Direct Measurements Of Average

Molecular Weights
Mn and Mw can be measured directly without
knowing the full MWD; not Mz
Primary versus Secondary methods

Membrane
Osmometry
(MN )

Intrinsic
viscosity
GPC / SEC

Light scattering
( MW )
Ultracentrifugation ( M Z )
for biological polymers

Polymer Characterization

SIZE
Length, radius, characteristic dimension
MW and MWD

SHAPE
Coil, sphere, rod

CONFORMATION
Extended, compacted, cross-linked

CONSTITUTION
Functional groups, branches, distribution of
blocks in copolymers

MW Characterization Techniques
MN methods
Boiling point elevation
Freezing point depression
Vapour pressure change
Osmotic pressure change
End-group analysis

information on
solution
thermodynamics

MW methods
Light scattering
Sedimentation, centrifugation
MV methods
Viscometry
MWD methods
Chromatographic techniques
Size exclusion chromatography (SEC)
Gel permeation chromatography (GPC)

PRACTICAL ASPECTS OF
MW MEASUREMENTS
MN METHODS
A) End-group analysis
MW is determined by chemical analysis of reactive
functionalities in polymer
e.g. polyester, titration of alkali
Major drawbacks: precision of the analysis;
restricted to MW 10,000 g/mol; assumptions
about structure
Condensation polymers

B) Colligative methods
Rely on colligative solution properties; depend on
the number of dissolved solute molecules and not
on their sizes
Depend on the lowering of the chemical potential
of a solvent by introduction of a solute
Solution thermodynamics

Property measured

Technique

Vapour pressure reduction VPO

Lowering of freezing point
Cryoscopy
Elevation of boiling point
Ebulliometry
Osmotic pressure
Membrane
osmometry

Membrane osmometry
Osmotic pressure
=hg
oA (T,P) = A (T, P+, xA)

Ideal solutions

RT
=
c
M

Vant Hoff Equation

Non-ideal solutions

= R T[

1
Mn

+ A2 c + A3 c 2 + ... ]
Virial equation

Practical range of MW's :

30,000

membrane
permeability

1,000,000

smallest

Membranes
open versus fine membranes
cellophane / PTFE -rays

Instrumentation
- Static
- Dynamic

Osmotic Pressure
In ideal solutions
expressed as

cm RT
Molar concentration

RT
MV
Mass
concentration

RT
M
37

Molecular Weight Determination

Membrane Osmometry:

Dh = 0

Semipermeable membrane membrane.

Allows passage of solvent molecules

38

Molecular Weight Determination

RT
1

2
RT A2c A3c ..... c

0
c
M
M

Non ideal
solution

Mass
concentration

Dh > 0

Dhg

Membrane
Osmometry:

39

Molecular Weight Determination

Membrane Osmometry Numerical Application:
Plot of /c against c at 310 K in toluene for poly(vinyl acetate).
What is Mn?

RT
1

2
RT A2c A3c ..... c

0
c
M
M

40

Molecular Weight Determination

Membrane Osmometry Numerical Application:

RT
1

RT A2c A3c 2 ..... c

0
c
M
M

RT
1
c

16
.
2
J
.
kg

0
c
M

M = 8.31 (J.mol1.K1) 310 (K) / 16.2 (J.kg1) = 159 kg.mol1

41

Molecular Weight Determination

Membrane Osmometry:

RT
1

2
RT A2c A3c ..... c

0
c
M
M

slope = RT A2

42

Molecular Weight Determination

Membrane Osmometry:

poly(methyl methacrylate)

RT
1

RT A2c A3c 2 ..... c

0
c
M
M

toluene

acetone

acetonitrile
slope = RT A2 = 0?

theta-solvent.
43

What does an ideal polymer

solution mean?

