786

Dynamic Light Scattering (DLS)

 Dynamic Light Scattering
• Dynamic Light Scattering (DLS, also referred to as Photon
Correlation Spectroscopy or Quasi-Elastic Light Scattering)
is a technique for measuring the size of particles in the sub
micron regions down to 1 nm diameter.

• These can be colloidal particles, macromolecules, bubbles

or droplets. Typical applications are emulsions, micelles,
polymers, proteins, nanoparticles or colloids.

• DLS is based on the extraction of spectral information

derived from time-dependent fluctuations of the light
scattered from a spatially limited volume within the
sample.
 Basic principle

• The sample is illuminated by a laser beam and the

fluctuations of the scattered light are detected at a
known scattering angle θ by a fast photon detector.

• The particles scatter the light and thereby imprint

information about their motion. Analysis of the
fluctuation of the scattered light yields information
about the particles. Experimentally intensity
fluctuations is characterized by computing the intensity
correlation function g2(t), which provides the diffusion
coefficient (D) of the particles.
 Dynamic Light Scattering: Setup
Incident light Diffusing colloids Transmitted light

Scattering
angle
Light scatters in
all directions
Detector

Fluctuating scattered light intensity

Fluctuations in scattered light arise from diffusion

 Scattered Light Intensity: t = 0
Particles in fixed
positions
Incident light
Unperturbed light

If particles remain
fixed, so does Detector
intensity at detector
I = I0

Static scattering reveals micro-structure; e.g. x-ray crystallography

 Scattered Light Intensity: t = Δt
Particles have
diffused
Incident light
Unperturbed light

If particles move,
intensity at detector Detector
changes
I = I(Δt) = I0
Duration of Δt before intensity changes
gives time scale of motion

Dynamic light scattering reveals ensemble average motion

DLS Set up and out put
 Reflection and Scattering
Difference between scattering and
just normal reflection:
Scattering occurs when a particle
of light is fully absorbed and then
emitted while reflection is when a
wave/particle is simply reflected
off the surface without interacting.

Scattering - Particle size matters

 Signal fluctuates in time
The net result is a fluctuating scattered intensity . The corresponding measured
normalized intensity correlation function is written as:

• How fast? Over what time scale?

• Instrument calculates correlation function:

 Compare the signal I to itself:

I (t ')
I (t '+ t)
I (t '+ 2t)
.…

I (t '+ 9t)
t
Lag time: D
If: I (t '+ D t) » I (t '), then G(D t) is large

As: I (t '+ D t) ¹ I (t '), then G(D t) diminishes

What does the correlation G look like?
• Siegert approximation
• Where

where g(1)(t ) = is the sum of all the

exponential decays contained in the
correlation function.
.
By means of the Siegert relation can be related to the electric
field correlation function g1(q,τ).
 Meaning of decay time-scale
Fluctuations in scattered light arise from diffusive motion
Detector Correlation function of scattered
light intensity: exponential decay

Real-time hardware
correlators measure
lag time Δt at which
I(Δt) = I0
 From time-scale to size scale
• Units of Diffusion = [length2/time]
• Length scale given by scattering vector q

( 2)
q = 4p nsin q l

l : laser wavelength
J : scattering angle
n: solvent index of refraction

q has units 1/length; can be controlled by adjusting 

Diffusion through area 1/q2 occurs at time scale τ
 Measured Diffusion Constant
• Diffusion D has units length2/time
• Time is τ, as obtained through exponential fit
• Length scale is 1/q.
• Area particle diffuses through in length scale is
1/q2

• Hence measurement of D is: 1

D= 2
qt
 Particle size from D
• Use Stokes Einstein relation, assuming
spherical particles:
kBT h : Viscosity of medium
D= , where:
6p h a a : Radius of particles
• Combine measured D with Stokes Einstein:
kBT 1
D= = 2
6p h a q t
• …a d sol e for radius a kBT 2
a= qt
6p h
 Challenges
• The Rayleigh approximation tells us that I  d6
and I 1/λ 4.
• The d6 term tells us that a 50nm particle will
scatter 106 times as much light as a 5 nm particle.
Hence there is a danger that the light from the
larger particles will swamp the scattered light
from the smaller ones. This d6 factor also means
it is difficult with DLS to measure, a mixture of
1000 nm and 10 nm particles.
• The inverse relationship to 4 means that a higher
scattering intensity is obtained as the wavelength
of the laser used decreases.
 Factors to consider
• Decay rate depends on the wave vector and thus the scattering angle.
• Particles of different sizes scatter with different intensities in dependence
of the scattering angle. Thus there is an optimum angle of detection for
each particle size.
• A high quality analysis should be performed at several scattering angles
(multiangle DLS). This becomes important in case of polydisperse samples
with unknown particle size distribution since at certain angles, the
scattering intensity of some particles will completely overwhelm the
weak scattering signal of other particles, thus making them invisible to
the data analysis at this angle.
• DLS instruments working exclusively at a fixed angle can only deliver good
results for some particles. Therefore, special attention should be paid
while considering a precision of an DLS instrument. For the fixed angle
instruments such indications are only ever true for certain particles.
Hydrodynamic radius
The DLS measured radius is the
radius of a hypothetical hard
sphere that diffuses with the
same speed as the particle
under examination.

