SOFT CONDENSED MATTER

PHYSICS
PHY F416
Prof. MANJULADEVI. V
Department of Physics
BITS Pilani, Pilani Campus
[email protected]
The essential characteristic of Elastic soft matter is that they have a
well-defined, conserved shape: they deform when external forces are
applied, but recover the original shape when the forces are removed.
This is distinct from the liquid state: liquid does not have its own
shape and can be deformed without any work.
 The elasticity of hard elastic materials such as metals and glasses comes from the fact that
the atoms in the material are trapped in the state of local energy minimum, and resist any
change from the state.

 Soft elastic materials such as Rubbers and gels are distinct from these materials in the sense
that atoms are moving vigorously, very much like in the fluid state (polymer melts and
polymer solutions)

 Rubbers and gels are made by introducing cross-links in the fluid state of polymers. The
fraction of cross-links is usually very small (less than a few percent), and most of the material
remains in the same state as that of fluids. Nevertheless, a small number of cross-links is
often sufficient to change the fluid into an elastic material.
 Theory of Polymers
Figure 3.1 shows a schematic comparison between the fluid state
(solution) and the elastic state (gel) of polymers. In polymer
solutions, long-chain-like molecules are entangled with each
other. Therefore, a polymer solution is a viscous material. It is a
material that resists flow, but it can flow. Indeed, a polymer
solution in a container can be poured on a table if sufficient time
is given. On the other hand, in polymer gels, the polymers are
chemically cross-linked and form a large molecular network.
Such a material cannot flow, and cannot be poured: if the
container is placed upside down, the material may fall out, but
will not spread on the table.

A fluid does not have a well-defined shape, and can be deformed indefinitely. On the other
hand, an elastic material has its own shape and can be reversibly deformed to a finite extent.
Though this distinction may seem very clear, it is not so in many soft matter systems.
Viscosity and elasticity

Shear stress: 𝜎 = 𝐹 𝑠

Shear strain: 𝜸 = 𝑑 ℎ

Shear modulus: 𝜎 = 𝐺𝜸 (Hookean Solid)

𝜎 = 𝑛𝛾̇ (Newtonian fluid)

For soft materials (incompressible material) E=3G For more details refer to 3.1.3 of TB1

E: Young’s Modulus(Elongational modulus)

Continuum mechanics for elastic materials
Uniform deformation

r⃗ = 𝐸 ⋅ 𝑟⃗ Constant tensor E

𝜕𝑟
𝑟 =𝐸 𝑟 𝐸 =
where 𝜕𝑟

As local deformation is always uniform since a small vector 𝑑𝑟 can be mapped into

Hence, total energy of deformation

𝐹 = − d𝑟 𝑓 𝐸 𝑟⃗
 Random Walks and dimensions of of a Polymer chain
The freely jointed chain Model:

End to end vector: a

Mean end to end distance:

Picking out N cases where i=j

For a freely jointed chain

 The distribution of possible end to end distances is given by the Probability function:

Configurational entropy:

When we stretch a polymer chain its entropy is lowered, resulting in an increase in the free energy
 In real polymer systems, the crosstime does not vanish

Assume breaking the chain into subunits, whose size is larger than that of correlations
 𝒄~ 𝑵
𝒓𝟑

In polymer coil, there is a positive contribution to the free energy due to the excluded volume

Ftot= Frep+Fel Minimising this total free energy w.r.t r

𝟑
𝒓~𝒂𝑵 𝟓
Substitute

𝟑
 < : : 𝒓~𝑵 𝟓 : polymer chain is expanded
𝐠𝐨𝐨𝐝 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 𝐛𝐞𝐡𝐚𝐯𝐢𝐨𝐮𝐫

𝟏
 = : 𝒓~𝑵 𝟐 :Polymer chain is an ideal random walk
theta condition

 > : attractive effect of polymer-solvent interaction

outweights excluded volume interaction;
Chain collapses to form a globule
 Spatial correlation in soft matter solutions

Let us assume that the solution includes N solute segments in volume V , and let rn (n = 1, 2, . . .,N)
be their position vectors. The average number density 𝑛 of the solute segment is given by
𝑵
𝒏=
𝑽
the local number density fluctuates around this value.
 If we consider a spherical region of radius a, the local number density at point r can be defined by

Here the integral on the right-hand side represents the number of solute segments in the spherical region |r − r’| < a.
Clearly, the value of the local number density depends on a, the radius of the sphere.

Consider the limit a → 0, and denote the local density in this limit by

and
 Density correlation functions

The uneven distribution of solute segments is characterized by the spatial correlation function for the
local number density.

pair correlation function:

For a macroscopic sample at equilibrium, the correla on ˆn(r)ˆn(r) has transla onal invariance
gm(r) represents the average density of segments at the point which is separated by
vector r from a particular segment m. Therefore g(r) represents the average density
of segments at the point which is separated by r from an arbitrary chosen segment.

At large distance |r|, g(r) becomes equal to the average density ¯n. At
small distance g(r) differs from ¯n since segments are attracted or repelled
by the segment at the centre.
 If the segments form clusters, g(r) is larger than ¯n over the distance of
the cluster size. The number of excess segments in a cluster can therefore
be estimated by

Nc represents the number of correlated segments, and is called the correlation

mass. In a dilute solution of polymers, Nc corresponds to the
number of segments in a polymer chain. In micellar solutions, Nc corresponds
to the average number of surfactant molecules in a micelle. The
cluster size can be estimated by the length lc defined by

The length lc is called the correlation length

spatial correlation of the fluctuation in the number density:
Scattering functions
For scattering by point-like objects located at rn (n = 1, 2, . . .,N), the
scattering intensity is proportional to the following quantity

In isotropic materials, g(r) depends on r = |r| only.