In a good solvent, the polymer want to maximize polymer-solvent contacts, the coil
is expanded and the bonds are strained. A2 > 0
2
1
vB
A2 AB
2
VM

In a poor solvent, the polymer wants to minimize polymer-solvent contact, the coil
is compact and the bonds are strained. A2 < 0
44

Ideal polymer solution

What does it mean?
In a qsolvent, the forces that try to collapse
or expand the polymer coil cancel each other.
Consequently, the polymer adopts its ideal
conformation, that of a random coil.
A polymer solution in a qsolvent is said to
be ideal.
Ideality is reflected by a zero second virial
coefficient,
i.e. A2 = 0.
45

Virial Coeffients
Give an idea of the non-ideality of the
polymer/solvent system.
Most important is A2.
A2 can be related to polymer solubility
characteristics in particular solvents.
2

1
v

B
A2 AB
2
VM

MW methods
Light scattering
Rayleigh scattering / Debye (1944)
Mathematically very complex

2
=
R
r
Io
R90 Rayleigh ratio

Molecular Weight Determination

(scattered light)
Light Scattering
Iq/ 8 4 2
4 2 (1 cos 2 q )
I0 r

q
r = distance to detector

Iq r
Rq
I o (1 cos 2 q )
Light scattering from
a single centre:

http://math.ucr.edu/home/baez/physics/General/BlueSk
y/blue_sky.html

51

Molecular Weight Determination

(scattered light)

Light scattering: Multiple

Centres
q

Iq r
Rq
2
I o (1 cos q )
dn
2 n
dc

K
N A4
2

8 2 N
Rq 4
V
4

Rq is called the Rayleigh

(scattering) ratio.

2
o

System/sample constant
52

Variables
Io light intensity at source.
I/ light intensity measured at detector. Instrument factors
q angle of detector from incident direction
r distance from scattering cell to detector
wavelength.
NA avagadros number
no refractive index
Sample factors
excess polarizability
dn/dc refractive index increment.

Molecular Weight Determination

Light Scattering
Bottom line for M analysis
After rearrangement of
terms for

Rq KcM
Applies in situation with no interference
(external or internal).
So Rq can be equated with M
OK For gas phase scattering

c = mass concentration
M = molar mass

Molecular Weight Determination

Light Scattering
For polymers
Zimm equation in
solution

Kc 1

2 A2c
Rq M

Only true for relatively small molecules

Applies in situation with no__internal

interference____________

polymers having a polymer coil size < /20 (~25 nm for = 500
nm).
Low angle light scattering
At bigger angles if the polymer coil size is > /20, then one
must deal with internal interferences and non-ideal solutions
55

Example
The excess Rayleigh ratio
Rq of cellulose acetate
in dioxane was measured
as a function of
concentration by Low
Angle Light Scattering
measurements. Data are
given in the Table. If the
RI of dioxane is 1.4199,
refractive index increment
for CA in dioxane is 6.297
x 10-2 cm3/g and the
wavelength of light was
6328 A, calculate the MW
and second virial
coefficient

C x 103 (g cm-3)

Rq x 105(cm-1)

0.5034

0.239

1.0068

0.440

1.5102

0.606

2.0136

0.790

2.517

0.902

Kc 1

2 A2c
Rq M

56

Molecular Weight Determination

Light Scattering

Light scattering - Internal

Interferences:
For higher angles there is a big difference between the
two path lengths destructive interferences
57

Molecular Weight Determination

Light Scattering
q

Large angles: destructive interferences

Small angles: less affected by destructive interferences

Kc
1

2 A2c
Rq M w P(q )
58

Molecular Weight Determination Light Scattering

Light scattering - Interferences:
Scattering Intensity

Small molecules
polymers

Note P(0 1

59

Molecular Weight Determination

Light Scattering

Variation of Pq with molecular weight and angle for PS

Disymmetry Factor for Different Types

of Polymer Molecules

X axis
R/

61

Molecular Weight Determination

Light Scattering
P(q) is the form factor which depends on
the size and shape of the molecule
The form factor of polymer coils was
derived by Debye in 1947.
It handles the intra-particle interferences
needs to work with low polymer concentration
(c < 10 g.L1 = 1 wt%).

