CHEM-E2130

Polymer Properties
Tapio Saarinen, Sami Lipponen, Steven Spoljaric

Contact details:
tapio.saarinen@aalto.fi
Room E428, Chemical Engineering Building (Kemistintie 1)
Polymer Properties (5 credits)

Learning outcomes:

After completing the course, the student understands:

1) The basics of polymer physics and structure hierarchy of polymers

2) The basics of the most important methods of polymer analysis
3) Theories of polymer rheology
4) Stability and degradation of polymers
5) The ability to calculate the above mentioned phenomena
Topics covered:
• Structure and average molecular weights
• Solid-state properties:
– Crystallinity
– Thermal transitions
• Characterization methods:
– Thermoanalytical methods (DSC, DMTA)
– Structure analysis (FTIR and Raman, NMR, fractionation, SEC/GPC)
• Rheological properties and their measurement
• Solubility and gas permeability
• Microscopy methods, X-ray analysis
• Stability and degradation
 Schedule for the course

• 6 Lectures, split into 2 sessions:

– Mondays from 10:15-12:00, R001, Otakaari 1,
various lecture rooms)
– Tuesdays from 8:15-10:00 R001, U1 (154)

• 5 Problem solving exercises on Tuesdays from

14:00-16:00
– R001, Otakaari 1, various lecture rooms)
• Exam: 10th December, 9:00-13:00, R011 / A301
(Ke1)
• Textbook for the course: Polymer Science and
Technology, Fried JR.
Schedule for the course, locations

Week 44 Week 45 Week 46 Week 47 Week 48 Week 49

Structure, MW Crystallinity DSC, DMA, IR, Rheology Solution Stability,
NMR fractionation and degradation,
permeation microscopy

Lectures
5.11.2018 12.11.2018 19.11.2018 26.11.2018 3.12.2018
mon 10.15-12.00 29.10.2018
U4 (U142) U3 (U141) U3 (U141) U4 (142) U4 (142) U1 (U154)

tue 08.15-10.00 30.10.-04.12.18

U1 (U154)

Excercises
6.11.2018 13.11.2018 20.11.2018
tue 14.00-16.00 30.10.2018 27.11.2018 4.12.2018

R011 A304
U5 (U147) U3 (U141) (Ke2) U3 (U141) U3 (U141) U3 (U141)
Course assessment

• Written examination (70 %)

– 10th December, 9:00-13:00, R011 / A301 (Ke1)

• Problem solving exercises (30 %)

• The grade will be a weighed average of both the examination and

the exercise
Lecture overview

• Active learning / support from teaching staff balance

• Broad spectrum of material:

– However, key concepts/learning outcomes will be highlighted at
the start of each lecture
– You will know what the crucial/important/relevant information is

• Lecture structure
– Going-over and clarifying the course material
– Visiting instruments and processing equipment
• ’Hands-on’ experience where possible
Problem solving exercises
• 5 problem solving exercises, every Tuesday 14:00 – 16:00
– All exercises are available on MyCourses
• Exercises can be worked together in Tuesday’s exercise sessions
14:15-15:45
• Comleted exercises are to submitted by next Thursday 23:55 in
.pdf format for correction in the MyCourses page under
assignments
• Grading of exercises is done in a peer review process i.e.
everybody who has returned their work in time will get a paper to
review
• Taking part in peer review process is mandatory for getting your
own exercise points accepted
• Feel free to ask me and/or work with one another!
Lectures and corresponding book chapters
(Fried)
• Lecture I (Structure and Molecular Weight) – Chapters 1 and 3.3

• Lecture II (Crystallinity) – Chapter 4

• Lecture III (Spectroscopic analysis techniques) – Chapters 2.6 and

4

• Lecture IV (Rheology) – Chapters 5 and 11

• Lecture V (Solution fractionation and permeation) – Chapters 3.2

and 12.1

• Lecture VI (Stability, degradation and microscopy) – Chapter 6

Other recommended references

• Spectroscopy of Polymers, Jack L. Koenig

– Good for further information about spectrsocopy
and characterisaton (Lecture III)

• Polymer Physics, Ulf Gedde

– A good all-round textbook, includes some
information about microscopy (Lecture VI)
Questions?

