RUBBER ELASTICITY

1.0 Introduction
1.1 Network structure
1.2 Thermodynamics of rubber elasticity
1.3 Statistical theory
1.3.1 The entropy of a single chain
1.3.2 The tension on a chain
1.4 Elasticity of a molecular network
1.4.1 Entropy of deformation
1.4.2 Work of deformation
1.5 Stress-strain relations
1.5.1
1.5.2
1.5.3

Simple tension
Uniaxial compression
Simple shear

1.6 Network defects

1.7 Phenomena theory
1.7.1 Mooney Rivlin Theory

1.0 Introduction Basic Concept

Of all the materials known to man, no other class can match or
even approximate the remarkable behaviour of polymeric
rubberlike materials
1. Classification of polymers: Thermoplastics (crystalline and
amorphous), thermosets and elastomers
2. Differences between rubbers and elastomers. An elastomer is a
polymer which exhibits rubber elastic properties as described below.
3. The word rubber is derived from the ability of this material to
remove marks from paper- obervation made by a chemist Joseph
Priestley in 1770.
4. Unique physical characteristics of rubber-resulted in an enormous
difference compared to materials such as ceramics and metals:
i. high degree of deformability (eg. 3X to 10X their original
dimensions) exhibited under the action of comparatively small
stresses. Maximum extensibility: 500-1000 %
ii. in the crosslinked state, rubbers possess the remarkable ability of
being able to retract rapidly to near their original dimensions when
the stress is removed. This recovery must be achieved with little
permanent set or deformation.

Figure 1: Stress-strain properties of unvulcanized and vulcanized

natural rubber
Important features:
- the curve is markedly non-linear (i.e Hookes law does not apply)
- Youngs modulus can only be assigned in the region of small
strains i.e by drawing the tangent to the curve at the origin.

5.

Different deformation mechanisms between rubber and ceramics and

metals

6.

Rubber elasticity may be defined operationally as very large

deformability
with essentially complete recoverability.

7.

The development of rubber elasticity theory represents one of the most

promising attempts to relate our knowledge of the behaviour of a
polymeric
material on a molecular level with its behaviour on a gross, macroscopic
level.

8.

Requirements for a material to exhibit rubber elasticity:

i.

the material must consist of polymeric chains. The ability to exhibit

rubber elasticity is a property unique to polymers.
the chains must have a high degree of flexibility-weak secondary forces
between the molecules. The individual chain must be allowed to have the
freedom to take up the variety of statistical conformation (i.e. its motion
must not be impeded by the surrounding molecules) upon which the
phenomenon of rubber-like elasticisty ultimately depends. In order to
maintain the high-segmental mobility for rapid stretching, it must be used
well above the glass transition in the unstretched state.

ii.

Figure 2: Typical variation of modulus with temperature for a

polymer
the chains must be joined into a network structure- to prevent permanent
deformation and to allow for rapid retraction. The extent of crosslinking
should
be low to maintain segmental mobility.

9. Vulcanization process: interlocking of the molecules at a few places along

the length to form a 3 dimensional netwrok structure. The number of such
points of cross-linkage required to achieve the elasticity behaviour is not that
high to the extent to interfere significantly with the requisite local freedom of
movement or statistical fluctuation of the individual chains.

Figure 3: Schematic sketch of a typical elastomeric network.

Important features:
types of crosslinking:
chemical crosslinking
resulted in the formation of chemical bonds eg. occur in sulfur
vulcanized natural rubber
physical crosslinking
resulted from the complex geometrical entanglement between chains,
which produce a local enhancement of the residual (van der Waals) forces.
cross

under prolonged loading such entanglement-cohesions or physical

linkages will slowly break down, giving rise to the phenomena of stress
relaxation and creep.
network defects: origin and effect

Important features:
types of crosslinking:
chemical crosslinking
resulted in the formation of chemical bonds eg. occur in sulfur vulcanized
natural rubber
physical crosslinking
resulted from the complex geometrical entanglement between chains,
which produce a local enhancement of the residual (van der Waals) forces.
cross

under prolonged loading such entanglement-cohesions or physical

linkages will slowly break down, giving rise to the phenomena of stress
relaxation and creep.
network defects: origin and effect

Figure 4: Chain defects in network

 10. Historical development of rubber elasticity

i. The elasticity of materials can either be energy-driven or entropydriven.
ii. The discoveries by Gough (1805), Kelvin (1857) and Joule (1895)
lead to the
conclusion that rubber exhibit predominantly entropy-driven
elasticity. The following
observations known as thermoelastic phenomena were made
through the
measurements of force and specimen length at different temperatures:
- a stretched rubber sample subjected to a constant uniaxial load
contracts reversibly on
heating
- a rubber sample gives out heat reversibly when stretched
These observation were consistent with the view that the entropy of the
rubber decreased on
stretching.

