Electrophoretic Light Scattering

(Zeta Potential)

Barathithasan.R
Application specialist,
 What is Zeta Potential?

What does the

The zeta potential is the zeta potential
charge a particle acquires of a particle
in a particular solution dispersion tell you?

What do
you mean
It can help predict by stability?
the long term
stability of the sample
 Dispersion Stability

Stability is the
resistance What is
to change of meant by this?
a particle dispersion

If a particle
dispersion is produced
today we need to know
that it will be exactly
the same in a few months time
i.e. it has a long shelf life
 Some Examples of Particle Dispersions
Requiring Long Term Stability

Paints and Coatings Pharmaceutical Suspensions

 Maintaining Dispersion Stability

How do we
maintain stability?

The most popular

way of achieving this What’s that?
is by electrostatic
repulsion
 Zeta Potential and
Dispersion Stability

So if all the particles have a zeta

potential which is more negative than –30mV
or more positive than +30mV
the dispersion should remain stable

The lower the zeta potential

value is, the more likely the dispersion
will not remain stable
 Zeta Potential and
Dispersion Stability
Positive
zeta potential
STABLE
+30mV

0mV NOT STABLE

-30mV
STABLE
Negative
zeta potential
 Can We Change The
Zeta Potential?

Yes you can alter the

Often the simplest way
zeta potential to try and
to do this is to alter the pH
make your particle dispersion
of the sample
less or more stable

What do you The pH of sample is a

mean measure of how
by pH? acidic or basic it is
 pH

pH is measured on a scale of 1 to 14

Acid Neutral Base

1 2 3 4 5 6 7 8 9 10 11 12 13 14
Stomach Lemon Vinegar Rain Milk Baking Ammonia
Acid Juice Water Soda

The zeta potential will be dependent

upon the pH of the sample
 Zeta Potential and pH

60

40 STABLE
Zeta Potential (mV)

20 Isoelectric
Point UNSTABLE
0

-20

-40
STABLE
-60
2 4 6 8 10 12

pH
 How Do We Measure
Zeta Potential?

Zeta potential is measured

by measuring how quickly
particles move in an
applied electrical field

How do
we do that?
 Measuring Particle Mobility
in an Electric Field
- +
 Measuring Zeta Potential Using
Laser Doppler Electrophoresis
Measurements are made
in a Zetasizer Nano
instrument using
laser Doppler electrophoresis

The Nano series incorporates

the patented technique
of M3-PALS
(Mixed Mode Measurement
Phase Analysis Light Scattering)

Electrophoresis is the movement of a charged

particle relative to the liquid it is suspended
in under the influence of an applied electric field
 Measuring Zeta Potential Using
Laser Doppler Electrophoresis
Laser Doppler electrophoresis is a technique used to
measure the movement of charged particles in an electric
field which utilizes the well-known Doppler effect

Everyone has experienced

the Doppler effect

Meeeeeeeeeeeeeeeeeeooooooooooooooooooooooow!
 Measuring Zeta Potential Using
Laser Doppler Electrophoresis
Light scattered from a moving particle experiences a
frequency shift
Particle velocity V=0

F1

Scattered light has

F1 same frequency
as incident laser
Particle velocity V>0

F1 v

Scattered light now has

F2 greater frequency
than incident laser
 Measuring Zeta Potential Using
Laser Doppler Electrophoresis
Since the frequency of light
is so high (1014Hz), the shift in
frequency can only be measured by an
optical mixing or interferometric technique

This is done in practise using a

pair of mutually coherent laser beams
derived from a single source and
following similar path lengths
 Measuring Zeta Potential Using
Laser Doppler Electrophoresis
One of these beams must
pass through the particle dispersion
(this is called the scattering beam)

The other beam (called the reference beam)

is routed around the cell

The scattered light from the

particles is combined with the
reference beam to create intensity variations
Zetasizer Nano ZS Optics

Modulator
How Do These Intensity
Variations Arise?
 How Do These Intensity
Variations Arise?
Reference beam F1
F1
 How Do These Intensity
Variations Arise?
Reference beam F1 and scattered beam F2
F1

F2

Lets combine them

 How Do These Intensity
Variations Arise?
Reference beam F1 and scattered beam F2
F1

F2
 How Do These Intensity
Variations Arise?
Reference beam F1 and scattered beam F2
F1

F2

F1- F2= f
 How Do These Intensity
Variations Arise?
Reference beam F1 and scattered beam F2
F1

F2
A A The two waves interfere
constructively at A and
B destructively at B

F1- F2= f
 How Do These Intensity
Variations Arise?
Reference beam F1 and scattered beam F2
F1

F2
The two waves interfere
A A constructively at A and
B destructively at B

F1- F2= f

The interference produces a modulated beam having a much

smaller frequency equal to difference of F1 and F2
 The Beat Frequency is
Focussed onto the Detector

It is the intensity variations of the “beat” frequency which are

carried onto the detector
Determining the Sign of the Doppler Shift

The sign of the Doppler shift is

determined by comparing this
beat frequency with that
of a reference frequency

This reference frequency is produced

by modulating one of the laser
beams with an oscillating
mirror (modulator)
 Determining the Sign of the Doppler Shift

The mobility of the particles

in an applied field will therefore
produce a frequency shift away
from that of the modulator frequency

This gives an unequivocal measure

of the sign of the zeta potential

Analysis of this data was performed

in the “old” Zetasizer by
a technique called Fourier Transformation
 Determining the Sign of the Doppler Shift

In the Zetasizer Nano, a technique called

Phase Analysis Light Scattering is used

The electrophoretic contribution

to the motion can only be
detected by sampling many oscillations
of the frequency shifted signal

This is fine for high mobility particles since they pick up a lot of
energy from the electric field which moves them quickly through
the beam, producing many oscillations in a short space of time
 Why use PALS?

Intensity For high mobility particles enough data is

collected within the measurement time to
produce an accurate determination of the
particle motion

t/s

Intensity For low mobility particles only a fraction of

an oscillation may have been completed
within the measurement time.
In this case it would be impossible to
determine the particle’s motion
t/s
 Applications Where
PALS is Beneficial
Non-aqueous dispersants
with low dielectric constants
(mobility is proportional High viscosity samples
to dielectric constant)

Any sample where the

particle mobility is slow

High salt
(must work at low voltages
to avoid heating effects)
 Disposable Zeta Potential Cell
The Zetasizer Nano represents a
significant step forward in
electrophoretic mobility
measurement technology with the
inclusion of the patented Folded
Capillary Cell
Cell is designed to be disposable on
an aliquot by aliquot basis
In a nutshell: New Sample – New
Cell
This removes cross contamination
completely and means that the cell
does not need to be cleaned
 Universal Dip Cell
Primarily used for non-
aqueous applications and
aqueous measurements where
detailed distributions are not
required
Conclusions

The Zetasizer Nano is the only commercial

instrument which can measure particle size, zeta
potential and molecular weight
Disposable (low maintenance) capillary cell
Widest concentration range of any DLS instrument
on the market (NIBS)
Widest size range of any DLS instrument on the
market (NIBS)
Questions ?

PLEASE DO CONTACT
BARATHITHASAN.R
87545 92940
barathithasan@aimil.com