1. Have you completed the course ‘Polymeerien valmistus’ (Polymer

Synthesis)?

2. For those who haven’t completed Polymer Synthesis, have you

completed any organic chemistry course?

3. What would you like to know more about regarding polymers?

What do you think will be the topics in this course?

4. Any comments or wishes at this moment?

Polymer Structure
Key learning outcomes

• Tacticity and isomers

• Different molecular weights
– How they influence polymer properties
– How the can be determined
– What needs to be known to determine them
• Instrumentation used to determine molecular weight
– Operating principles
– Data obtained
– Advantages and limitations
 Skeletal (’line’) formula
• Every angle represents a carbon bond
• Hydrogens are not shown =
• Single line is a single bond
• Atoms/functional groups added as needed

Solid lines represent bonds in the plane of the paper or screen

Solid wedges represent bonds that point out of the plane of the
paper or screen, towards the observer

Dashed wedges or dashed lines (thick or thin) represent bonds

that point into the plane of the paper or screen, away from the
observer
Wavy lines represent either unknown stereochemistry or a
mixture of the two possible stereoisomers
Polymer Stereochemistry

• Stereochemistry: Three-dimensional arrangement of atoms and

molecules, and their effect on properties

This consists of two distinct factors:

• Conformation:
– Different orientations of atoms and substituents in a molecule
– Result from rotations around single bonds
• Configuration:
– Relative position of atoms in a polymer that can only be
changed by breaking and reforming primary chemical
bonds
Conformation

Different conformations: the

different shapes a cat can make by
moving its limbs around
Configuration

Different configurations: the same

number of limbs, but different order and
locations where they are connected
Tacticity

• Stereochemical arrangement of units in the polymer main

(backbone) chain: not including hydrogens

• This determines the overall order of the polymer chain:

– If the ‘R’ groups are randomly distributed on the two sides of the
planar backbone, the polymer does not have order and is
atactic
• Ordered structures are isotactic and syndiotactic
– When the sterocenter of each repeating unit has the same
configuration, the structure is termed isotactic
– When the stereocenter alternates from one repeating unit to the
next, the structure is syndiotactic
Tacticity: structures

Atactic (random)

Syndiotactic
(alternating)

Isotactic (same)

NOTE: ’R’ groups are not hydrogens!!!

Tacticity: influences

• In general:
– isotactic and syndiotactic polymers are partly crystalline
– atactic are amorphous

• Tacticity affects also other properties such as thermal and

mechanical properties

• The tacticity of a polymer can be controlled by several factors:

– Polymerization temperature
– Pressure
– Catalyst
– Solvent
Draw the stereoregular polymer structure 1:

n CH2 CH CH3 CH2 CH Poly(propylene)

CH3
n
Tacticity in commercial polymers

• Polypropylene (PP) used and sold is mostly isotactic but it is also

possible to produce syndiotactic or atactic polymer

Tm (Melting point) Isotactic

~180 – 220 0C

No melting point Atactic

(doesn’t crystallize)

Tm ~170 – 190 0C Syndiotactic

Draw the stereoregular polymer structure 2:

CH3
CH2 C(CH3)2 CH2 C Poly(isobutylene)

CH3
n

No stereoregularity differences:
• When there are two identical substituents on the same carbon
• Polyethylene is the other exception
Isomerism

• In chemistry, isomers are molecules with the same molecular

formula but different chemical structures.

• In other words, isomers contain the same number of atoms of each

element, but have different arrangements of their atoms in space
Geometric isomerism (cis-trans isomers)

• Geometric isomers have the same structural formulas but differ

in the arrangement of groups at a single atom, at double bonds,
or in rings

CH2 CH CH CH2 Unsaturated carbons

• Polybutadiene isomers:
(double or triple bonds)
1,3-butadieeni
result in different
isomers:

CH2 CH n CH2 CH2

C C n cis
CH CH2 H H

1,2-poly(1,3-butadieeni)
CH2 H
C C trans
H CH2
n

1,4-poly(1,3-butadieeni)
Optical isomerism (enantiomerism or chirality)

• Optical isomers (also called enantiomers) are mirror images that

are not superimposable (that is, they can’t be put on top of one
another – the phenomenon is called chirality)

• They differ in only one characteristic; their interaction with plane

polarized light (specifically, the direction in which they rotate it)

https://www.youtube.com/watch?v=6vd7S3T7R8k
Spotting optical isomers

• Four different groups on a carbon: chiral (no plane of symmetry)

• The trick to identifying them is to look at the wedged and dashed

bond lines:
– Flipping them 180° gives the opposite
 Optical isomers: subtle differences matter!!!