1
16
2
2
1
sin
(
q
/
2
)

R
G
2
P(q )
3
2

62

Molecular Weight Determination Light

Scattering
Light scattering Radius of Gyration: RG
Mi

ri

G: Center of mass of
the polymer coil

2
G

point Mi along the chain at ri

distance from G

1
2

ri

n i
63

Molecular Weight Determination

Light Scattering
Light scattering Non ideal solutions:

K c
Rq

1
2

2 A2c 3 A3c .....
P(q ) M w

The ratio Kc/Rq depends on polymer concentration (c)

and the angle of observation (q).
In practice, one prepares a set of solutions at different
polymer concentrations.
The light scattered by each polymer solution is
monitored at different observation angles

Zimm Plot!
64

Molecular Weight Determination

K c
1
2

2 A2c 3 A3c .....

Rq
P(q ) M w

Light scattering Zimm plot:

q1

q2

q3

q4

q5

K c
Rq

q6 q7
C (#6)
C (#5)
C (#4)
C (#3)
C (#2)

C (#1)

sin2(q/2) + bc
65

Molecular Weight Determination

K c
1
2

2 A2c 3 A3c .....
Rq
P(q ) M w

Light scattering Zimm plot:

q1

q2

q3

q4

q5

K c
Rq

q6 q7
C (#6)
C (#5)
C (#4)

C (#3)
C (#2)
C (#1)

sin2(q/2) + bC
66

Molecular Weight Determination

K c

Light scattering Zimm plot:

Rq
q1

q2

1
2

2 A2c 3 A3c .....
P(q ) M w

q3

q4

q5 q6 q7

K c

C (#6)

Rq

C (#5)
C (#4)
C (#3)
C (#2)
C (#1)
C0

1/Mw
slope = 162RG2/(Mw 32

1
K c 16 2
2
2

1
sin
(
q
/
2
)
R

....
G
2
Rq
3

Mw
sin2(q/2) + bc
67

Molecular Weight Determination

Light scattering Zimm plot:

K c
Rq

q 0,

q1 q2 q3

1
2

2 A2c 3 A3c .....
P(q ) M w

q4 q5

q6

K c
Rq

q7
C (#6)
C (#5)
C (#4)
C (#3)

Slope = 2A2

C (#2)
C (#1)
C0

1/Mw
sin2(q/2) + bc
68

Molecular Weight Determination

Light scattering Zimm plot:

Zimm plot of poly(vinyl acetate) in
butanone at 25 oC

What is Mw?

69

Molecular Weight Determination

Light scattering Numerical Application: What is Mw?

Mw1 = 0.8 106 mol.g1 Mw = 1.25 106 g.mol1

slope = 162RG2/(Mw 32

70

Multi Angle LS
Zimm Plot
Very useful for determining multiple pieces of
info
Mw
Rg
A2

BUT.

Very laborious !!!

Very sensitive to dust etc.
Time consuming.

Used for fundamental studies rather than as

a quality control or routine research tool.

MV methods
Viscosity of dilute polymer solutions higher than
that of pure solvent
A polymer solution has a higher viscosity than the
solvent, because:
Solvent trapped in-between the coils can not attain
the velocities which the liquid would have
-

polymer coil has the same effect on the

viscosity of the mixture as a sphere

Viscosity increase depends on T, nature of solvent

and polymer, C, and the sizes of polymer
molecules
-

Mv depends to some extent on the solvent

used

Dilute Solution Viscosity

Viscosity is the quantity that describes a fluid's
resistance to flow.
Viscosity of polymer solutions depends on
Concentration
Solvent
Temperature

Molecular weight
Can be used to determine molecular weights
Viscosity Average MW
2

Molecular Weight Determination

Viscometry:
The concept of the equivalent hydrodynamic sphere:
Solvent molecules located inside the polymer coil move almost in
unison, like polymer beads, as though the solvent molecules were
bound to the polymer.

capillary

Viscometer

V hydrodynamic volume
3

Molecular Weight Measurement

Viscometry
Secondary method
A polymer solution
has a higher viscosity
than pure solvent.
Solvent trapped in
coils cannot attain
velocities of free
solvent
http://www.pslc.ws/welcome/tour/macrog/vis
.htm
4

Viscosity Relationships
Newton

dv
F
A
dx

Einstein. viscosity
increase for
spheres in liquid
Poiseuille.
Viscosity of a
liquid in a tube
related to flow
time

Not really considered for polymer

solution

o (1 2.5 )

r Pt
4

8Ql

o solvent viscosity
volume fraction of
dissolved species

r =radius
l = length
t = time
P =pressure drop
Q = volume exiting
in t
5

Effect of Polymer Concentration

individual
polymer coils

overlap concentration

entanglements

Simple relationships only apply to low concentrations

6

Molecular Weight Determination

Viscometry:

o (1 2.5 )

(1 2.5 )
0

1 2.5
0

hydrodynamic volume

Volume
fraction of
solute

N AcVh
P
M
c = mass
concentration

77

Intrinsic Viscosity
How do we relate viscosity to MW ?

