Malvern Instruments

Training Course
 Describing Particle Size
Particles come in
all different
shapes and sizes

The problem is
deciding on the
best way to
describe them
 Microscopy
A very powerful technique as it allows
direct observation of particles within the
approximate size range 1 -150 microns.

Produces a number distribution based on

measurement of diameters - or more usually
projected area diameters.
 Microscopy - Advantages

Allows direct observation of the particles

rather than observing a property dependent
on particle size.
The dispersion of the sample can be
assessed
Initially easy to set up and use
A good back-up with other methods (e.g.
Diffraction and S.O.Ps)
 Microscopy -Disadvantages
Sampling of the distribution is poor! It is
impossible to measure all the particles
present!
The result is a number distribution not a
volume distribution.
Ignoring one 10um particle is the same as
ignoring 1000 1um particles!!
 Sedimentation

A technique used in the paint and ceramics

industries.

Requires particles in a fluid to settle under

gravity

Limited particle size range since...

 Sedimentation
Largest particles fall quickly through the
medium and can be missed.

Smallest particles are held in suspension for

extensive periods
Sedimentation - Advantages

A relatively cheap technique to use if you

have the time!

Capable of producing reproducible results if

used in the right hands.
Sedimentation.

gd
s f
2

u st
18
 Sedimentation - Disadvantages
Since Stokes law depends on the viscosity
of the fluid, temperature has to be well
controlled.
Unable to handle mixtures of different
density.
The technique is slow
Tends to underestimate sizes
Sieving.
 Sieving

A widely used method of particle sizing.

Woven wire sieves cover size range of

20um to 125mm.
Punched hole sieves available to cm range
Micromesh sieves extend the range down to
5um.
 Sieving...

In practice particles will look more like this and

there will always be some that in volume or
weight terms are larger than their equivalent
sieve measurements.
Shape must be considered for this technique
 Sieving - a common question

I sieved my material to 110um but laser

diffraction tells me I still have particles
larger than 110um. How can this be so?

Imagine we have a sieve of 110um hole

construction...
 Sieving

100um

100um

Volume of cube = 106 um3.

Diameter of sphere with the same volume as cube =124um

 Sieving
The situation gets worse as the shape of the
particle changes

200um

100um
Volume of particle is now 2x106 um3

Diameter of sphere with same volume as particle

is now 156um
 Equivalent Spheres

The best way of describing irregularly

shaped particles is to compare some aspect
of their shape or size to the diameter of a
sphere.
Equivalent sphere.
Equivalent spheres
 Characterising distributions
Whatever method we choose...
We need to be aware that different techniques
will give different results.

This is because we are measuring a different

property of the particle;
e.g. a length or a Stokes diameter or a
volume.
 Graphical data. Volum e %
30 100

90

80

70
20
60

50

40
10
30

20

10

0 0
0.1 1.0 10.0 100.0

Particle Diam eter (m .)

 An MS2000 Measurement.
1. A source of light.
2. A means of passing the light through the
particles to allow scattering.
3. A means of measuring the light intensity at
a range of scattering angles.
4. A method of analysis which converts the
measured scattering to a particle size
distribution.
 Modules.
The transmitter module containing the laser,
power supplies and spatial filtering.
The sample area with any cell and sample
dispersion accessories.
The receiver module containing the detector
arrays
The computer.
 Scattering from particles

Incident light
Small angle scattering

Incident light
Large angle scattering
 Scattered Light
Large particles scatter light mainly in the
forward direction i.e. at small angles.
Small particles scatter light at larger angles
-but this scattered light is much weaker
than forward scattered light.
We need to choose our light sources with
care!
 Laser Light Source
Intensity of laser source allows sensitive
measurements of all sizes and low
concentrations.
Monochromatic light helps resolution.
A Stable Laser output permits high
reproducibility.
 The Red light optical System
Sample cell
Focal plane detector
Laser

Laser monitor
Obscuration monitor
Range Lens
 Sample region.
Particles must be well dispersed so that we
are measuring, as far as possible, the
scattering from individual particles.
Multiple scattering could be a problem for
high obscurations.
Need to assess the effects of multiple
scattering on size distribution - is it
significant?
 Effect of High Obscuration
Detector High ring no
Wet cell
High ring no
scattering
indicates small
particles
Low ring no

Increasing the obscuration (concentration) makes

multiple scattering more likely. This leads to higher angle
scattering which corresponds to smaller particle size.
 Multiple Scattering
The effects of multiple scattering are
negligible for a wide range of obscuration
values but a very high levels of obscuration
the effects increase dramatically.
But remember, you can have more
confidence in your result if you know it has
been calculated from good data. Signal to
noise ratio is important.
The Whole Detector Array
How is the scattered light organised?
The laser is illuminating 100s or 1000s of
particles at any instant.
The light scattered from these particles is
focussed onto a detector.
The detector records the amount of energy
falling onto its light sensitive zones.
The detector thus records the amounts of
energy scattered at particular angles.
 The Fourier transform