Sedative, hypnotic, Teratogen

antiemetic (prevents (causes birth
nausea/vomiting) defects), low
survival rates
Spearmint Carroway seed (kumina)
Optical isomers and polymers:
Lactic acid-based materials
• Commercial optically-active polymers are lactic acid based
– Poly(lactic acid) (PLA)

• Lactic acid based polymers are either optically-active or not

depending on the monomer used
– Optically active: materials that rotate polarized light
Optical isomers in polymers: applications

• Chromatographic/separation applications
• Catalysts
• Liquid crystals
• Microwave absorbents
• Membrane separation technology
• Optical switches
• Biomedical equipment
• Optoelectronics
Lactic acid monomers

H
*
H3C C COOH
OH
L-MAITOHAPPO
L-lactic acid (optically active)
DL-MAITOHAPPO
D,L-lactic acid is a mixture of the two
H (50/50 seos)

C* COOH
H3C
OH
D-lactic acid D-MAITOHAPPO
(optically active)

Lactic acid is available both in optically-active enantiomers as well as an

optically-inactive racemic mixture
Lactide monomers

O O O
H C H C H C
H3C *C [L] O H3C *C [D] O H3C *C [L] O

H H H
[L] [D] [D]
O C O C O C
* * *
C CH3 C CH3 C CH3
O O O
L-LAKTIDI D-LAKTIDI MESO-LAKTIDI

D,L-LAKTIDI
(50/50 seos)

Polylactide is polymerized with Ring Opening Polymerization (ROP)

Polylactides

Partly crystalline
PLA

Amorphous
PLA
Average molecular weights
Molecular weight vs. molar mass

• Molecular weight is the mass of one molecule of a substance

• Usually provided as an average distribution:

– Following polymerisation, polymer chains rarely have the same
degree of polymerisation (number of repeating monomer units)
and molar mass

• Molar mass is the mass of one mole of a substance

Average molecular weights

In alphabetical order…

http://www.ias.ac.in/initiat/sci_ed/resources/chemistry/MolWeight.pdf
Average molecular weights

• Number average molecular weight: Mn 

 ni M i
 ni

Mw 
 wi M i 
i i
n M 2
• Weight average molecular weight
 wi  ni M i

  ni M
1a
a 1
i

Mv   
• Viscocity average molecular weight   ni M i 
Average molecular weights

• Z-average molecular weight

(Z = zentrifuge/centrifuge) Mz 
 i i
n M 3

 i i
n M 2

• Polydispersity Mw
PDI 
Mn
– If PDI = 1, the polymer is monodisperse

ni = Number of molecules with molecular weight Mi

wi = weight fraction with molecular weight Mi
a = constant, depends on polymer/solvent combination
Molar mass distribution for a narrow and broad
polystyrene (molar mass averages are also given)

http://www.polymer.de/solutions/molar-mass-determination.html
Determination of average molecular weights

• Primary (absolute values) methods:

– Osmometry (Mn)
– Scattering (Mw)
– Sedimentation (Mz) Z-average molecular weight is obtained from
centrifugation data

• Secondary (relevant to reference or calibration) methods:

– Gel permeation chromatography (GPC), also called size
exclusion chromatography (SEC) to obtain molecular weight
distribution
– Intrinsic viscosity for determining viscosity average molecular
weight
Determination of average molecular weights
Method Relative/ Average Range of Comments
absolute molecular molecular
weight weight

Ebulliometry A Mn < 104 Insensitive

Cryoscopy A Mn < 104 Small sample size
Membrane Difficulties with the membrane, slow
A Mn 5x103 - 106
osmometry measurement
Vapor pressure Mn
A < 3x104 Only few suitable solvents
osmometry

