Introduction to Polymer Theory

Gert Jan Vroege

Van t Hoff Laboratory for Physical and

Colloid Chemistry
Utrecht University
The Netherlands

Introduction
chemical details vs. universal properties

A polymer is a statistical mechanical system,

for which the role of entropy is very important

Programme
1. Ideal polymers:
conformations: Gaussian coil
in an external field
in a Self Consistent Field (SCF)
2. Non-ideal polymers
excluded volume
attractions
3. Concentrated solutions:
Flory-Huggins theory
scaling theory (semi-dilute solutions)

Polymer conformations
segment
End-to-end vector
bond length
bond vector

End-to-end vector: R =

N
i =1

R =0

ri

Polymer conformations
End-to-end vector: R =

ri

i =1

= RR =

i =1 j =1

N
i =1

ri 2 +

R2 N
R 2 N 1/ 2

N
i =1 j i

ri rj
ri rj
smaller if j-i larger

Chain models (1)

Freely jointed chain:

ri 2 = ri ri = b 2
ri rj = 0 (i j )

R2 =

N
i =1

ri 2 +

N
i =1 j i

ri rj = Nb 2 ( + 0 )

Chain models (2)

Freely rotating chain:

ri 2 = ri ri = b 2
ri ri +1 = b 2 ( cos )

ri ri + 2 = b ( cos )
2

ri rj = b 2 ( cos )

j i

Chain models (3)

R

N
i =1

b 1 + ( cos ) + ( cos ) + ( cos ) +

1

= Nbeff

1 + cos
= Nb
1 cos
2

1 + cos
with beff b
1 cos

General result when NO INTERACTION between segments

R 2 = Nbeff 2

with more general beff

End-to-end distribution (1)

P( R, N ) : probability of finding R after N segments?
recursion relation:
P( R, N ) = P( R rN , N 1)

Taylor expansion (N

1 and R

rN

rN ):

P
P
P( R rN , N 1) P( R, N ) +
rN , )
( 1) +
(
N
= x , y , z
1
2 P
+
rN , ) ( rN , ) +
(
2 = x , y , z = x , y , z

End-to-end distribution (2)

apply

rN

rN

rN

=0

rN rN
rNx 2

rN

rN

= rN

= rN y 2

rN

rN

rN

= rNz 2

rN

rN

=0
1
= b2
3

( )

End-to-end distribution (3)

P
2
2
1 2
+ 2 + 2 P+
P ( R, N ) P ( R, N ) +
( 1) +
2
6 x
N
y
z

2
2
2
With the definition of the Laplacian 2 + 2 + 2
x
y
z
we thus find that P ( R, N ) is the solution of:

P( R, N ) b 2
= P( R, N )
N
6
cf. the diffusion equation for c( R, t ) :
c( R, t )
= Dc( R, t )
t

End-to-end distribution (4)

Cf. one diffusing colloidal particle (Einstein):

R 2 = 6 Dt
b2 N

An (ideal) polymer is like the trajectory of a diffusing particle!

End-to-end distribution (5)

P( R, N ) b 2
The solution of
= P( R, N ) is (by analogy):
6
N

3
P ( R, N ) =
2 Nb 2

3/ 2

3R 2
exp
2 Nb 2

Central Limit Theorem

Consider the sum of N independent, stochastic variables (N is large).
This sum has a normal (= Gaussian) distribution with 2 N .

R=

N
i =1

ri

Variation in R 2 :

R =
2

R =
2

R0

(R

= R 2 N ( beff 2 )

2 2
=
Nb
3

A Gaussian coil is a strongly fluctuating object!

Conclusion: many (global) properties of polymers do not

depend on the (local) details of the model.

Entropy of a Gaussian coil

S ( R) = k B ln W
= cst + k B ln P( R)
3k B 2
= cst
R
2
2 Nb
3k BT 2
A( R) ( = TS ) = cst +
R
2
2 Nb

ENTROPIC SPRING

Conditional probability

probability

conditional probability

P( R, N ) = GN ( R | 0)

GN ( R | R)

independent end points: G ( R | R) GN ( R | R)

integrate over R

GN ( R | R)

(OK for Gaussian chains)

Additional polymer models

Gaussian bond model:

Every single bond Gaussian exp

3 r i2
2 (1) b 2

Bead-spring model:
3k BT
spring constant:
2 (1) b 2
(used in the Rouse/Zimm models for polymer dynamics)