Figure 5: Entropy-driven elasticity of rubber materials

11. Metals or other highly crystalline materials (which exhibit Hookean elastic
behaviour at strains
typically less than 0.2%), their elasticity is dominantly energy-driven.

Figure 6: Energydriven elasticity of crystalline solids

The displacement of the atoms in the lattice accompanying the stress causes
an increase in internal
energy. The entropy remains approximately constant.
If entropic effects are neglected, the elastic force causing the displacement of
the atoms from their
equilibrium states is equal to the slope in the plot of potential energy (U) against
displacement R. The
potential exhibits the following approximate r dependence near the equilibrium
point:
U = C (r - ro)2
(2.1)
where C is a constant and ro is the equilibrium bond length.

The elastic force is:

dU
f = --- = 2C (r - ro)
dr
The stress, is:

(2.2)

f
2C (r - ro)
= ---- = -------------A
A

(2.3)

where A is the cross-sectional area.

Eqn.2.3) can be rewrite as:
2C (r - ro)
= -------------- = E (2.4)
A
where E dan is modulus of elasticity and strain, respectively.
Eqn. 2.4 is the Hookes law which relates stress to strain.

1.1 Thermodynamics of rubber elasticit

1. The objectives are to develop
i. relations between force, length and temperature
ii. relationships between thermodynamic parameters i.e internal energy and
entropy.
iii.relationships between i and ii.
The required relations are obtainable directly from the first and second laws of
thermodynamics.
From the first law of thermodynamics the change in internal energy dU in any
process is given by:
dU = dQ + dW

(2.5)

where dQ dan dW are respectively the heat absorbed by the system and the
work done on it by external forces.
The second law of thermodynamics defines the entropy change dS in a
reversible process by the relation:
TdS = dQ
(2.6)
where T is temperature.

Since elastomer deformation can be regarded as a reversible process,

then the change in internal energy can be given as:
dU = TdS + dW

(2.7)

In discussing the equilibrium of a system which is subject to reversible

changes (e.g. elastic deformations), it is convenient to introduce the
Helmholtz free energy, A defined by the relation
A = U - TS

(2.8)

For a change taking place at constant temperature we have then

dA = dU - TdS

(2.9)

Combining this eqn with 2.7 we obtain the standard thermodynamic

result:
dA = dW (constant T)
(2.10)
which signifies that in a reversible isothermal process the change in
Helmholtz free energy is equal to the work done on the system by the
applied forces.

We are concerned primarily with the work done by the applied stress,
corresponding, for example, to a tensile force, f acting on an elastic specimen
of length l, in which case the work done in a small displacement is
dW = fdl

(2.11)

When in addition, a hydrostatic pressure (e.g. atmospheric pressure) is also

present the total work done by the applied force becomes
dW = fdl - pdV

(2.12)

where p and dV are pressure and volume change.

But in the case of rubbers, the volume change dV is usually very small and if
p is the atmospheric pressure, the term pdV in equation 2.12 is very small
compared to fdl by a factor of 10-3 or 10-4. This means the contribution of
pdV to dW is very small and can be neglected. With that, equation 2.11 can
be used.
By making use of equations 2.10 and 2.11, the tension f at constant
temperature may be expressed in the form
f = (dW/dl)T = (dA/dl)T

(2.13)

which shows that th tensile force is equal to the change in Helmholtz free
energy per unit increase in length of the specimen.

