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(, )
, = ln 3 (, ) + ln ,
2
3
, =
+ (, 0)
2
2
the higher ,
the lower the entropy
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
http://www.thenakedscientists.com/HTML/experiments/exp/heat-shrink/
Chapter 3
Methods for the
characterization of polymers
3.1
3.1.1
3.1.2
3.1.3
Size-exclusion chromatography
Osmometry
Light scattering
3.2
3.2.1
3.2.2
3.2.3
3.2.4
3.2.5
3.2.6
3.2.7
Rubinstein, Colby
determine
average molar mass
molar mass distribution
in dilute solution
for instance
,
, molar mass distribution
size exclusion chromatography
osmometry
light scattering
detector
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)
Mn = 183000 g/mol
= 1.10
Mn = 54500 g/mol
= 1.07
Elution volume / ml
3.1.2 Osmometry
osmotic pressure:
thermodynamic colligative property,
i.e. sensitive to the
number of polymers present
h
membrane
solution
solvent
membrane permeable
for solvent only
lim
lim =
=
+ 2, +
2, : weight-average
second virial coefficient
9
poly(-methylstyrene)
in toluene at 25C
axis cut at 1
106
slope = 2,
[/]
2, > 0
increases with
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
, = cos 2
scattered amplitude:
4 2
= 2 cos 2
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
4 2 2
=
= 4 2
Rayleigh ratio:
2 4 2 2
1
= 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
106
1/
22
2 2 + 100
concentration dependence of
scattered intensity leads to
determination of
15
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
refractive index
(@ = 546 nm)
1.59
1.56
poly(dimethylsiloxane)
1.40
water
1.33
toluene
1.50
17
18
polystyrene
(nm-3)
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
:
:
:
:
:
12
10
8
6
4
2
0
PS
PDMS
H2O
toluene
19
KWS-1, FRM II
20
Element
1
H
D
C
O
Si
Scattering length bi
[10-12 cm]
-0.37
0.67
0.66
0.58
0.41
21
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
PS
dPS
PDMS
H2O
D2O
22
: scattering centers
=
23
/2
scattering vector
elastic scattering:
2
= =
= = 2 sin
=
sin