Mn Restricted to low molecular weights,

End-group analysis A 102 - 3x104
assumption of 2 end-group/molecule

Mw Insensitive for small molecules, slow

Light scattering A 104 - 107
measurement
MALLS, LALLS A Mw 104 - 106
Slow measurement, expensive
Ultracentrifugation A Mw 2x103 - 107
instrument

Mv Simple measurement, inexpensive

Viscometry S% 102 - 107
instrument
Gives molecular weight distribution.
SEC (GPC) S% all 102 - 107
Requires calibration.
Effect of molecular weight on
polymer properties
Properties dependent on Molecular Weight and
Molecular Weight Distribution

• Melt Viscosity Polymer

• Tensile Strength
• Toughness or Impact Strength
• Resistance to heat
Monodisperse Polydisperse
• Corrosive properties (uniform) (non-uniform)

Proteins, nucleic All synthetic

acids polymers
 Molar mass, properties

Degree of Molar mass, Softening State of matter (25 °C)

polymerization, g/mol temperature, °C
DP(=n)
1 28 -169 Gas
6 179 -12 Liquid
35 1000 37 Oleaginous (Fat-like)
140 4000 93 Waxy
250 7000 98 Hard Wax
430 12000 104 Hard plastic
750 21000 110 Hard plastic
1350 38000 112 Hard plastic
DP >100 000= UHMWPE, teflon-like properties regarding friction
http://www.servicethread.com/blog/is-ultra-high-molecular-weight-polyethylene-uhmwpe-right-
for-your-product
Effect of the molecular weight on polymer
properties
• Huge effect on properties!!!
– Some properties have a limit (eg. Tg and strength at break)
– Some can change without any limit

• Dependence of glass transition temperature (Tg) on number

average molecular weight (Mn):
A
Tg  Tg ,  
Mn  B
- A and B are experimental constants
- Tg, is glass transition temperature of a extremely high molecular
weight polymer
Effect of the molecular weight on polymer
properties
• Many mechanical properties exhibit a similar dependence on
molecular weight:

P  P  K '/M n

P = property value (strength, toughness, stiffness …)

K’ = empirical constant
Mn = number average molecular weight
Effect of the molecular weight on polymer
properties

Tensile strength (Mpa)

• Tensile strength of PS in
proportion to molecular
weight

Inverse of molecular weight

(106/M)
Effect of molecular weight and PDI on
properties
• Examples of how average molecular weight and molecular weight
distribution affect different properties:
Property Molecular weight Molecular weight
increases distribution
narrows
Property:
Tensile strength + +
+ = improves
Tensile strain + - - = worse
Strength at yield + - o = little effect
Ductility + +
Brittleness + -
Hardness + -
Softening point + +
Melt viscosity + +
Adhesion - -
Chemical endurance + +
Solubility - o
Number average molecular weight
Number average molecular weight

• Determination methods based on various phenomena or factors:

– End groups on polymer backbone
– Property changes
• Osmotic pressure
• Increase in boiling point
• Decrease in freezing point or vapour pressure
Osmometric measurement

• Pure solvent and a dilute solution

of polymer in the same solvent are
placed on opposite sides of a semi-
permeable membrane

• Membrane will allow the solvent to

pass through but will retain the
polymer molecules in solution

• In equilibrium the difference in the

heights of the solvent and solution
in capillaries can be used to
calculate the osmotic pressure
Osmometric measurement

• Van’t Hoff equation for the osmotic pressure of an ideal, dilute

solution:

p = osmotic pressure
RT p RT
p c 
c = concentration (g/m3) Mn c Mn
R = gas constant 8.314 J/mol/K
T = temperature (K)
M n= number average molecular weight (g/mol)

g = gravitational constant 9.80665 m/s2 p  gh

ρ = solvent density
.
.

Osmometric measurement

• Van’t Hoff equation is for ideal, dilute solutions. In real solutions

the equation will be following:

1
p  RTc (  Bc  Cc 2  ....) B, C are virial coefficients
Mn

• In dilute solutions (c<1g/dL) the second and higher concentrations

can be ignored. Then, when plotting p/(RTc) as a function of
concentration, a linear correlation
1 is obtained where the slope is A2
and the y-axis intercept M n
.
.