Figure 2.5 represents diagrammatically the variation of Helmholtz free energy for an
elastic body as a function of its length, l when an elastic sample is stressed or
compressed uniaxially. The unstressed state is such that the Helmholtz free energy is
a minimum, so that (dA/dl)T = 0 when there is no force being applied on the sample
(or when l = lo). When a uniaxial tension or stress is applied, the length of the sample
increases (l > lo) and (dA/dl)T becomes positive. On the other hand, when
compression becomes dominant, (l < lo), (dA/dl)T becomes negative.
The sum of both equations (2.9) and (2.13) will give an equation combining force with
the variation of Helmholtz free energy, internal energy and entropic variations, which
is:
f = (dA/dl)T = (dU/dl)T - T(dS/dl)T
(2.14)
with (dU/dl)T and (dS/dl)T representing the change in internal energy and the second
the change in entropy, per unit increase in length under constant temperature. Writing
equation 2.8 in differential form, we have for any change (either isothermal or not),
changes in the Helmholtz free energy can be written as:
dA = dU - TdS - SdT
(2.15)
From equations 2.7 and 2.11 we get:
dU = fdl + TdS

(2.16)

Combining equations 2.15 and 2.16 will give

dA = fdl - SdT

(2.17)

Hence, the partial differentiation at a constant temperature followed by a constant

length will give:
(dA/dl)T = f and
(dA/dT)l = -S
(2.18)
By a well-known property of partial differentials
d/dl(dA/dT)l = d/dT(dA/dl)T

(2.19)

From equation 2.18 the entropiy change per unit extension can be given as:
(dS/dl)T = -(df/dT)l
(2.20)
Equation 2.20 gives the entropy change per unit extension in terms of the
experimentally measurable quantity (df/dT)l, the temperature coefficient of
tension at constant length. Insertion of this relation in equation 2.14 gives for the
corresponding internal energy change:
(dU/dl)T = f - T(df/dT)l
(2.21)
Subsequently, equation 2.21 can be changed to a more relevant form which is:
f = (dU/dl)T + T(df/dT)
(2.22)

Equations 2.20 and 2.22 are of fundamental importance in rubber elasticity,

since they provide a direct means of determining experimentally both the
internal energy and entropy changes accompanying a deformation through
experiments.
Thus the internal energy and entropy contributions to the force at any given
value of the extension are directly obtainable from the experimental forcetemperature plot. This is shown in Figure 2.6.

For an isothermal extension at the temperature T, the entropy change per

unit extension (dS/dl)T given by equation 2.20 can be obtained from the
slope of this graph. In a corresponding way, the intercept OA of the tangent
to the curve is equal to the change of internal energy per unit extension (see
equation 2.21). If the force-temperature plot is a straight line passing through
the origin, the internal energy term is zero, i.e. the elastic force arises solely
from the change in entropy on extension. It should be stressed that the
force-temperature plot at a constant length can be linera or otherwise. If the
plot is linear as seen in Figure 2.6, both internal energy and entropy terms
(thermodinamic parameters) are independant of temperature. Detailed
research on using thermodynamic analysis have been undertaken by
Anthony, Caston and Guth in 1942.

Figure 2.7 shows the stress-temperature plot at a constant length (given by the
extension ratio, ) for natural rubber. It is seen that for extensions exceeding
1.13, the stress increases with increasing temperatures, as shown in Figure 2.6.
This clearly shows the typical elastic deformation behaviour of elastomers which
are controlled by entropy. However, the opposite trend is observed at extensions
below 1.13, i.e. stress at a constant length decreases with increasing
temperatures.

The phenomena related to the change from a positive to a negative temperature

coeffision is known as thermo-elastic inversion. It takes place as a result of thermal
expansion which in turn brings about an increase in the initial length, Lo when the
temperature increases. An increase in Lo brings about a reduction in real values
at a constant length L. This phenomena can be overcome by measuring Lo at
each temperature and also if a constant real are used. Other results obtained by
Anthony, Caston and Guth are also shown in Figure 2.7 and 2.8. These two
figures are stress-strain plots of natural rubber at 20oC. From Figure 2.7, it is
observed that the contribution of internal energy towards force is only important at
a low strain. When the strain increases (especially more than 100 %), the
dominant component of the force is the entropy component, as opposed to internal
energy. An observation made from Figure 2.7 is that as the extension is
decreased, this internal energy term becomes relatively more important, and in the
regions of small extensions (0 - 10 %) it is the major factor in the situation,
surpassing the total force, f, and the contributional value of the entropy component
is negative.