Macromolecules in solution are

non-spherical, dynamic and
solvated. As such, the radius
calculated from the diffusional
properties of the particle is
indicative of the apparent size
of the dynamic
hydrated/solvated particle.
Hence the terminology,
hydrody a ic radius.
 Challenges
• The theory of DLS is only valid for single scattered light. The
interpretation becomes difficult for systems with
contributions from multiple scattering. Small contributions of
multiple scattering can result in large analysis errors.
Particularly for larger particles with high scattering contrast,
this limits the technique to very low particle concentrations.
• A large variety of systems are therefore excluded from
investigations with conventional DLS.
• It is possible to suppress multiple scattering in DLS via the
cross-correlation approach. The idea is to isolate singly
scattered light and suppress undesired contributions from
multiple scattering.
• Alternatively, in the limit of strong multiple scattering, a
variant of dynamic light scattering called Diffusing Wave
Spectroscopy (DWS) can be applied.
 Zeta Potential Analysis

• The zeta potential is an fundamental indicator of

dispersion stability.
• Large zeta potentials predict a more stable
dispersion.
• Measurement of the zeta potential, or
electrostatic attraction / repulsion, is important
to many industries from pharmaceuticals to
mineral processing and from water treatment to
additives for electronics.
 Benefits of ZP
• ZP measurement brings detailed insight into the causes of
dispersion, aggregation or flocculation, and is applied to improve
the formulation of dispersions, emulsions and suspensions.

• Speed of introduction of new formulations is the key to product

success. ZP measurements improve formulation stability and
shelf life and reduce formulation time and cost.

• In water treatment, monitoring dosage using zeta potential

measurements reduce the cost of chemical additives by optimizing
the dosage control.

• The measurement of zeta potential has important applications in a

wide range of industries including; ceramics, pharmaceuticals,
medicine, mineral processing, electronics and water treatment
 Controlling Particulate Suspensions
Suspension behavior is significantly affected by surface
interactions.
And that is controlled by

Size of interface Chemistry of interface

Particle size distribution Surface charge

Particle shape Surface tension
Porosity Contact angle
 What is Zeta Potential?
• Zeta potential is the
charge on a particle
at the shear plane.

• The potential difference

existing between the
surface of a solid
particle immersed in a
conducting liquid (e.g.
water) and the bulk of
the liquid.
 How do Surfaces Acquire Charge?
• Ionization of surface groups

H+

-COO- H+
-COO- H+
-COO-H+

-COO-
H+ H+
-COO-
-COO-H+
-COO-H+
-COO-
 Differential loss of ions from the
surface

Ag+

Ag+
Ag+
Ag+
Ag+ Ag+
I- I-

I I Ag I Ag I I Ag I Ag Ag I Ag I I Ag Ag I Ag I Ag I I Ag Ag I Ag I Ag I
Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag I Ag
 How do Surfaces Acquire Charge?
• Specific adsorption of ions, e.g. ionic
surfactants

H+

H+
H+

H+ H+
 Why ZP?
Good way of evaluating electrostatic stabilization of suspensions
Can use to predict interactions
provides information about the
material surface-solution interface
The presence/or absence of surface
charged moieties on materials affect
their performance and processing
characteristics in suspension
The sig a d ag itude of ζ affects
process control, quality control and
product specification
at simplest level: help maintain a
more consistent product
at complex level: can improve
product quality and performance
 Stability and Zeta Potential (ζ)
• The magnitude of the ZP gives an indication of the potential
stability of the colloidal system. A colloidal system is when one of
the three states of matter: gas, liquid and solid, are finely dispersed
in one of the others.

• If all the particles in suspension have a large negative or positive ZP

then they will tend to repel each other and there is no tendency to
flocculate.

• If the particles have low ZPvalues then there is no force to prevent

the particles coming together and flocculating.

