to be considered.
Figure 13 represents a segment of the rubber chain containing two isoprene
units, C,-C, being the chain carbon atoms. The system C, C, C, C, is
rigid, hence. it is equivalent to a link of length 3.09.4. (assuming the usual
bond lengths and angles), rotating freely about the axis C, C,. C, C, bas
the length 1.54 A., and rotates freely about C, C,. The next long link, C5 C,,
has the same motions relative to C4 C, that C, C, has. The relatively short
C, C, link -therefore acts. approximately as a universal joint between the
links C, C, and C, C,, and the rubber-chain therefore approximates rather
closely to a system of universally jointed isoprene units. 'The isoprene umt
 The structure and elasticity of rubber I35
has the weight 68 on the molecular-weight scale, hence for M=13,000 the
appropriate value of 2 is 13,000/68, or 191, and the maximum uni-directional
extension is given by a = 30. This is about four times the actual extensibility
(a-7.6).
(ii) Tmo-dimensional extension
By an argument similar to that under $13 (i), the maximum two-dimensional
extensibility may be estimated. If rl, r 2 . .. are the projections of the lengths
of molecules in the plane (yx) perpendicular to the direction of compression,
these all approximate to ,I when the network is fully extended. The maximum
extension (measured by the change in length of a line in the yx-plane) is therefore
l,,JF, where r is the mean value of rl, r2, . . ., etc. For the distribution of Y values
the appropriate function (analogous to (2) ) is

p(r)dr = 13". 2m e-pzr"dr;

57

whence f =n3/2/3, and

*
maximum linear extension = (6Z/n) = 1e 3 8 Z - i .
If a is the length in the x-direction of a line of original length unity, the linear
extension in the yx-plane is l/d (since the volume is unchanged). The linear
extension corresponding to the smallest value of 01 recorded by Sheppard and
Clapson, i.e. 0.0257, is therefore 6.25. Taking M=8,400, 2 becomes 123,
and the corresponding maximum theoretical extension is 15-3,i.e. about 2.5 times
the experimental figure.
The divergence between the experimental extensibilities for both one-
dimensional and two-dimensional extension, and the extensibilities calculated
on the basis of the molecular weights derived by the application of Wall's
equation to the experimental data, is considerable. Various reasons may be
suggested to account for the dis-repancy. Firstly, there is the obvious point
that breaking will occur before the network is completely extended ; the actual
extensibility will therefore always be less than the theoretical, but the difference
would not be expected to be large. Secondly, the theory assumes that all the
molecules have the same chain len ,th,' whereas in practice there must be a
wide distribution of chain lengths. It is not easy to see what effect this mill
have on the extensibility. The third, and probably the most important, source
of error lies in the use of Kuhn's formula for the distribution of molecular
Iengths, which forms the basis of Wall's theory. The derivation of Kuhn's
formula involves assumptions which cannot apply accurately to real molecules.
They are : (i) that each link of the chain possesses complete freedom of rotation,
so that all configurations may be considered to have the same energy ; and (ii)that
the space occupied by the chain may be neglected, so that one part of the chain
offers no obstruction to the motion of any other part. This would be inaccurate
even if the atoms had no volume; the additional volume of the atoms renders
it still more inaccurate. With regard to (i) it has been pointed out (Huggins,
1939) that t h e , energy barriers restricting rotation about a single bond in a
typical case are such that certain positions, spaced at 120" with respect to each
other, are most likely to be occupied. If the three energy barriers were of the
 136 L. R. G. Treloar
same height, the probability of occupation of each position would be the same,
and the resultant distribution of configurations would be nearly the same as if
the rotation were free (provided.that the height of the barriers did not stop
rotation altogether). But if the potential barriers were of different magnitude
a certain position would be more probable than the others, and a considerable
departure from complete randomness might result. Each of the effects (i) and
(ii) is likely to produce an increase in the average length of the chain, i.e. a
reduction in extensibility. The above analysis of the experimental data
suggests that the actual average length of the rubber chain may be as much as
2.5 to 4 times the average length arrived at from the statistical calculatioc.

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