2.

11 Free energy of an ideal chain

entropy: = ln , : number of states
(, ) = ln (, )

(, ): number of conformations of a freely jointed chain

having monomers and the end-to-end vector
3 , =

(, )

, = ln 3 (, ) + ln ,
2
3
, =
+ (, 0)
2
2

the higher ,
the lower the entropy

Helmholtz free energy

= .

No interactions , = 0

2
3
, =
+ (, 0)
2 2

elastic force
when separating the chain ends by in direction:
,
3
=
=

entropic elasticity
origin of rubber elasticity

elastic spring constant

increases with increasing

http://www.thenakedscientists.com/HTML/experiments/exp/heat-shrink/

Chapter 3
Methods for the
characterization of polymers
3.1

Measurement of molar mass

3.1.1
3.1.2
3.1.3

Size-exclusion chromatography
Osmometry
Light scattering

3.2

Measurement of the radius of gyration

3.2.1
3.2.2
3.2.3
3.2.4
3.2.5
3.2.6
3.2.7

Contrast in scattering experiments

Scattering wave vector
Form factor
Zimm plot
The Guinier approximation
The Debye function
Dynamic light scattering

Rubinstein, Colby

3.1 Molar mass measurements

determine
average molar mass
molar mass distribution
in dilute solution
for instance
,
, molar mass distribution
size exclusion chromatography

osmometry

light scattering

3.1.1 Size-exclusion chromatography (SEC)

or gel permeation chromatography (GPC)
measurement of molar mass distribution
column

detector

continuous solvent stream through column

consisting of swollen polymer beads
pores with wide size distribution
polymer solution is injected at given time
detection: refractive index, UV, IR, light scattering, viscosity

 measurement of time when polymer

of certain molar mass passes column
conversion of time to elution volume
by means of a siphon
calibration curve molar mass vs.
elution volume

large polymers
are excluded from all but the largest pores
elute from column first
small polymers
explore also smaller pores
elute later
separation by polymer size

challenges/problems:
choice of solvent
choice of column material
(avoid adsorption of
polymers to wall)

Differential refractive index

Mn = 183000 g/mol
= 1.10

Mn = 54500 g/mol
= 1.07

Elution volume / ml

measurement of the polymer under question

convert distribution of elution volumes
to distribution of molar masses by
means of the calibration curve
(for chemically different polymers:
only apparent molar mass values!)
,
, dispersity obtained by

weighted integration over the peaks

peak shape synthesis mechanism,
or possible problems during synthesis

3.1.2 Osmometry
osmotic pressure:
thermodynamic colligative property,
i.e. sensitive to the
number of polymers present

h
membrane

free energy difference between

polymer solution and solvent
free energy gain upon mixing

solution

solvent

membrane permeable
for solvent only

solvent flow into solution

until chemical potential equal
difference in (osmotic) pressure

vant Hoff law:

=
0

R: gas constant, R = 8.314 J/(molK)

T: absolute temperature

lim

for polydisperse polymer solution:

lim =

osmometry determination of the number-average molar mass

measurements at various low concentrations
extrapolation to c = 0
because polymer-polymer interactions
1

=
+ 2, +

2, : weight-average
second virial coefficient
9

poly(-methylstyrene)
in toluene at 25C

axis cut at 1

106

slope = 2,

data from I. Noda et al.,

Macromolecules 16, 668 (1981)
replotted by Rubinstein, Colby

[/]

2, > 0

increases with

repulsion between polymers (and vice versa)

10

3.1.3 Light scattering

laser
sample

detectors:
avalanche
photodiodes

,
determination of the weight-average molar mass,
and of the second virial coefficient, 2 ,
by measuring the intensity of the scattered light
at small scattering angles
at small angles, polymers look point-like
Rubinstein, Colby

11

Scattering from gases

gas of small, non-interacting particles in scattering volume
vertically polarized laser beam
incident wave

, = cos 2

scattered amplitude:
4 2

= 2 cos 2

intensity of light scattered by

= particles per Volume :

16 4
=
4 2 2

2 = 2 + 2
:
:
:
:
:
:
:
:

polarizability of molecule
sample-detector distance
wavelength in vacuum
frequency
speed of light
particle concentration (g/l)
Avogadros constant
intensity of incoming wave
12