These peculiarities reflect the changes in slope of the force-temperature

relations at constant length, and may similarly be eliminated by appropriate
adjustment of the unstrained length to compensate for the thermal expensivity
of the unstrained rubber. The results are shown in Figure 2.8.

This figure clearly shows that the elastic deformation of rubber is wholly
controlled by the changes in entropy and not by internal energies. Figure 2.9
shows results obtained by Wolf dan Allen (1975) after running tensile tests on
natural rubber at room temperature. The internal energy elastic force component
is found to only contribute around 15% while the other 85% is the contribution of
entropy. This observation further reinforces the earlier explanations given to
explain the unique behaviour of elastomeric materials compared to other
conventional materials. As we will observe in subsequent discussions, the elastic
deformation process which is controlled by changes in entropy is an important
fundamental in the development of various rubber elasticity theories used to
explain the physical and mechanical behaviour of elasomers.

2.3 Statistical Theory

The statistical theory for rubber elasticity was first suggested by Meyer,
Susich and Valko at 1932. Their effort was further continued by Guth and
Mark (1934) and Kuhn (1936). Later on, the theory was further developed
again by James and Guth (1942), Wall (1942), and Flory and Rehner
(1943). There are three main assumptions considered for this theory:
1) Individual rubber molecules are present in the form of long chains, with
each chain capable of displaying different conformations,
2) Cross-links exist between the molecule chains. This brings about a
coherent network structure. However, the number of cross-links are
relatively small and not sufficient to hinder the chain movement
subastantially,
3) The molecular chains are prone to be in a maximum entropy state (which
is a set of random conformation) except if an outside force is applied.

In equation, dxdydz represents the volume of the element which is the location of
point P.
This situation is explained schematically in Figure 2.10.

Equation 2.23 enables us to get the entropy of a single chain using the
Boltzmann function made from thermodinamic statistics. From that function, we
can conclude that the entropy, s for a single free linked chain is proportionate
with the logarithm of the number of conformations possible for that chain,
which is:
s = kln

(2.26)

with k the Boltzmann constant.

From equation 2.23, if the volume of element dxdydz is constant, the number of
conformations possible for a chain is proportionate with the probability per unit
volume, W(x,y,z). As such, the entropy can be given as:
s = kln W(x,y,z) dxdydz

(2.27)

The equation above can be further expanded to become:

3
s = kln [------exp (-2 r2)d]
3/2

(2.28)

with d being the elements volume, dxdydz.

From equation 2.28, s can be written as
3
s = kln (-------)2 r2 + ln d
(2.29)
3/2
Since (3/3/2) and the volume element d is assumed constant, this may be
written in the form:
s = C - k 2 r2
(2.30)
where C is an arbitrary constant which includes the volume element d.
Equation 2.30 shows the entropy to have its maximum value when the two ends
of the chain are coincident (r = 0). In other words, the chain conformation is most
random when the chain ends coincide. When there are disturbances from
external forces, the free movement of the chains are hindered. This will bring a
reduction in the conformation and the entropy values will be reduced. This
situation is explained in Figure 2.11. It can be seen that when the chains are
stretched fully, the minimum entropy situation happens.

2.3.2 Effect of tensile force on a chain

From section 2.2 we know that changes in Helmholtz free energy, dA can be given
as:
dA = dU - TdS
(2.9)
For a free linked molecular chain (there are no hinderences in the movement of
the chain at the links) the internal energy for that molecule is the same for all
conformasi. This means that the change in Helmholtz free energy is determined by
the entropy changes, ds, which is:
dA = -TdS
(2.31)
Consider a chain where one end is fixed at a point and is separated by a distance
r. This is shown in Figure 2.12.

The work needed to move one end of the chain from distance r to a new
distance, r + dr refering to the other end is the same as the change in the
Helmholtz free energy, which is:
dW/dr = dA/dr = -TdS/dr
(2.32)
It is known from section 2.3.1 that entropy is related to distance by:
s = C - k2r2
(2.30)
By differentiating the entropy function above with reference to r gives us:
dS/dr = -2k2r
(2.33)

Inserting equation 2.33 into equation 2.32, enables us to correlate between the
change in work and the distance r, which is:
dW/dr = 2kT2r

(2.34)

Since work is done in changing the end-to-end distance, r to r+dr, it follows that
there must be a tensile force f acting along the direction of r. The work done by this
force in a displacement dr being given by:
dW = fdr
(2.35)
The relationship between this force and the end-to-end distance can be obtained
by joining equations 2.34 and 2.25 which is:
f = 2kT2r
(2.36)
Equation 2.36 shows that the tensile force is proportionate to r. This means that
the conformation of a chain will be reduced when the force increases.