For small k, sin(kr)/(kr) is approximated as 1 − (kr)2/6 + · · · .
 The scattering function
S(k) starts with Nc at k → 0, and
decreases with k for kc > 1.
This behaviour is often fitted by the
following function (often called the
Ornstein–Zernike form)

Fig. 8.3 Typical behaviour of the density correlation function

g(r), and the scattering function S(k). Panels (a) and (b)
schematicaly show how the number of correlated segments Nc
and the correlation length lc are obtained from these functions.
 Space–time correlation functions

Let rn(t) be the position of the segment n at time t. The local segment density at time t is defined by

The space–time correlation function of the segment density

Dynamic scattering function:

 The dynamic scattering function can also be measured by scattering
experiments (for example by analysing the time correlations of the intensity
of the scattered beam). The dynamic scattering function Sd(k, t)
agrees with the static scattering function S(k) at t = 0:

Dynamic scattering function written as a time correlation of nk(t) (Fourier transform of the segment density at time t ) :
 The long wavelength limit

The behaviour of the dynamic scattering function in the small k limit can be expressed in terms of
macroscopic material parameters.

the number of correlated

segments is given by

In the case of dilute polymer solutions, Π is given by (n/N)kBT, where N is the number of segments in a polymer
chain. Therefore Nc is equal to N, and the correlation effect is very large. With the increase of polymer
concentration, however, the osmotic pressure increases quickly, and Nc decreases with the increase of polymer
concentration. At high concentration, Nc becomes about the same order as that of simple liquids.
The correlation effect can be important in solutions of simple molecules, if Π’ is small. This happens
near the critical point. At the critical point, Π’ becomes zero (see Section 2.3.4). Near the critical point,
Π’ is not zero, but becomes very small. Therefore there is a strong correlation effect. This creates
various anomalies in the static and dynamic properties of the solutions, which are generally called
critical phenomena.
Correlation effects in friction constants and diffusion constants

Fig. 8.4 Comparison of the friction

constant ξ of a bed of obstacles (represented
by dots) for two situations.
(a) The obstacles are placed uniformly
in space, and (b) the obstacles are
placed non-uniformly forming clusters.
The friction constant ξ in (a) is larger
than that in (b).

The diffusion speed is determined by the balance of 2 forces: the thermodynamic

force which drives the spreading of solute molecules, and the frictional force
which resists the spreading. The former is represented by Π’ = ∂Π/∂n, and the
latter is represented by the friction constant ξ. Both parameters are affected by
the spatial correlation of solute segments.
 The correlation in the particle configuration strongly affects the friction constant ξ.

If the segments are uniformly distributed as in the case of (a), each segment acts as a hydrodynamic
friction centre, and ξ can be estimated by ξ0 = 𝒏6πηa.
On the other hand, if segments form clusters as in (b), it is the cluster which acts as a
hydrodynamic friction centre. Since the fluid velocity is strongly damped
within a cluster, the fluid cannot pass through the clusters. Accordingly,
an individual cluster behaves as a solid friction centre. Let Nc be the
mean number of obstacles in a cluster. The number density of clusters
is 𝑛 /Nc and the radius of the cluster is lc. Therefore ξ is estimated by

which is less than ξ0 by the factor lc/(aNc). Usually Nc and lc are

related by

The exponent d is called the fractal dimension. The fractal dimension

d is equal to 3 if segments are densely packed in the cluster, but is less
than 3 if they are loosely packed.
 Therefore the friction constant decreases with the increase of the cluster size.
Many phenomena are explained by this result. (i) Water moves faster through pebbles than sand
since the cluster size is larger in pebbles than sand,
(ii) colloidal particles sediment faster when they aggregate,
(iii) tiny water droplets in a cloud start to fall when their size becomes
large, and (iv) the sedimentation speed of a polymer in a solution increases with the increase of the
molecular weight.
In terms of density correlation function g(r):

This expression is known to hold in many

solutions which have long-range
the collective diffusion constant
correlation such as polymer solutions,
micellar solutions, and
solutions near the critical point.
 𝟑
𝒓~𝑵 𝟓 : polymer chain is expanded
𝟏
𝒓~𝑵 𝟐 :Polymer chain is an ideal random walk

𝒓~N for strongly stretched polymers

Kuhn’s theory of Rubber Elasticity
Change in free energy

For small strain, young’s modulus E = 3nkBT

The number density of the subchain n is expressed by using the average

molecular weight between the cross-links Mx as n = ρ/(Mx/NAv),
where ρ is the density of the rubber, and NAv is the Avogadro number.

where R=NAvkB is the gas constant.

The shear modulus (G) of a rubber is the same as the bulk modulus of a gas which has the same
number density of molecules as that of the subchain. This gives an idea of why rubber is soft.
In the case of a gas, the bulk modulus is small since the density ρ is small.

In the case of a rubber, the shear modulus is small since Mx is large. As long as the polymer
maintains the network structure, Mx canbe made very large by decreasing the cross-link density.
For example,for Mx = 104, G is about 0.25MPa, which is about the same as the bulk modulus of air.
In principle, we can make an elastic material which has nearly zero shear modulus.
Viscoelasticity in Polymers and Reptation Model
If an oscillatory strain of the form is

Phase angle response :

G’: Storage Modulus: Elastic component of the response
G’’: Loss Modulus: Viscous component of the response
Zero shear Viscosity
Section 5.5.4 of Text book 2 discussed in detail in class
Here Mx becomes Me ,
Average molecular
weight between
entanglements
Terminal time, time taken to escape the tube of length L

This is close to the

experimentally observed
value of N3.4
Hence

experimentally observed
value is N-2.3
 Modifications to reptation Theory

Why there are deviations in values of terminal time and Diffusion

coefficient from the predicted values?