Continuous model:
permits the use of path integrals

A polymer in an external field (1)

assume a segment at position R has energy ( R)
the recursion relation now changes to:
P( R, N ) = P ( R rN , N 1)

rN

exp

( R)
k BT

Taylor expansion:
P
P( R rN , N 1) P ( R, N ) +
( 1) +
N

etc. 1

( R)
k BT

P b 2
( R)
P
= P
k BT
N 6

cf. diffusion in an external field

A polymer in an external field (2)

similarly for the conditional probability GN ( R | R)
G
b2
( R)
G

= G +
6
k BT
N

R is a parameter, but: R R

cf. i
=
+ V ( R)
2m
t

( )

QM: time-dependent Schroedinger equation for R, t

linear, partial differential equations; solution method:

separation of variables

Separation of variables
G
b2
( R)
G

= G +
6
k BT
N

assume G can be written as: G = f ( N ) ( R)

f ( N )
b2
( R)
f ( N ) ( R) +
f ( N ) ( R)
( R)
=
6
k BT
N
divide by f ( N ) ( R) :
1 f ( N )
b 2 ( R) ( R)
=

=
+
f ( N ) N
6 ( R)
k BT

f ( N ) = c exp ( N )

eigenvalue equation

b2
( R)
( R) = ( R)
( R) +
6
k BT

eigenvalues n , complete set (orthogonal) eigenfunctions n ( R)

G = n ( R) exp ( n N )

or any linear combination for different n

A polymer in an external field (3)

linear combination: GN ( R | R) =
using R R
bilinear expansion: GN ( R | R) =

cn n ( R) exp ( n N )

n ( R ) n ( R) exp ( n N )

b2
( R)
n ( R) = n n ( R)
where n ( R) +
6
k BT
1) continuous spectrum of eigenvalues

example: ( R) = 0

k = eik

here we need all eigenfunctions

and k = 16 b 2 k 2
Gaussian coil

A polymer in an external field (4)

bilinear expansion: GN ( R | R) =
n

n ( R) n ( R) exp ( n N )

2) discrete spectrum of eigenvalues

lowest eigenvalue 0 dominates for large N

GROUND STATE DOMINANCE
GN ( R | R) 0 ( R) 0 ( R) exp ( 0 N )
chain ends are decoupled!

A polymer in an external field (5)

segment density c( R) ?
integrate over: beginning
end

c( R)

( )

N 0 R

cf. QM: bound state

A polymer in an external field (6)

Lifshitz entropy: derivation

(for ground-state dominance)

Partition function Z : # conformations

(weighed with Boltzmann factors exp( ( R ) / k BT ))

Z = dR dRGN ( R | R)
Z

0 N

dR 0 ( R)

GN ( R | R) 0 ( R) 0 ( R) exp ( 0 N )

end effects
free energy:

A = k BT ln Z

k BT 0 N + end effects

entropy:
UA
1
S=
( R)c( R) dR k B 0 N
=
T
T

use c( R)

N 0 2

and the eigenvalue equation

and eliminate 0

Lifshitz entropy: result

1 2
S = Nk B b 0 ( R ) 0 ( R) dR
6
2
1 2
S = Nk B b 0 ( R ) dR partial integration using
6
1 2
S = k B
b
24

[ c ( R ) ]

c( R)

dR

using c( R)

N 0 2

independent of ( R)
also valid for a collection of polymers
S decreases because of concentration gradients
S = S[c( R)] ( S is a functional of c( R))

Self-consistent field method

this method incorporates inter-segment interactions:
free energy:
A[c( R)] = U [c( R)] TS [c( R)]
U [c( R)] represents e.g. a non-ideal gas of segments

ceq ( R) is then obtained by functional minimization

THIS APPROACH NEGLECTS FLUCTUATIONS/CORRELATIONS !