2.4 Elasticity of a molecular network

The discussion thus far has only taken into account a single polymer chain. However, we are
more interested to know how the entropy approach can be used to understand the elastic
behaviour exhibited by an elastomeric material which has many chains. It is known that
vulcanized rubber consists of a large number of long molecule chains cross-linked together to
form a 3 dimensional network (See Figure 2.3).When using the statistical theory, each segment
of molecules between subsequent cross-link points can be considered as a Gaussian chain. A
few important assumptions have to be made before discussing the topic of elasticity of a
network. They are:
1) The network contains N chains per unit volume, a chain being defined as the segment of
molecule between succesive points of cross-linkage.
2) The mean-square end-to-end distance r2 for the whole assembly of chains in the unstrained
state is the same as for a corresponding set of free chains, and is given by the equation
r2 = nl2
(2.37)
3)The deformation process does not bring changes in the volume. In other words, a constant
volume is maintained.
4) The junction points between chains move on deformation as if they were embedded in an
elastic continuum. As a result the components of length of each chain change in the same ratio
as the corresponding dimensions of the bulk rubber. This is known as the affine deformation
assumption.
5) The entropy of the network is the sum of the entropies of the individual chains, the latter
being given by:
S = C - k 2r2
(2.30)

2.4.1 Deformation entropy

In the case of a simple homogeneous extension, the main extension ratios
1, 2, 3 along three perpendicular axes x, y, z. This is further explained in
Figure 2.13 which shows a unit cube in an unstrained state and in a strained
state.The extension ratios at a certain axes is dependant on the type of
loading. These extension ratios may be either greater than 1, corresponding
to a stretch, or less than 1, corresponding to a compression, provided that
the condition for constancy of volume (assumption 3 above), namely:
1, 2, 3 = 1
is satisfied.

(2.38)

Let us consider an individual chain having an end-to-end distance represented

by the vector ro, with components P(xo, yo, zo), in the unstrained state of the
network, and let P' (x, y, z) be the components of the vector length r of the
same chain after deformation and the end-to-end distance becomes r. (See
Figure 2.14.)

Then by the affine deformation assumption (changes in the vactor

components of the strained state is proportionate with the changes in the
sample dimensions). As such,
x = 1 xo, y = 2yo, z = 3zo
(2.39)
Refering to equation 2.30 which we got earlier, the entropy of an unstrained
chain is given by:
Whereas the entropy of the same chain after being strained is:

By combining equations 2.40 and 2.41, in a strained state, the chain entropy
can be given as:

The contribution to the total entropy of deformation for the network due to this
chain will therefore be:
The total entropy for all the N chains contained in unit volume of the network is
obtained by summation of the equation 2.43. Assuming for the moment that the
chain contour length or chain molecular weight is the same for all the chains, the
parameter b (which is a function of chain length) will be constant, and we may
write for the total entropy of deformation:

Equation 2.57 is of the utmost importance in the elastical aspects of rubber because it
defines the elastical characteristics of a certain rubber in the Gaussian area and also
enables the stress-strain relations for any type of strain to be derived. (tension,
compression and shear). This will be discussed in detail in Section 2.5. From this
equation, it can be seen that the elastic constant, G, more known as the elastic
modulus, is related to N.
In equations 2.56 and 2.57, N values, or the number of chains per unit volume, which is
itself determined by the degree of cross-linking of the polymer chains. N is
proportionate to the mean molar mass number for the chains between cross-link points,
Mc, and is obtained from:

where , R and Na are the rubbers density, the gas constant and Avogadros
number respectively.
Equation 2.58 was derived by considering that there were no network defects
which might have been due to the chain ends and chain entanglements. Both
these defects do not contribute towards the strength of the network. This aspect
will be discussed further in Section 2.6. By combining equation G = NkT and
equation 2.58 we get:
Equation 2.59 shows that the value of G will increase when the chain lengths
between cross-link points or Mc is reduced. This means that when the cross-link
density increases with the reduction in Mc values, the network becomes more
dense and increases the stiffness of the samples.
Equation 2.57 can also be given alternatively as:

2.5 Stress-strain behaviour of rubber

In Section 3.4, it is shown that the statistical network theory leads to an expression for the
work of deformation in a pure homogeneous strain of the most general type, which involves
only a single material constantor modulus, which is related to the degree of cross-linking or
number of chains per unit volume of the network.
The stress-strain behaviour of rubber can be predicted using statistical theories. These
forms of behaviour, however, depend on the loading geometry or types of strain applied. To
explain this, a few simple strain such as uniaxial strain, uniaxial compression and shear will
be considered. The more complex problems such as pure homogeneous strain can be
referred from specific books such as "The Physics of Rubber Elasticity" by Treloar.

It should be stated that G can also be explained

as given by equation 2.59. The relationship
between nominal stress, f and elongation ratio,
for a rubber specimen can be predicted using
equation 2.64. Besides that, comparison with
experimental results can be done by by
comparing the theoretical curve with the
experimental data after choosing a suitable G
value. This can be seen in Figure 2.17 which
shows an example of comparisons done on
vulcanized rubber which was subjected to tensile
load. The G value chosen was 0.39 MNm-2.
Comparison of experimental and theoretical
curves at an elongation ratio lesser than 1.5.
After this value, there are deviations between
data obtained experimentally and theoretical
data. It is observed that at an elongation ratio in
the range of 1.5 < < 6, the experimental curve
lies below the theoretical curve. When > 6, the
tangent of the experimental curve increases
drastically and lies above the theoretical curve.
There are two factors that possibly bring about
this deviation at high elongation ratios.

First, the Gaussian formula cannot give an exact prediction because the value
of the elongation ratio has exceeded the extensibility of the network. The
Gaussian statistical theory is valid only so long as the extension is not too
great. When the elongation ratio is high, > 6 as in the case above, the finite
extensibility effect for the chain (and hence the network) must be taken into
account. For that, the non-Gaussian theory would be a better approach to
provide a basis for the interpretation of the upward curvature at large strains.
Readers can refer to "The Physics of Rubber Technology" for detailed
explanations.
The second factor is the possibility of strain induced crystallization happening
in the rubber sample. This phenomena is known to happen in a few types of
elastomers. However, this factor is hard to accept as tensile tests done on
vulcanized rubber samples at high temperatures around 100oC still exhibit the
same stress-strain properties exhibited by samples tested at room
temperature. It is predicted that strain induced crystallization will decrease
when the temperature is increased until 100oC. Other than that, the truth of
this factor is also questionable because the same stress-strain curve shape is
observed in uncrystallized rubber. With that, we can conclude that if this
crystallization phenomena happens in an elastomer, it is one of the elastical
behaviour of rubber and cannot be predicted by statistical theories.

2.5.2 Uniaxial compression

Using equations 2.54 and 2.55, the changes in plane dimensions is in a -1/2 ratio and the
compression ratio is lesser than 1 for uniaxial compression loading. Same as uniaxial
stress mentioned above, the force per unit cross sectional area is measured in an
unstrained state or the nominal stress can be given as:

Figure 2.18 shows the relationship between nominal stress, f and elongation ratio, for
rubbers of the same type used in tensile tests, but which underwent a uniaxial
compression type of loading. It can be seen thaqt the values of f and are each negative
and lesser than 1, which shows that the specimen is under compression.
It is observed that there is good agreement between experimental and theoretical data in
the ratio range of 0.4 < < 1.3. In the figure, the > 1.0 area refers to the nominal stresselongation ratio behaviour of specimens undergoing uniaxial tensile loading. As explained
in setion 3.5.1, there is very good agreement between experimental and theoretical data in
the range of = 0.0 to 1.3.
From Figure 2.18 we can conclude that in the range of 0.4 < < 1.3, the Gaussian
formula can predict the stress-strain behaviour of rubber very well in both forms of loading,
be it uniaxial tensile or uniaxial compression. This means that the statistical theory is
useful to predict the stress-strain behaviour of rubber when the elongation ratio is not too
high.

Figure 2.18: Stress-strain under compression mode

2.5.3 Simple shear

Consider a cube shaped specimen that undergoes changes at its side surfaces to become a
rectangular cube when subjected to shear stress xy. This is shown in Figure 2.19.