1 0 2.5 N AVh

c lim 0
c 0
M
Intrinsic Viscosity
http://www.ias.ac.in/initiat/sci_ed/resources
/chemistry/Viscosity.pdf Link now on Learn

Note

4
Vcoil RG3
3
8

Molecular Weight Determination

Viscometry - Definitions:
Real Viscosity is expressed in Pa.s
Relative viscosity

Specific viscosity

Reduced viscosity

Intrinsic viscosity

r
o
o
sp
o

sp 1 o

c c o

sp

1 o
[ ] lim
lim
c o c
c o c
o

Note: units for IV are reciprocal concentration

Molecular Weight Measurement

Radius
Depends on M
and solvent

F Varies depending on the solvent

2.1 x 1023

Chanda

Intrinsic Viscosity and Molecular

Weight
4
Vh Rh3 k M P3
3

3 = Flory exponent = 1.5 in theta solvent

= 1.8 in good solvent

KM

Mark-Houwink-Sakurada equation.
Generally 0.5 < a < 0.8.
Good solvent
For q solvent a = 0.5
11

Intrinsic Viscosity and Molecular

Weight Distribution

K M

a
v

Viscosity average molecular weight

12

Viscosity Average Molecular Weight

Definition of the
viscosity-average
molecular weight:
1
a

N i M ia 1

M v
N M
i
i

w M
i

1
a a
i

13

Molecular Weight Determination

Experimental Viscometry
Timing mark A

Step #1:
Step #2:

mark B

Step #3:

Flow
Capillary

Polymer solution is placed in tube A.

Tube D is blocked and the polymer
solution is sucked into bulb C above the
mark A.
Tube D is unblocked. The solution starts
to flow and the time it takes the solution
to flow between mark A and mark B is
measured.

CLASSIC METHOD. Nowadays automated available

Hagen-Poiseuille equation: = K t
14

Molecular Weight Determination

Experimental Viscometry:

mark A
mark B

Concentration Time
(g.L1
(s)

c0 = 0

to

c1

t1

c2

t2

c3

t3

c4

t4

(solvent)

1 o 1 Kt Kto 1 t to

c o
c Kto
c to
15

Molecular Weight Determination

Experimental Viscometry:

1 o 1 Kt Kto 1 t to

c o
c Kto
c to

mark A
mark B

1 o
c o

c, g.dL1
16

Molecular Weight Determination

Experimental Viscometry:

1 o
c o

c, g.L1

a
1 o
[ ] lim
KM v
c 0 c
o

Huggins equation: Accounts

for deviations from linearity
at higher c

1 o
[ ] k H [ ]2 c
c o
17

Modern Method
Use pressure drop
differences

r 4 Pt
8Ql

http://www.malvern.com/LabEng/technolog
y/dilute_solution_viscosity_theory/dilute_so
lution_viscosity_theory.htm

Viscometry Notes
A given polymer sample has only 1 M N or M W
May have more than one M v
Because a varies with solvent

The broader the MWD the more M v may vary with

solvent.
What happens with branched polymers and
copolymers?
Copolymer composition and microstructure has an effect
on polymer-solvent interactions
Branching gives a more compact structure for a given MW.
For a given MW, viscosity will be lower for branched compared to
linear (see later for GPC).

