3.2.

7 Dynamic light scattering

fluctuations of scattered intensity in time

due to the mutual diffusion of the polymers
in the solution
time

time

monochromatic,
coherent light

scattered
intensity
fluctuation time 

average
intensity

time
average fluctuation time
diffusion coefficient  of the polymers
hydrodynamic radius  of the polymers
time range:
-range:

picoseconds - seconds
0.01-0.04 nm-1
2

Time-resolved autocorrelation function



1
 (,
 +
)

 , 0 (,
) = lim


,


  



= 0:  , 0 (,
) =  , 0

= 

: lim  , 0 (,
) =  , 0


(,
) = 

 , 0 (,
)



mono-exponential decay


Diffusion coefficient hydrodynamic radius

 , 0 (,
) =  , 0
=

$
,
%&'

+  , 0

  , 0

 : polymer diffusion coefficient

in practice:

exp 
2
exp 2 

 , 0 (,
) = Aexp 2  
+ )

dilute PS solutions in toluene

molar mass dependence
of diffusion coefficient

figure from Rubinstein, Colby

hydrodynamic radius:

* =

+, ./01 '

Stokes-Einstein relation
s: solvent viscosity

34 = 10. 5/789 in toluene with :; = 5.6 10@A BC D

e.g. PS with 2
 = 1.3

&

F
10@$$ ;

* = 30 G7 at  = 0.01 G7@$ :  = 0.38 7D

ratio between radius of gyration and hydrodynamic radius:

IJ

IK

1.24  1.56 for N-solvent and good solvent

Chapter 4
The real chain

komplett

4.1

Introduction

4.2

Excluded volume and self-avoiding walks

4.3

Solvent quality

4.4

Polymer in a good solvent

4.5

The thermal blob

4.6

Scattering from dilute solutions of real chains

4.1 Introduction
so far neglected:
interactions between monomers
separated by many bonds
along the chain
total interaction
= number of monomer-monomer contacts
x effective monomer-monomer interaction

probability for given monomer to encounter another monomer:

number of monomers per chain x overlap concentration
mean-field idea:
consider polymer as an ideal gas
of O monomers in pervaded volume ~3

overlap volume fraction:

UO
UO
T
T
Q U

TO $

O @$ 1

TU : monomer volume
TU O: polymer volume
U : pervaded volume

i.e. probability that a given monomer

comes in contact with another monomer is very low

but the number of monomer-monomer contacts is high:

OQ O $ 1

for high O.

How does the energy arising from these contacts

affect the conformation of a real chain?

4.2 Excluded volume and self-avoiding walks

consider energy cost Y(Z)

of bringing two monomers
from to distance Z
from each other in a solvent
solvent

U
Two contributions to Y(Z)

1. repulsive hard-core barrier

due to steric repulsion of
overlapping monomers
2. attractive part
(effective monomer
-monomer interaction)

U
if monomers like each other
more than solvent:
additional attractive well
0

if interaction monomer-monomer
= interaction monomer-solvent:

only hard-core potential

athermal solvent
0

U
if monomers like solvent
more than other monomer:
additional repulsion
0

10

relative probability of
finding two monomers
separated by distance Z
in solvent at temperature [
exp Y(Z)/]^ [
(Boltzmann factor)

U
relative
probability

zero at small r

large in attractive well

2
1
0

r
11

Mayer f-function

f(r)

a Z = exp Y(Z)/(]^ [)  1

1
0
-1

no interaction
e.g. at Z

probability of finding
another monomer
is enhanced
r

excluded volume:
_   a Z U Z

12

f(r)