Osmometric measurement

• For the determination of molecular weight, 4-6 pressure

measurements with different concentrations are required. When
solutions are dilute enough, p/c can be obtained by extrapolation of
c to 0. Average molecular weight can be calculated from:

• Polymer concentration is g/m3 and p/c in J/kg

p RT
lim 
c 0 c Mn
Osmometric measurement: determining π/c

PS in toluene

PS in acetone

c (g/m3)
Osmometric measurement: challenges

• Simple experimental procedure, but can be very time consuming

• Performance of the membrane can be a problem

• Membrane can let some smaller polymer molecules through and

this will result in an artificially-higher Mn value

• Thus, the method is considered accurate for molecular weights

above 20,000 g/mol

• The upper limit for molecular weight is 500,000 g/mol due to

inaccuracy in measuring small osmotic pressures
Vapor-pressure osmometry

• When a polymer is added to a solvent, the vapor pressure of the

solvent is lowered due to the decrease in solvent activity

• Vapor-pressure osmometry uses two matched thermistors that are

in a closed chamber containing saturated solvent vapor

• A drop of solvent and a drop of dilute polymer solution is placed on

thermistors

• Condensation of solvent vapor onto the solution causes the

temperature of the solution thermistor increase until vapor pressure
of solution equals to that of a solvent
Vapor-pressure osmometry: measurement
principles

Closed chamber

Pure solvent

• For the characterization of low molecular weight oligomers and

polymers, vapor-pressure osmometry is recommended
Vapor-pressure osmometry cont.

• The difference in temperatures is recorded in terms of difference in

resistance DR, which is calibrated by use of a standard low
molecular weight sample

• Several polymer concentrations are measured and extrapolation of

DR/c to zero concentration yield Mn (requires calibration constant
obtained with the standard sample hence VPO is secondary
method)
Ebullioscopic method

• The determination of molecular weight, in which the differential

thermometer is used to measure the rise in boiling point

• Boiling point of the polymer solution is compared to the boiling

point of the solvent. An increase in boiling point is comparable to
polymer properties:
DTb = increase in Tb
W A 1000 Kb = ebullioscopy constant
DTb  K b
WS M n WA = mass of the polymer
WS = mass of the solvent
• Top limit of the measurement is 50 000 g/mol
Cryoscopic method

• Resembles ebullioscopy method

• Compares the freezing point of a polymer solution and pure

solvent

• For dilute solutions:

WA 1000 Kf = cryoscopic constant
DT f  K f
WS M n

• Top limit of the measurement is 50 000 g/mol

End group method

• The structure of the polymer chain must be known!!!

• End groups to be either quantitatively determined with appropriate

reagents (titration) or determined by IR spectroscopy or NMR

• IR spectroscopy: Number average molecular weight can be

calculated assuming the chain is linear with no branch points
– Number of end groups of the polymer is thus one or two per
molecule
– End groups are not spectroscopically coupled to the remainder of
the chain, low molecular weight analogs can be used for calibration
– Particularly useful for insoluble systems (eg. fluorocarbons)
Viscosity average molecular weight
Viscosity average molecular weight

• Widely used for routine molecular weight determination

– Cheap equipment and simple measurement procedure

• In this method, the viscosities of pure solvent and dilute polymer

solutions are compared

• To determine the molecular weight, the empirical constants K and

a, that are specific for a given polymer, solvent and
temperature, need to be known
– Extensive libraries of the values for constants exist for different
polymer solvent combinations
Related terms

[h]= intrinsic viscosity

hsp = specific viscosity

hr = relative viscosity

hred = viscosity number or reduced viscosity

hinh = Logarithmic viscosity number, inherent viscosity

Staudinger equation

• Staudinger equation is valid only for a relatively narrow

molecular weight distribution

h sp  K m Mc

hsp = specific viscosity

c = solution concentration
Km = constant for specific polymer-solvent combination
Mark-Houwink equation

• Mark-Houwink equation is valid for broad molecular weight

distribution:

  a
h  Km M v
[h ] = intrinsic viscosity
Mv = viscosity average molecular weight
KM, a = constants for particular polymer-solvent combination

For flexible polymer chains a is 0.5 - 0.8, for stiff and rod like
chains a is 2.0.
Mark-Houwink equation: K and a constants

• Values for the constants can be found in:

– ‘Polymer Handbook’, Bandrup, J., Immergut, EH. (ed.)