19

Example
The data shown were obtained for polystyrene
dissolved in cyclohexane, when viscosity
measurements were made at the q
temperature of 308K.
Solvent flow time = 100 s
c (g cm-3)

t (s)

0.001

109.5

0.002

120

0.003

135

0.004

144

Determine the average MW if K = 8.6 x 10-2 Ans 1.1M

20

Example
The following data were obtained for the
intrinsic viscosity of polystyrene fractions in
C2H4 Cl2 at 22oC using LS as the measurement
of MW. Evaluate the MHS constants.
[]
(cm3/g)

260

278

142

138

12.2

4.05

Mw X
10-4

178

157

56.2

48.0

1.55

0.308

21

Measuring Polymer Molecular Weight

Gel Permeation Chromatography

What about distributions???

Gel Permeation Chromatography

Previous methods give molecular weight
averages.
Gel Permeation Chromatography (GPC).
Gives molecular weight distributions

Based on separation of polymer sizes by

differential flow through a stationary bed of
particles.
SIZE EXCLUSION CHROMATOGRAPHY (SEC)
23

Molecular weight
SEC: schematic diagram

24

Gel Permeation Chromatography

http://www.malvern.com/LabEng/technology/gel_permeation_chromatography_t
heory/separations_theory.htm

Small molecules held up more than large.

Large molecules elute through to detectors more
quickly.
Detector responses are acquired with respect to
time measured from injection of sample.

25

Gel Permeation Chromatography

Nature of packing
Porous solids

Figure from
Allcock and
Lampe

26

Gel Permeation Chromatography

Detectors
Traditional
concentration detectors
Refractive Index
UV

Modern
LS
Viscometry
IR (rare)

How do we get MW
information?
Conventional calibration
Universal calibration
Multi detector
calibration

What are these?

27

GPC Trace
Conventional calibration is based on the use of one detector (concentration).

High MW

Low MW

MW related to the time (volume) required to reach the detector

28

Gel Permeation Chromatography

Remember smaller molecules
take more time to pass through
columns

Higher retention volumes (RV)

Columns specific to particular
MW ranges

29

Gel Permeation Chromatography

Columnmaterials
Depend on
mobile phase
Relates to
polymer
solubility

Polymer
Laboratories
Column
manufacturer

Gel Permeation Chromatography

Conventional Calibration

http://www.malvern.com/LabEng/technology/gel_permeation_chromatography
_theory/conventional_calibration_gpc_theory.htm

31

Gel Permeation
Chromatography
Conventional
Run multiple standards
Prepare calibration curve

For sample of unknown

distribution
M for each slice is based
on RV and relationship
with calibration line.
Concentration of polymer
for each slice is
proportional to area
(height) of slice.

32

Gel Permeation Chromatography

Mi comes from
calibration with
Elution Volume

hi

Software breaks chosen area for

integration into slices based on fixed
time intervals
Note: known concentration of sample not
necessary for analysis.

34

Gel Permeation Chromatography

Conventional
Run multiple standards
Prepare calibration curve

For sample of unknown distribution

M for each slice is based on RV and relationship with
calibration line.
Concentration of each slice is proportional to area
(height) of slice.

35

Gel Permeation Chromatography

Problems with conventional calibration
Polymer standards are not available for every type of
polymer.
Separation is based on polymer hydrodynamic
volumes (size when dissolved) not on molar masses.
Hydrodynamic volumes are a function of polymers
chemical structure and the degree of interaction
there is between polymer and solvent
Conventional gives MW values w.r.t. polymer standard
used.
36

Intrinsic Viscosity

1 0 2.5 N AV

c lim 0
c 0
M
How we relate intrinsic viscosity to MW.

Universal Calibration

[ ]M 2.5N AV
37

Gel Permeation Chromatography

Universal calibration
Use intrinsic viscosity
along with RV to get
molecular weight values.

If system has IV
detector then MW
obtained by using UC
and measured IV values
Otherwise calculations
necessary

M [ ]i

log M i log i
[ ]i

Found from measurement

or MHS

Found from calibration curve

38

39

Gel Permeation Chromatography

Universal (conventional)
calibration conversion
to MW data.
Two polymers ( x and y)
with known MHS
constants.
Calculation of Mx from
calibration based on My.