Detector
f
X

Since particles of equal size scatter at equal angles, the

scattered light from the particles will be parallel and thus
brought to the same point on the focal plane; i.e. the
detector.
The Reverse Fourier System
Lens Detector

Wet cell

d
 Analysis options
General purpose
Multimodal
Monodispersed
With an explanation of which analysis model
is best for your application
 Detection system.
Scattering pattern sampled at a range
of angles.
Pattern must be captured in a very
short time [ 10 s ].
A large number of snaps must be
collected.
 Analysis.
Transfer data to P.C.
Calculate size distribution as % in band.
Calculate undersize distribution.
Calculate derived parameters.
 Theory of LALLS - aims .
The basic theory of LALLS [ Low Angle Laser Light
Scattering ].
The method of analysis used in the Malvern
Mastersizer range of instruments.
The important choices of parameters in performing
an analysis.
When those choices are critical.
How to obtain information to allow you to make
correct choices.
Scattering intensity vs. Angle.
Scattering Intensity

0.3 micron
3 micron
30 micron

0 1 2 3 4 5 6 7
Angle / degree
 Calculation of scattered light.
Mie model.
Optical parameters - refractive index and
absorption.
 Mie Theory

Dates from 1907/8

Accounts for the interaction of light with
matter - solves Maxwells equations
exactly
Valid for all sizes of particle, wavelengths,
and scattering angles
Gives correct answers and accounts for
secondary scattering
 Mie Theory
We need to feed Mie theory with more info.
Refractive of particle np
Refractive index of dispersant nd
Absorption of particle abs
The relative values if refractive index and
absorption are calculate
np abs
nd nd
Mie scattering.
 Mie Theory
Give Mie theory a particle size
distribution and it will happily calculate a
scattering pattern.
The Mastersizer will produce a
scattering pattern from a size
distribution.
We need to turn the scattering pattern
into a size distribution!
This is not easy!
 Mie Theory
1. Question?
4 + 5 =?
Ans = 9
2. What does 9 equal?
4+5 7+2 (81)0.5
9+0 6+3 (27/3)
8+1 3 X3 10 -1
etc.etc.etc
 Calculation of size distribution
Comparison

Mie
Guess
Scattering Size Distribution Scattering

Comparison
Size distribution
Scattering
 Complementary information.
PCS.
Microscopy.
Microscopy
 Please remember.
The quality of the result obtained depends
mainly on the dispersion state and stability
of the sample you wish to measure.
The biggest source of error in particle size
analysis is the user.
 Users 3 - 50%

Sources of variation
Sampling
2 - 30%

Sample
Handling
Units
Optical Bench
1 - 2%
0.5 - 2%
How do you make sure you have
a good result?
General appearance of result.
Quality of data
Inspect fit
Optical properties
Residual.
Choosing the refractive index.
From standard lists.
Measure in refractometer.
Estimate by analogy.
Average values for composite materials.
 Choosing the absorption.
Standard lists.
Physical appearance ( microscope ).
Confirmation from concentration
measurements.
Effect of choosing the wrong
model
The effect of changing the presentation

%
10 100
90
80
70
60
50
40
30
20
10
0 0
0.01 0.1 1.0 10.0 100.0 1000.0
Particle Diameter (m.)
How do I tell if a presentation
code is inappropriate.
Shape of curve
Examining the fit
Residual
 Fit and residuals
To fit data, the software takes the data and the
optical properties and performs a series of
calculations.
The end result is the size distribution which is
most likely given that data and optical
properties.
The residual is a measure of the goodness of
fit. The fit at any point can also be examined.
Fit and residuals

A low residual (<1%) = A good result,

right?
Not always!
Many very different shaped distributions
can give similar low residuals.
Different distributions similar
residuals
Differing plots, similar residuals

%
10 100
90
80
70
60
50
40
30
20
10
0 0
0.01 0.1 1.0 10.0 100.0 1000.0
Particle Diameter (m.)
 More on fit and residuals

Examine how the fit hugs the data

especially for the higher data channels.
This can flag inappropriate imaginary
refractive indices if the particle refractive
index is known.
Sample A - 0 imaginary

20 Residual = 0.344 % Data Fit

18

16

14

12

10

2
0
8 16 24 32 40

Detector Number
Sample A - 0.01 imaginary

20 Residual = 0.159 % Data Fit

18

16

14

12

10

2
0
8 16 24 32 40

Detector Number
The imaginary refractive index

What is it?
It takes into account everything that
happens on or in the particle other than
scattering.
Absorption / reflection
What imaginary value do I use,
and how do I get it?
Reference books?
No.
Examine the fit at different imaginary
values
Microscopy
Examination under the
microscope

0 Glass beads

0.001 Emulsions

0.01 Calcium Carbonate

0.1 Most materials

1.0 Pigments and metal powders