Polymer Solvent T (°C) K x 104 a

Linear Polyethylene tetrahydronaphthalene 130 4.60 0.72
Linear Polyethylene tetrahydronaphthalene 105 1.65 0.83
Linear Polyethylene p-xylene 105 1.62 0.83
Polystyrene toluene 30 1.05 0.72
Polystyrene methylethylketone 30 3.14 0.61
Polyvinyl chloride tetrahydrofuran 25 1.63 0.77
Viscosity parameters

Capillary viscometers are used to carry out the measurement:

– Ostwald-Fenske or Ubbelodde type capillary
– Constant temperature, typically 25 or 30°C
– The time required for a dilute solution and pure solvent to pass
through the capillary is measured
– 4-6 polymer solutions are measured
– Efflux times need to be more than 100 s, which can then be
used to calculate the relative viscosity:

hr  h / h0  t / t 0 t
t0
= efflux time for dilute polymer solution
= efflux time for pure solvent
h  dynamic viscosity of the solution
h0 = dynamic viscosity of the solvent
Capillary viscometers (‘U’ tubes)
Ostwald Uppelohde Reverse flow
• The time for the fluid to fall
or rise between marks A
and B determines the flow
rate (Q)

• The pressure drop (DP) is

calculated from the head
of fluid

• The viscosity can be

determined from these
values and the geometry
of the viscometer

http://www.adhesivestoolkit.com/Docs/test/Physical%20Analysis%20-%20Viscometry.xtp
Viscosity parameters

• Specific viscosity can be calculated from viscosities or the efflux

times:
h  h0 t  t 0
h sp  
h0 t0
• The viscosity number or reduced viscosity is obtained by
dividing specific viscosity by the solution concentration:

h sp h  h0
h red  
c c h 0

Molecular weight determination, Rheological measurements in Polymers:

Polymer Characterization and Analysis, Ed. J.I. Krowchwitz, John Wiley &
Sons Inc, 1990
Viscosity parameters

• Logarithmic viscosity number, inherent

viscosity:

h
ln
ln hr h0
hinh  
c c

• Limiting viscosity number, intrinsic viscosity is obtained from the

parameters of logarithmic viscosities
Viscosity measurement
h  h0 t  t 0
h sp  
h0 t0
• Unit used in concentration is g/cm3

 h sp   h  h0  h
h   lim    lim  ln hr
ln
h0
c 0
 c  c 0  h 0 c  hinh  
c c

ln hr  ln( h / h0  
 h  lim c  lim  c 
c 0 c  0 
Viscosity measurement

• Measuring viscosity for several polymer solutions with different

concentrations, the intrinsic viscosity can be determined
graphically:

h red
hsp /C

h inh
Huggins/Kraemer Plot
C
Weight average molecular weight
Light scattering in nature

• Why is the sky blue?

• How can we see clouds?

incident
beam
scattered
light

• When light passes through matter, most of the light continues in its
original direction but a small fraction is scattered in other directions
Light scattering in the lab

• In the lab we can control polarization, wavelength (l) and intensity

(Ii) of the coming light

• We can detect the scattered light (Is) as a function of angle (q)

• Scattered light is proportional to the concentration and

molecular weight of the polymer
Light scattering

• The weight average molecular weight can be obtained directly only

by scattering experiments

• Most commonly used is light scattering from dilute polymer solution

• Polymer molecules in solution cause stronger scattering than

solvent molecules
– The intensity of the light is proportionate to the absolute
molecular weight of the particle causing the scattering
Light scattering procedure

• Polymer is dissolved in appropriate solvent

• The particles have interactions in solution and self organize

– Local changes in concentration and density in solution

• Light scattering is observed in different angles

• Measurements with several concentrations and angles

Light scattering
Intensity distribution of LS at various angles for a small particle
(dashed line) and a large polymer molecule (solid line)
Light scattering instrumentation