Excluded volume

_  1  exp Y(Z)/(]^ [)  U Z

describes the net two-body

interaction between two
monomers in a solvent

-1

hard-core repulsion
(for small Z):
positive contribution to _

attraction between monomers

(for large Z):
negative contribution to _

_ > 0: net repulsion

_ < 0: net attraction

13

4.3 Solvent quality

athermal solvents: _ = T U
only hard-core repulsion
e.g. polystyrene in ethyl benzene
(same chemical structure)
_ is equal to geometric volume
_ is not [-dependent
good solvents: 0 < _ < TU
monomer-monomer attraction slightly
stronger than monomer-solvent attraction
because dispersion forces favor identical species
net attraction, small attractive well
e.g. polystyrene in benzene

for decreasing temperature, _ decreases

14

theta solvents: _ = 0
at -temperature
contribution from attractive well
equal to the one from hard-core repulsion
nearly ideal chain conformation
e.g. polystyrene in cyclohexane at = 34.5C
nearly ideal chain conformation
poor solvents: T U < _ < 0

at [ < N, attractive well dominates

monomers more close together
e.g. polystyrene in ethanol
collapsed chain conformation
15

non-solvents: _ = T U
limiting case of poor solvent
polymer has strong preference for its own monomers
nearly all solvent excluded
e.g. polystyrene in water

16

4.4 Polymer in a good solvent

conformation of real chain in athermal or good solvent:
swelling of the chain due to repulsion energy between monomers
but entropy loss due to increased end-to-end vector
consider chain with  >  = TO$/
energetic cost of O monomers being excluded
g
from all other monomers: def ]^ [_O h
I

number of monomer-monomer contacts:

ih g
O h
I

= TU O

g
Ih

_ T U is a measure of the interaction

mean-field assumption: monomers evenly distributed
(This is an approximation.)
17

entropic contribution to free energy

I&
]^ [ &
gi

of real chain: djf

(approximation: ideal chain statistics is used)
energy required to stretch an ideal chain:
O

d = def + djf ]^ [ _ U +

OT 
From

kl
kI

= 0, the minimum of the free energy is found

and leads to

l _ $m Tm O Um .

18

PS in the good solvent benzene: n O .mo

PS in the theta solvent cyclohexane: n O .m
from Rubinstein, Colby. Data compiled by L.J. Fetters, J. Phys. Chem. 1994
19

4.5 The tension blob

For the ideal chain:  TO $
This holds also for subsections of the chains
of size Z containing G monomers: Z TG$

stretch with force a

the subsections (blobs) do not know that they are stretched

20

subdivide each chain into blobs of size

containing 5 monomers each
on length scales smaller than , chain statistics unperturbed
on larger length scales: fully extended arrays of tension blobs
p T5$

p
5=
T

end-to-end distance Rf in stretched state:

p: blob size,

O/5: number of blobs

q p

g
n

coefficients of order unity are neglected

OT  

q

p
p
p
q
21

The free energy for stretching of the chain is ~])[/T98T

g
]^ [
n

]^ [

Ir

kl(g,Ir )

a=

+, - Ir
It It

d(O, q )

q
d(O, q ) ]^ [


force: a =

kIr

O/5: number of blobs

qi
+, -

Ir

gi

log (a)
])[/T

ideal:
slope 1

a is proportional to q

])[/8
8

7Cw

log (a)
22

The tension blob for the real chain

mU

p
m
m
U
U
l TO
p T5
5=
T
end-to-end distance for the stretched chain:

OT mU lm U
lm 
q U U p U
p
p

q

free energy for stretching of the chain:

force: a =

+, - Ir U
Ix Ix

qi
+, -

Ir U

gi

d(O, q ) ]^ [

Ir m/

Ix

a is non-linear with q

23

log (a)
])[/T

ideal:
slope 1

])[/8

real:
slope 3/2

])[/d
8

d

7Cw

log (a)

aZyC9 < azyC9

because the real chain loses less entropy upon stretching
Reason: In the unstretched state, the real chain
has already lower entropy than the ideal chain.

24

4.6 Scattering from dilute solutions of real chains

: fractal dimension of the chain

 = 1/|
ideal chain:  = 1/(1/2) = 2

real chain:  = 1/(3/5) = 5/3

for high q-values ( 1/): intramolecular scattering

{() G% , G% : number of monomers in volume 1/3
{() (T)@'

25

for low -values ( 1/): {  = O

coincides with {  =

I}
~t

for high q-values ( 1/): {  =

$
%

coincides with Debye form factor in the case of ideal chains

26