Professional Documents
Culture Documents
( )
N V
i' =
( )
I0 8
4 4
( )
2
1 + cos 2 r
2
(10.46 )
# scatterers
per unit volume
TO A FIRST APPROXIMATION
1 = 2
( dn ) M dc A
FLUCTUATIONS
Pure liquids - density Solutions - concentration . . . . . .
= 1 ( 1 + 22c + ------ ) Mw
K (1 + cos 2) c R
0
(10.59)
But a polymer is too large to Be considered a single oscillator (ie a point source of radiation). Must consider interference effects
Incident beam B
P2 P1
ZIMM PLOT
K (1 + cos 2) c 2 = 1 ( 1 + 22c + --- ) 1+ S sin 2 R Mw
Experimentally measured parameters
5
( ))
= 0 line
Virial Expansion
c = 0 line
100 c + sin
( ) 2
0.8
1.0
1.2
Pr = 8 l
where P is the pressure difference maintaining the flow, r and l are the radius and length of the Capillary and is the viscosity of the liquid.
Relative Viscosity
Defined as the viscosity of a polymer solution divided by that of the pure solvent and for dilute solutions:
t rel = t 0 0
where t is the time taken for a volume V of solution (no subscript) or solvent (subscript 0) to flow between the marks.
1.6
+ ......
Plot of rel versus c for PMMA in chloroform. Plotted from the data of G. V. Schultz and F. Blaschke.
If viscosity measurements are confined to dilute solution, so that we can neglect terms in 3 and higher: c
rel - 1 c
1 = c
- 0 0
-1
= [ ] + k c
sp =
rel
Note also that as c goes to zero (infinite dilution), then the intercept on the y-axis of a plot of ( sp/c ) against c is the intrinsic viscosity, []:
[] =
( c )
sp
c 0
ln rel 2 = [ ] + k"[ ] c c
sp ln or c rel c
sp c
sp c
sp ln or c rel c
[]
[]
ln rel c
ln rel
c
Concentration, c (g/dl)
0.25
Concentration, c (g/dl)
0.25
If the log of the intrinsic viscosities of a range of samples Schematic diagram of the Determination of the Mark-Houwink-Sakurada constants is plotted against the log of their molecular weights, K and "a". then linear plots are obtained that obey equation:
[] = KM
a
Monodisperse standards
Temp
log []Solvent
3
PS
PMMA
Intercept = log K log M
Slope = a
Log []
1 1
0 4 5 6 7 4 5 6 7
Plots of the log [h] versus log M for PS and PMMA. Replotted from the data of Z. Grubisic, P. Rempp and H. Benoit
Note that KKand "a" are not universal constants, Note that and "a" are not universal constants, but vary with the nature of the polymer, but vary with the nature of the polymer, the solvent and the temperature. the solvent and the temperature.
( sp )
i
( sp)
ci
=KM
a
i
Hence: sp =K
Ma c
i i
And:
K sp [] = c =
Ma c
i i
Mv =
N i Mi i N i Mi
i
(a +
1)
Note that the Viscosity Molecular Weight is Not an Absolute Measure as it is a function of the solvent through the Mark-Houwink parameter "a".
FRACTIONATION
POLMER SOLUTION
COLUMN
Injection Port
Void Volume
Mixing Valve SEC Columns
Pump
Pores
Detectors
For aagiven volume of solvent flow, molecules of different size travel different pathlengths For given volume of solvent flow, molecules of different size travel different pathlengths within the column.The smaller ones travel greater distances than the larger molecules due within the column.The smaller ones travel greater distances than the larger molecules due to permeation into the molecular maze.Hence, the large molecules are eluted first from the to permeation into the molecular maze.Hence, the large molecules are eluted first from the column, followed by smaller and smaller molecules. column, followed by smaller and smaller molecules.
wi = 1
wi
Intensity
Concentration
Monodisperse Standards
Elution Volume
Vi
wi =
Mw =
Total Permeation
hi
w i Mi
hi
Mn =
Vi Elution Volume
wi Mi
a
[] =
w i [i ] = K w i Mi
Star-shaped PolyA
Linear PolyA
Elution Volume
VA L
A VS
VB L
If we model the properties of the polymer coil in terms of an equivalent hydrodynamic sphere, then the intrinsic viscosity, [], is related to the hydrodynamic volumehV via the equation: Benoit and his coworkers recognized that the product Benoit and his coworkers recognized that the product 2.5 A V of intrinsic viscosity and molecular weight was directly h of intrinsic viscosity and molecular weight was directly [] = M proportional to hydrodynamic volume. proportional to hydrodynamic volume.
A is Avogadro's number and M is the molecular weight.
10
linear polystyrene linear PMMA log linear PVC polystyrene combs polystyrene stars PS/PMMA graft copolymers (comb) PS/PMMA heterograft copolymers Poly(phenyl siloxane) ladder polymers PS/PMMA statistical copolymers
8 Log [] M 7
5 18
20
22
24
26
28
30
Elution Volume
A universal calibration plot of log []M vs elution volume for various polymers. Redrawn from the data of Z. Grubisic, P. Rempp and H. Benoit.