Conventional LS instrumentation showing incident and

scattered light, sample cell, and photomultiplier (Fried et al.)
Light scattering

In order to determine molecular weight, the following information

must be known/determined:

• Refractive index for the solvent

• Difference between refractive indices for the solution and solvent
• Polymer concentration
• Absolute light intensity for certain scattering angles
Light scattering

1 2 p 2 n02  
dn 2
c
• Rayleigh formula:  4   I0  
M w  N 0 Rb  dc   R  c  0, q  0
n0 = refractive index for solvent
l = wavelength of the light
N0= Avogadro number
Rb= Rayleigh constant
I0= light intensity at 90o angle that scattered from solvent
c = polymer concentration in solution
q = measuring angle
R = measured intensity, contains the angle and correction
for concentration
• Problem is determining R(q) value, which should be known for all q
values
Low-Angle Laser Light scattering (LALLS)

• Helium-Neon lasers have replaced conventional light sources in

scattering instruments

• The high intensity of the light sources permits measurements at

much smaller angles (2–10 o). Then, the scattering by small
spherical particles can be expressed:

Kc 1  2 p 2 n 2  dn  2
  2 A2 c K
R( q  M w 4  
 N 0  dc 

• Only at one single angle chain dimensions cannot be obtained

Multi-Angle Laser Light-Scattering (MALLS)

• Several detectors (18 angles, 20–150 o )

• Absolute molar mass (Mn, Mw, - Mz) and size (Rz , rh)

• No standard references, more reliable than calibration techniques

– Information about molecules and particles (conformation,
branching, partly cross-linked fractions)
– Co-polymer, protein, aggregate detection
– Easy and fast to use
DAWN 8+

• 8 angles (23-155 °)

• Molar mass range <10³-107 g/mol

• Molecular size range 10-500 nm

photodiode detectors

• Laser wavelength 658 nm

– (50mW GaAs linear polarized laser)

• All solvents compatible (aqueous and

organic) incident beam
Gel permeation chromatography
(GPC )
aka: Size-exclusion chromatography (SEC)
Gel permeation chromatography (GPC)

• GPC is the most widely used technique for the analysis of polymers

• Can be used for samples soluble in organic and aqueous eluents

and molecular weights from approximately 100 to several million

• Yields all molecular weight averages and the molecular weight

distribution

• Room temperature GPC or operating at higher temperature (for

polyolefins 120 ᵒC)
Gel permeation chromatography (GPC)

Separates samples of polydisperse polymers into fractions of

narrower molecular weight distributions
Principle of GPC:
The largest fractions of polymer come through
the column first

Polystyrene gel
Polystyreenigeeli

Polymeerimolekyyli
Polymer molecules
GPC measurement

• Columns are packed with small, highly porous beads or gel

– Pore diameters of the beads range from 10 to 107 Å
– Approximately the dimensions of polymer molecules in solution

• During GPC operation, pure pre-filtered solvent is continuously

pumped through the columns at a constant flow rate. Then a small
amount of dilute polymer solution is injected into the solvent stream
and carried to through the columns

• Polymer molecules diffuse from this mobile phase into the

stationary phase in the pores. The smallest polymer molecules
penetrate deeply into the pores whereas the largest molecules
pass through the columns first
GPC measurement

Comprehensive Analytical Chemistry vol 53: Molecular Characterization and Analysis of

Polymers, editors John M.Chalmers, Robert J. Meier, 2008
GPC measurement

• The concentration of polymer molecules in each eluting fraction is

monitored by a detector, such as IR

• The elution volumes are calibrated with know Mn standards (PS and
PMMA standards are most common)

• Only apparent molecular weights are determined unless:

– Molecular weight standards exist of the same composition and
topology as the samples
– LALLS or viscometry is used
– Mark–Houwink parameters of the standards and sample are
known
Molar mass distribution for a narrow and broad
polystyrene (molar mass averages are also given)

http://www.polymer.de/solutions/molar-mass-determination.html
Next week:

Crystallinity
Thermal transitions