K y (a y 1)
1
log M x
log

log M y
(ax 1)
K x (ax 1)

Gives calibration line for second polymer based on first

40

GPC In line viscometer

Alternative to
traditional glass
viscometers
4 capillary tubes
Differential pressure
transducers measure
pressure drop across the
bridge
Pressure drop related to
IV
http://www.malvern.com/LabEng/technolog
y/gel_permeation_chromatography_theory/
viscometer_detector_theory.htm

41

Gel Permeation Chromatography

Multi Detector Systems

GPC system same as for

conventional and UC
except for the detectors.
Commercial systems have
various options.
Viscotek (Malvern)

LALLS (7o angle)

90o = RALLS
Viscometer
RI
Triple detection methods
for MW determination
42

Polyethylene Triple Detection Data

Light

scattering
clearly shows this is
a complex material
LALLS

RALLS
Viscometer

RI

From Agilent Technologies

Molecular Weight Determination

Light Scattering

Important for 7o LALLS Pq 1

Variation of Pq with molecular weight and angle for PS

44

GPC Triple Detection

Calibration
Single standard
Accurately known
concentration
Known dn/dc
Known M
Known IV

Zimm equation
assumed for ideal case
Detector constants are
found.

Kc 1

2 A2c
Rq M
For GPC ci is low

Rq
M
Kc
http://www.malvern.com/LabEng/technology/gel_permeation_c
hromatography_theory/triple_detection_gpc_theory.htm

45

GPC Triple Detection

Unknown sample
Conc (c) of slice from
RI response.
M for slice from LS
response using Zimm
expression and
detector constants

46

Gel Permeation Chromatography

Other systems
Use responses from multiple (or
dual) angle detection to estimate
disymmetry factors.
Use Zimm equation for Mw.
Can also use viscosity information
to estimate Rh

Polymer Laboratories

RALLS
45o
Viscometer
RI

Rq
P(q )
Rq '

Wyatt, Brookhaven

MALLS
RI
(viscometer).
Absolute method
Use extrapolation to q = 0 for each
slice

47

Gel Permeation Chromatography

Each system has advantages/disadvantages.
Conventional
Simple equipment (cheapest).
Lengthy and careful calibration needed with multiple
standards.
Not so bad now. Companies sell multiple standard vials.

Calibration is only true for polymers of same type as

polymers for calibration.

Universal
Simple equipment
Can be applied to different polymer types.
Multiple standard calibration needed.
48

Gel Permeation Chromatography

Multi detector
Benefit
one standard calibration (for detectors).
not so time consuming as Conventional and Universal.

Direct measurement of molecular weights.

Can give branching information.

Disadvantage
one standard calibration for detectors
If there is a problem with the standard that will carry over to all
samples.

Low M species give low LS response at low concentrations

49

Branching Structures
Polymers may have a wide variety
of branching structures depending on
how they have been made or
modified

Dendrimers

are special cases of

polymer that combined the structures
of star and hyperbranched polymers

The

branching can further be

characterised by the length of the
branch into long chain or short chain
branching

Long

chain branching affects the

size and density of polymer
molecules and is easier to measure
by GPC
Slide from
Agilent

Effect of Branching on Molecular Properties

The effect of branching is to reduce the size and increase the density
of a polymer molecule at any given molecular weight in solution
If we can measure the density or size of a branched molecule and
compare it to a linear molecule of similar chemistry, we might be able to
get information on the nature of the branching

Estimation of Branching
Long chain branching has a significant effect
on polymer properties.
E.g Polymer rheology (melt behavior), crystallinity.

Long chain branching difficult to detect by

spectroscopic methods if the concentration of
branch points is low.
How to assess branching levels?
Light scattering

GPC/SEC
52

Estimation of Branching
Parameters for branched
polymers measured
relative to equivalent
properties for linear.

See Branching Level Detection in Polymers

Scorah M., R. Dhib and A. Penlidis. Encyclopedia
of Chemical Processing. Taylor and Francis . 251.

Mean square radius

s
Rg s

Branching factor (g)

ri 2

i 1 N
N

Ratio of mean squared radius values for

branched and linear polymers with
equivalent MWs.