Figure 2.19: Shear deformation

Because there is no deformation along the axis normal to the shear axis, CD, the elongation ratio
for that direction is 1.
By assuming that the specimen volume is constant (1, 2, 3 = 1) when deformation, we can
explain all three main elongation ratios in terms of the major axis of strain, i.e.:
The ammount of the shear, , may be related either to the angle or to the principal extension ratios
thus:
From section 2.4.2, we know that the common form for strain energy, W can be given by equation
2.52.Thus, by inserting the values of 1, 2, and 3 from equation 2.68 into equation 2.52, enables
the strain energy to be given as:
By combining equations 2.69 and 2.70, we get a simpler form for W which is:
By assuming that the work done on the cube is wholly done by the shear stress, xy, the
relationship between shear strss an shear strain is obtained:
The equation above shows that the shear stress, xy, is proportional to the shear strain, . This
means that Hookes law is obeyed in the case of simple shear. G in the equation above is known as
the shear modulus.

The equation above shows that the shear stress, xy, is proportional to the shear
strain, . This means that Hookes law is obeyed in the case of simple shear. G in
the equation above is known as the shear modulus.
Figure 2.20 shows the
comparison between experimental
results (obtained from vulcanized
rubber) and the theoretical curve.
Again, the shear modulus values,
G, chosen were 0.39 MNm-2.
There is good agreement between
experimental and theoretical data
until the shear strain reaches 1.0
and the value is 45o. After this
value, deviations start to occur
and the experimental curve drops
below the theoretical curve.

2.6. Network defects

Figure 2.21 shows two types of networks formed from the cross-linking process.
In Figure 2.21a the cross-linking process involves normal tetrafunctional crosslinks, where there are 4 network chains ending at each cross-link point. The
number of chains are two times the number of cross-link points. The presence of
this unique system enables each chain to have an equal contribution to the
network elasticity. This means that when a tetrafunctional network is deformed by
an external force, the network chains will react to form an effective retractive
stress.

The situation mentioned above is the case of formation of a unique network. In

practical terms, these types of network is very hard to be made. This is because it
is clear that in any actual process involving random cross-linking, not all polymer
chain segments of the original material (which are linear molecules with a high
molecular weight) can be joined to the network at two points. This brings about
imperfections in the network, as can be seen in Figure 2.21b. The presence of
imperfactions is proven when there still remains a small ammount of soluble
material left behind in the elastomer after the cross-linking process has ended.
Knowledge regarding network imperfections are important because it can effect the
elasticity of the elastomer.
There are three different types of departure, or network defects identified.

(a)

Physical entanglement between chains.

Figure 2.22a shows that there are two types of physical entanglements,
permanent and temporary. Permanent physical entanglements means that it will
not diminish eventhough an external force is applied on the network. However,
for the temporary entanglement, it will diminish when the network is subjected to
a force for a long period of time. The presence of temporary physical
entanglements can make a network incapable of exhibiting a perfect elastical
behaviour but otherwise the viscoelastic behaviour such as creep and stress
relaxation becomes more dominant. For the case of permanent physical
entanglements, when a force is applied on the network having the particular
entanglement, the chains slide against each other in the early stages.
Continuous force will bring about the formation of junction points which are
known as physical cross-linking. This will increase the effective chain.
Eventhough the presence of physical entanglements will increase the number of
effective junction points, its contribution on the chain movement resistance (or
contribution to chain elasticity) is small compared to increasing the number of
chemical cross-links. The effectiveness of physical entanglements in increasing
the elasticity of a network will increase if the degree of cross-linking increases.

(b) Intramolecular network

Figure 2.23b shows an example of the intramolecular entanglement
defect.This happens as a result of the linkage of two points on a single chain,
giving rise to a closed loop which makes no contribution to the network
elasticity; such intramolecular linkages should therefore be discounted in the
evaluation of the modulus.
(c) Free chain ends
It consists of chains which are connected to the network at one end only.
(Figure 2.22c). Generally, the number of free chain ends is directly related to
the number of chains ends in a polymer before vulcanization. The stress
transfer by the chain ends are not effective compared to other parts of the
chain, meaning its presenc does not bring any positive contributions to the
elastic force.
A quantitative approach to analyse the effects of chain ends on the elesticity of a
tetrafunctional network was proposed by Flory in 1946.
Taking the number of original or primary molecules before cross-linking to be Np,
and Np - 1 is the number of intermolecular linkages required to link these together
into a single ramified structure in which there are no closed loops.
A network will only start forming when Np - 1 linkages are present. After that,
each additional cross-link will produce on closed loop, or two network chains. This
means that only the additional cross-linking is effective in network forming.