Scattering from a dilute polymer solution

for small scattering angles: polymers point-like
change of refractive index for low concentration: 2 = 02 + 4
/

4 2 2
=
= 4 2

0: refractive index of solvent

Rayleigh ratio:
2 4 2 2
1

with the optical constant

4 2 2

= 4

13

polydisperse sample: =

measurement of weight-average
by plotting the inverse scattered intensity
vs. the polymer concentration
and by extrapolation to = 0:
2 2

interacting polymers
concentration fluctuations

osmotic compressibility

1
=

1
=
+ 22 +

14

plot (measured at very small )

vs. polymer concentration
slope = 22

106

This is part of the Zimm plot:

1/

22

2 2 + 100

concentration dependence of
scattered intensity leads to
determination of

the weight-average molar mass

the second virial coefficient

15

3.2 Measurement of the radius of gyration

assumption so far:
scattering angles (vectors) so small
that polymers seem point-like
determination of molar mass
and second virial coefficient

Rg

now:
extend range to
higher scattering vectors

determination of
radius of gyration and
second virial coefficient
16

3.2.1 Contrast
light scattering: light source typically a laser

in the visible range (400-800 nm)

detection angle typically

in the range = 30 150
light interacts with electrons

scattering contrast due to

refractive index difference
between polymer and solvent
substance
polystyrene
polybutadiene

refractive index
(@ = 546 nm)
1.59
1.56

poly(dimethylsiloxane)

1.40

water

1.33

toluene

1.50

values quite similar

contrast weak

17

Small-angle X-ray scattering

lab instrument: usually Cu anode: = 0.154

synchrotron: very intense beam, variable wavelength

(high flux, microbeams, sometimes sample damage?)

18

Contrast in X-ray scattering

interaction of X-rays with electrons
contrast due to difference in electron density

polystyrene

(nm-3)

number of electrons per monomer

scattering length of an electron: = 2.80 106
Avogadros number
monomer molar mass
electron density

X-ray SLD
(10-4 nm-2)

337

9.44

polybutadiene

296

8.28

polydimethylsiloxane

485

13.6

H2 O

334

9.35

toluene

285

7.98

14

X-ray SLD (10-4 nm-2)

:
:
:
:
:

12
10
8
6
4
2
0

PS

PDMS

H2O

substances with high electron density scatter X-rays strongly

toluene

19

Small-angle neutron scattering

source: reactor (e.g. FRM II) or spallation source (e.g. ORNL)
distribution of wavelengths ( 0.05 4.5 )
sample-detector distance 2 20 large -range accessible

KWS-1, FRM II

heatable sample cell

20

Contrast in neutron scattering

interaction of neutron with nucleus
contrast due to difference in
nuclear scattering length density /

: scattering length, i.e. strength of neutron/nucleus interaction

Element
1

H
D
C
O
Si

Scattering length bi
[10-12 cm]
-0.37
0.67
0.66
0.58
0.41

21

Contrast in neutron scattering

Polymer
polystyrene
fully deuterated PS
H 2O
D2O

molar
mass
[g/mol]
105
112
18
20

mass
density
[g/cm3]
1.05
1.13
1.00
1.11

b (neutrons)
[10-5 nm]

neutron SLD
[10-4 nm-2]

2.33
10.65
-0.16
1.92

1.40
6.45
-0.53
6.39

neutron SLD (10-4 nm-2)

strong contrast between

protonated and
deuterated substances

PS

dPS

PDMS

H2O

D2O

22

3.2.2 Scattering vector

A

: scattering centers

incident wave vector:

scattered wave vector: =

difference in optical paths: =

phase difference =

=
23

/2

scattering vector

elastic scattering:
2
= =

= = 2 sin
=

sin

range of momentum transfers q:

light scattering: ( = 546 , = 30 150)
= 104 0.03 1 1 = 33 10
SAXS/SANS: ( = 0.1 , = 0.005 1.8)
= 5 103 2 1 1 = 0.5 200

SAXS/SANS and light scattering allow measuring small length scales

gain information about inner structure of polymer (conformation)
24