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BW Theory

Kunal Garg
Introduction
Calculation

Bragg Williams Approximation

Conclusion

Kunal Garg
National Institute of Science Education and Research
kunal@niser.ac.in

March 31, 2015

Bragg Williams Approximation


BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

The crucial idea behind the model of Bragg and Williams is the
introduction of the order parameter to describe the degree of
order in the system at various temperatures; the free energy of
the system is then described in terms of this order parameter;
finally, the equilibrium of the system is determined by
minimising the free energy with respect to the order parameter.
More specifically, the order parameter gives the probability of
occupation of the given sites at the given temperature. In more
complex ordered structures, more than one order parameter is
needed to carry out the analysis.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

Bragg Williams Approximation is basically a mean field


model.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

Bragg Williams Approximation is basically a mean field


model.
Under certain conditions, BW theory reduces to Landaus
Mean Field theory.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

Bragg Williams Approximation is basically a mean field


model.
Under certain conditions, BW theory reduces to Landaus
Mean Field theory.
We use it here to determine mps for our model. mps polymer-solvent contacts.

Approach
BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

We make the assumption that polymers and solvent


molecules mix randomly on the surface.
Now to get mps , we need to calculate the probability of
P S contacts for random mixing.
This is called the Bragg Williams Approximation.
The expression for energy of mixing we have is


ss + pp
Umix = Usolution Uunmixed = ps (
) mps
2
Where is the energy of the contact.

Calculation
BW Theory

Probability that a lattice site contains a polymer segment is :

Kunal Garg
Introduction
Calculation
Conclusion

P =

Nnp
M

Calculation
BW Theory

Probability that a lattice site contains a polymer segment is :

Kunal Garg
Introduction
Calculation

P =

Nnp
M

Conclusion

For a single solvent molecule, average number of polymer


contacts is :


Nnp
#of contacts = Z P = Z
M

Calculation
BW Theory

Probability that a lattice site contains a polymer segment is :

Kunal Garg
Introduction
Calculation

P =

Nnp
M

Conclusion

For a single solvent molecule, average number of polymer


contacts is :


Nnp
#of contacts = Z P = Z
M
Thus total number of contacts is


Nnp
mps = ns Z
M

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

This gives us a new expression for energy of mixing:




ss + pp
Znp N
Umix = ps (
) ns (
)
2
M

BW Theory
Kunal Garg
Introduction
Calculation

This gives us a new expression for energy of mixing:




ss + pp
Znp N
Umix = ps (
) ns (
)
2
M

Conclusion

We define Flory-Huggins parameter as:




ss + pp
Z
ps (
)
=
kT
2
This is a unitless energy parameter.

BW Theory
Kunal Garg
Introduction
Calculation

This gives us a new expression for energy of mixing:




ss + pp
Znp N
Umix = ps (
) ns (
)
2
M

Conclusion

We define Flory-Huggins parameter as:




ss + pp
Z
ps (
)
=
kT
2
This is a unitless energy parameter.
Thus the change in internal energy now reduces to:
Umix ' Hmix =

kTns Nnp
= kb T s p M
M

Concluding Result
BW Theory
Kunal Garg
Introduction
Calculation

Now this result combined with molecular scale model gives us


expression for free energy of mixing for the regular solution:

Conclusion

p
Gmix
= p s + s lns +
lnp
kTM
N
np N
.
M
Here first term is the enthalpy and second and third term
constitute the entropy.
where p =

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

This theory is used to predict new behaviours in polymers


in this model.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

This theory is used to predict new behaviours in polymers


in this model.
BW can also help to understand phase transitions
appearing in Ising model of ferromagnetic to paramagnetic
transition. This is a second order phase transition.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

This theory is used to predict new behaviours in polymers


in this model.
BW can also help to understand phase transitions
appearing in Ising model of ferromagnetic to paramagnetic
transition. This is a second order phase transition.
It also helps in understanding Transition in gravity theories
from ordinary phase (or Anti deSitter phase) to a black
hole phase. This is an example of first order phase
transition.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

This theory is used to predict new behaviours in polymers


in this model.
BW can also help to understand phase transitions
appearing in Ising model of ferromagnetic to paramagnetic
transition. This is a second order phase transition.
It also helps in understanding Transition in gravity theories
from ordinary phase (or Anti deSitter phase) to a black
hole phase. This is an example of first order phase
transition.
While in one case, magnetisation works as the order
parameter, for black hole, it is the horizon radius acts as
the order parameter.

BW Theory
Kunal Garg
Introduction
Calculation
Conclusion

Thank You