2.7
The phenomena theory
Phenomena theory is an approach useful to ultimately explain a characteristic in a general
sense using mathematical points. Because this theory is not based on the molecular concept or
structural concept as found in the statistical theory for rubber elasticity, it cannot be considered a
molecular theory. However, it can still be used to understand the elastical behaviour of
elastomers as will be explained in detail later on.
2.7.1
Mooney-Rivlin Theory
This is one of the phenomena theory used very often to discuss the elasticity of rubber. It
considers an elastomer as a continuum and is very useful to understand the high elastic
deformation. The Mooney-Rivlin theory was actually derived before the Gaussian statistical
theory.

Equation 2.73 and equation 2.74 are two forms of explaining the Mooney-Rivlin theory.
In both equations C1 and C2 is the empirical constant.
Two assumptions were made to derive these equations. First, rubber cannot be compressed
and is in a non-deformed state. Second, Hookes Law is obeyed in the case of simple shear.
From Section 2.5, the Gaussian statistical theory has been used to derive the relationship
between nominal stress-strain which is given by:

In both equations C1 and C2 is the empirical constant.

Two assumptions were made to derive these equations. First, rubber cannot be
compressed and is in a non-deformed state. Second, Hookes Law is obeyed in the case of
simple shear.
From Section 2.5, the Gaussian statistical theory has been used to derive the relationship
between nominal stress-strain which is given by:
If we compare equation 2.64 and equation 2.74 we can observe that the Gaussian
statistical theory is one of the cases for the Mooney-Rivlin theory. This is because when C2
= 0, equation 2.84 can be simplified to become:
C2/ in equation 2.74 is a parameter which takes into account the non-linear behaviour at
high elongational values as observed in experiments and as shown in Figure. By
rearranging it a bit, equation 2.74 can be given in an alternative form:

Figure 2.20 shows the Mooney-Rivlin plot for a few natural rubber vulcanizates which was
done by Gumbrell, Mullins dan Rivlin in 1953 for the case of uniaxial tension. From their
research, the value of C1 was found to change depending on the degree of cross-linking,
from 0.10 Nmm-2 to 0.31 Nmm-2, whereas the value for the constant C2 is nearly constant at
0.10 Nmm-2. These results show that the value for the constant C1 is dependant on the
network structure or degree of cross-linking. This clearly proves there there exists a
relationship between the constant C1 and G as shown in equation . This fact can be better
understood by referring to work done by Ishikawa and Nagai in 1969. They ran their tests on
non-swellable cis polybutadienes which were prepared using various cross-linking techniques
such as electron beams, sulphur and dicumylperoxide. The Mooney-Rivlin they got is shown
in Figure 2.21. From the figure, it can be seen that the slope of the sulphur cross-linked and
dicumylperoxide cross-linked systems is higher or shows a higher C2 value compared to the
system cross-linked using electron beams. Other than that, the addition of constants C1 and
C2 which were obtained from the point that crosses th y-axis at 1/, is equivalent to 1 for the
system cross-linked using electron beams. This value is also the lowest among the other
systems. This is because the value for C1 which is related to the degree of cross-linking, is
small for the electron beam cross-linked system compared

to the C1 values for the other two systems. In other words, the sulphur and
dicumylperoxide cross-link systems are more effective in increasing the degree of crosslinking in cis-polybutadiene.
Since the Mooney-Rivlin equation was introduced, various efforts have be taken to
understand the importance and characteristics of the empirical constant C2. There are a
few general observations regarding C2 which were highlighted. Firstly, it does not depend
on the degree of cross-linking and the type of rubber used. Secondly, it is prone to
become zero when the rubber swells too much. Lastly, the constant C2 is very useful in
explaining the stress-strain behaviour of elastomers when the material is deformed in
tension mode. In other deformation modes, it does not show an obvious advantage if
compared to that highlighted by the Gaussian statistical theory.