Non-ideal polymer chains

U [c( R)] = Nk BTB c( R )
B is the second virial coefficient (B > 0 repulsion)

Edwards (1965): R 2 N 6/ 5
swelling
PURE REPULSION
total number of configurations (depending on R)
2
3
R
P( R, N ) 4 R 2 exp
2 Nb 2
but a certain fraction of these configurations is "forbidden":

p( R) 1

c
R3

N ( N 1) / 2

N 2 c
exp
2 R3

Non-ideal (repulsive) polymer chains

free energy:
A( R)
S ( R)
=
= ln [ p( R ) P( R, N ) ]
k BT
k BT
N 2 c
3R 2
cst 2 ln R +
+
2
2 Nb
2 R3

minimize A( R) with respect to R

c = 0 : R0* N 1/ 2b
c 0:
N

R
R0*
*

R
*
R0
*

c
b

N 1/ 2

Flory

1 : R* R0* N 1/10 N 3/5b SWELLING !

RG theory / simulations : R* N 0.588b

Repulsion combined with attraction (1)

Assumptions:
only attraction between nearest neighbours
coordination number: z

solvent-solvent
solvent-polymer
polymer-polymer
random pair contacts:

Repulsion combined with attraction (2)

attractive energy within a coil:

U attr = N c c( R) z ( )
( c c( R) is the probability to find a neighbouring segment)
U attr
N2
z
= 3 c
R
k BT
k BT

z
where
(chi-parameter)
k BT
usually > 0

N 2 c
A( R)
Compare with repulsive term in
, which was:
k BT
2 R3

c c (1 2 )

R
R0*
*

R
*
R0
*

c
b

1/ 2
1
2

N
)
3 (

Flory

Repulsion combined with attraction (3)

R
R0*
*

R
*
R0
*

c
b

1/ 2
1
2

N
)
3 (

Flory

CONCLUSION:
at = 0 swollen chain R* N 3/5
at = 1/ 2 ( - temperature): ideal chain R* = R0* N 1/ 2
1 cst
right-hand side only small if =
i.e. abrupt change if N large
2
N

> 1/ 2 : globule (bound state, cf. QM) R* N 1/3

in general R *

b N

Repulsion combined with attraction (4)

polystyrene in cyclohexane

Concentrated polymer solutions

c*
N
N
c* 3
3
R
(bN )

N 1/ 2 N 4/5
b

FLORY-HUGGINS:
concentrated systems: S ( R )

NO

homogeneous systems: SLifshitz

NO
YES

random mixing ( places)

very small !

Flory-Huggins theory (1)

translational entropy: Str , sp k B sp ln sp
polymer: Am, p k BT
solvent: Am, s

( sp = species )

ln

N
k BT (1 ) ln(1 )

Am k BT

1
ln + (1 ) ln(1 ) + (1 )
N

Flory-Huggins theory (2)

c =

1
1+ N

(highly) asymmetric

1
1
Tc follows from c +
2
N
Tc for large N , i.e. near the coil globule transition
note that fluctuations are neglected!

Polystyrene in methylcyclohexane

Scaling theory

Semi-dilute solution (good solvent)

N
4/ 5
* b c* b

N
(bN 3 / 5 )3
3

OSMOTIC PRESSURE

still very small !

TYPICAL LENGTH SCALE

DILUTE
c
( = R ) = bN 3/5
= k BT
N
m
m
c
SEMI-DILUTE
k BT
3/5
bN
(power law)
N *
*
c 4/5m m
3/5 4/5m m
independent of N
k BT
N

bN
N
1
N
m = 5/4
m = -3/4
k BT 9/4
5/4
k BTc

3
b 3/4
b
des Cloizeaux
de Gennes

What is the meaning of ksi ? (1)

Flory-Huggins:

k BT 2

3
b

k BT

3
b

k BT 9/4 k BT
5/4
des Cloizeaux:

b3
b3
probability of segment probability of contact w
probability of contact w: lower for scaling theory (correlations!)

Flory-Huggins:

des Cloizeaux:

What is the meaning of ksi ? (2)

on one chain: number of segments between contacts?

w 1

g monomers: g
bg

3/ 5

b (

5/ 4 3/ 5

5 / 4

b 3/ 4

distance between chain contacts !

1) volume fraction within one blob:

gb3

5 / 4b3
(b 3/ 4 )3

blobs touch !

What is the meaning of ksi ? (3)

2) a SEMI-DILUTE SOLUTION
is a collection of BLOBS !

3) des Cloizeaux:

4)

de Gennes:

b 3/4

k BT 9/4

3
b

k BT

blobs are the osmotic units

is also the screening length for the excluded volume

5) 1: ( b 3/ 4 ) b
chains in polymer melts are ideal! (Flory)