2 0.5

2
b

2
l

Contraction factor
53

Estimation of Branching
Branching numbers
Star shaped
f is functionality of
branch points

Randomly branched
(monodisperse).
Trifunctional
mb = number average
number of branch points
per molecule
tetrafunctional

3 5
g 2
f f
mb

g 3 1
7

mb

g 4 1
6

0.5

0.5

4mb

4mb

0.5

0.5

54

Mark-Houwink Plots of Hyperbranched Polyesters

Clear trend in Mark-Houwink plots

Increased branching/decreased molecular size leads to a decrease in IV
Slide from Agilent

Branching Affects Solution Viscosity

56

Estimation of Branching
GPC/Viscometry
Curvature in log MW vs
Log IV curves.
Gives a viscosity
branching factor g /

[ ]Br
g
[ ]Lin
/

57

Estimation of Branching
Calculation of g /

[ ]Br
g
[ ]Lin
/

g/ gx
Branching
factor

x is a structure factor
which depends on
the nature of
branching
0.5 < x < 1.8

b g / (, M ) KM a
slice molecular weight

mb

M
58

Finding mb
Find g

g g
/

mb

g 3 1

0.5

4mb

0.5

From g values use parameter estimation to find mb

59

Mark-Houwink Plot

Downward curvature of the

plot at high molecular weight
indicative of branching

Branching Number and g Plot

Branching

number Bn and
branching frequency calculated

Values are dependent on the

choice of branching model

Case Study (Painter and Coleman)

Long Chain Branching in poly(chloroprene).
Polychloroprene
Difunctional monomer gives possibility of
branching from vinyl sites on main chain.
Branching favoured as monomer concentration
drops.
Can assess branching with conversion using
SEC/viscosity method.

62

Polymer Rheology
The science that deals with the way materials
deform when forces are applied to them
The term is derived from the Greek words
= to flow, and
o = study

Most commonly applied to the study of liquids

and liquid-like materials
paint, blood, polymer solutions and molten plastics,
materials that flow,
63

Polymer Rheology
Newtonian Fluids
The simplest type of rheological behaviour for a
material that can flow.
For simple shear this type of behaviour is
described by a linear relationship between the
shear stress and the shear rate:
Viscosity is simply the proportionality factor for
shear stress with respect to shear rate.

Shear
stress

Shear
rate
64

Polymer Rheology
For polymeric liquids (non Newtonian Fluids)
the relationship between stress and strain rate is
no longer linear
cannot be described in terms of a single constant.
Relate steady simple shear experiment in terms of
a viscosity function defined as follows:

( )

65

Polymer Rheology
Zero shear viscosity

Newtonian

66

Zero Shear Viscosity and MW

Rudin and Chee Macromolecules

(1973), 6, 613-624

Bottom Line
Polymer melt
behaviour relates
to M.

67

Molecular Weight Related

Measurements
Industry
Rubber Mooney
Viscosity

Most important empirical test

in the rubber industry.

Measures torque for a

rotor embedded in
softened rubber at
specific T.
Results for Mooney

50ML 1+4 (100oC)

50M Mooney number
L = large rotor
1 time (mins) for specimen to warm
up
Time of test (minutes)
100oC temperature of test.

68

Mooney Viscosity
Empirical test
Mooney number may be
related to MW
Eg for nitrile rubber

http://techcenter.lanxess.com/trp/americas/en/pr
oducts/types/index.jsp?pid=444

MV k (M n )

69

Molecular Weight Related

Measurements
Melt Flow index (MFI)
Data from a capillary
rheometer
Ease of flow of a
thermoplastic through
capillary
Fixed temperature and
applied pressure (load)
Measure throughput as

MI

(
M
)
W
mass of polymer per unit
time http://www.exxonmobilchemical.com/Public_Products/Polyethylene/Polyet
hylene/NorthAmerica/Grades_and_Datasheets/HDPEXOM_IDESDataSheet.asp

70

Zero Shear Viscosity and branching

71

Estimation of Branching
Rheological properties
Melt behaviour

Branching has two

conflicting effects
Drops molecular sizes.

Zero shear viscosity

0 Br g 0l
a

Lower MW Fewer
entanglements.
Related to a critical chain
length.
a = 1.

Longer polymer chains

a = 3.4.
72

Summary:
Molecular Weight Determination Methods

73