• Particles with zeta potentials more positive than +30mV or more

negative than -30mV are normally considered stable.
 Zeta Potential and pH
• A zeta potential value on its own without a
quoted pH is a virtually meaningless number.
• pH affects ZP
 Electrokinetic effects
• Particles with charges on the surface will exhibit certain effects
under the influence of an applied electric field. The effects are
collectively defined as electrokinetic effects and defines the
induced motion , which are:
Electrophoresis :
• The movement of a charged particle relative to the liquid it is
suspended , under the influence of an applied electric field.
Electroosmosis :
• The movement of a liquid relative to a stationary charged surface
under the influence of an electric field.
Streaming potential :
• The electric field generated when a liquid is forced to flow past a
stationary charged surface.
 Electrophoresis
• When an electric field is applied across an electrolyte, charged particles
suspended in the electrolyte are attracted towards the electrode of
opposite charge. Viscous forces acting on the particles tend to oppose this
movement. When equilibrium is reached between these two opposing
forces, the particles move with constant velocity.

The velocity of the particle is dependent on the following factors:

• Strength of electric field or voltage gradient.
• The dielectric constant of the medium.
• The viscosity of the medium.
• The zeta potential.

• The velocity of a particle in an electric field is commonly referred to as its

Electrophoretic mobility.

Ffield = zeE Stokes la Fretardation = 6rs

 Henry equation
The Henry equation is:
UE = 2  z f(k a)
3
• z : Zeta potential. UE : Electrophoretic mobility;  : Dielectric constant.
•  : Viscosity; ƒ Ka : Henry’s function.

• Two values are generally used as approximations for the f(Ka)

determination either 1.5 or 1.0.
• Electrophoretic determinations of zp are most commonly made in
aqueous media and moderate electrolyte concentration, where
f(Ka) is 1.5, and is referred to as the Smoluchowski approximation.
Therefore calculation of zp from the mobility is straightforward for
systems that fit the Smoluchowski model, i.e. particles larger than
about 0.2 microns dispersed in electrolytes containing more than
10-3 molar salt.
• For small particles in low dielectric constant media f(Ka) becomes
1.0 and allows an equally simple calculation. This is referred to as
the Huckel approximation.
• Non-aqueous measurements generally use this.
 Measuring Electrophoretic Mobility

• From the electrophoretic mobility zeta potential

is inferred from theoretical considerations.
How is electrophoretic mobility measured?
• The essence of a classical micro-electrophoresis
system is a cell with electrodes at either end to
which a potential is applied. Particles move
towards the electrode of opposite charge, their
velocity is measured and expressed in unit field
strength as their mobility.
• The technique used to measure this velocity is
Laser Doppler Velocimetry.
 He ry s fu ctio
• The units of k are reciprocal
length and
1/k="thickness" of the
electrical double layer (the
Debye length)
• a = the particle radius
• ka = the ratio of particle
radius to double layer
thickness
• For particles in polar media
the maximum value of F(ka)
is 1.5 (Smoluchowski
approximation)
• For particles in non-polar
media the minimum value of
F(ka) is 1 (Hückel
approximation)
 Electrophoretic light scattering
• ELS measures the intensity of light scattered from
particles moving in an applied electric field. From
these intensity changes the electrophoretic
mobility (due to the movement in the electric field
on top of the diffusion) and then the zeta potential
can be obtained
 Doppler Effect

The Doppler effect (or the Doppler shift) is the change

in frequency or wavelength of a wave for an observer
who is moving relative to the wave source. It is named
after the Austrian physicist Christian Doppler, who
described the phenomenon in 1842.

When an electric field is applied to the cell, particles

moving through the measurement volume will cause the
intensity of light detected to fluctuate with a frequency
proportional to the particle speed.
(Velocity = Distance/Time = Distance*Frequency)
Doppler shift
Interference
 Doppler shift

Apply an electric field and probe the response

of particles to applied field.
Will see Doppler shift in scattered light due
to particle motion with respect to fixed
electrodes.
When the distance is decreasing, the frequency of the
received wave form will be higher than the source wave form.
 Henry equation
The Henry equation is:
UE = 2  z f(k a)
3
• z : Zeta potential. UE : Electrophoretic mobility;  : Dielectric constant.
•  : Viscosity; ƒ Ka : Henry’s function.

• Two values are generally used as approximations for the f(Ka)

determination either 1.5 or 1.0.
• Electrophoretic determinations of zp are most commonly made in
aqueous media and moderate electrolyte concentration, where
f(Ka) is 1.5, and is referred to as the Smoluchowski approximation.
Therefore calculation of zp from the mobility is straightforward for
systems that fit the Smoluchowski model, i.e. particles larger than
about 0.2 microns dispersed in electrolytes containing more than
10-3 molar salt.
• For small particles in low dielectric constant media f(Ka) becomes
1.0 and allows an equally simple calculation. This is referred to as
the Huckel approximation.
• Non-aqueous measurements generally use this.