Particle Sizing:

Size matters
Dr. Lara Matia-Merino
School of Food and Advanced Technology

with thanks to Skelta Anema (Fonterra, NZ)

Bryn McDonagh, Malvern Instruments, UK
David Horne (Hanna Research Institute, Scotland)

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 Outline
1. Introduction
2. Basic principles of particle size analysis
3. Techniques:
– Sieves
– Sedimentation
– Electrical Pulse Counter (Coulter Counter)
– Microscopy
– Light Scattering:
• Static Light Scattering:
* MALLS (Dawn, Wyatt Technologies)
* LALLS (Mastersizer, Malvern Instr.)
• Dynamic Light Scattering (PCS)
* DWS, Zetasizer (Malvern Instr.)
– Others: Ultrasonic attenuation spectroscopy (Ultrasizer), Nuclear
Magnetic Resonance (NMR), Neutron Scattering…..

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What is a particle?

• “Any condensed phase three-dimensional

discontinuity in a dispersed system may
generally be considered a particle”
NIST Practice Guide

• Some Food particles:

– Powder particles
– Cocoa particles
– Oil droplets
– Protein molecules and aggregates
– Polysaccharide molecules
– Casein micelles
– Starch granules
– Ice crystals
– Sugar crystals

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Size in Food Colloids

1 nm 1 mm
1 mm
Colloidal range
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Many different techniques commonly used to study foods
according to scales of constituent structural elements

Aguilera, 2006
ENGINEERING PERSPECTIVE

1 mm 10 mm 100 mm

NANOSCALE MICROSCALE MACROSCALE

Size Ranges of Various Techniques

0.001
Particle size and particle size
distributions why are they important?

• Quality control
– More consistent product---enhances end-use value,
improves profitability, reduces waste, reduces
processing costs, energy requirements

• Size governs product performance

– Phase separation process, dusting tendency, drug
delivery

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Measuring size for determining…

1.Bulk properties 2.Primary particle

properties
• Flow ability • Activity/reactivity rate
• Viscosity • Dissolution rate
• Agglomeration • Hydration rate
• Dusting tendency • Moisture absorption

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Measuring size for…

3.Examining product stability

or industrial processes
• Monitoring particle size reduction or growth in
suspensions, emulsions

• Examination of the effects of homogenization

conditions on emulsions

• Impact of milling conditions on organic or inorganic

pigments..

• Optimizing and assessing the stability of disperse

systems

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Example: Particle size and drug
performance (Metered dose inhalers)

• Drug adsorption into the lungs is controlled by the

size of the drug particle

• Size must be in the range 0.5-5 µm for the drug to

be properly adsorbed

• Too large and the particles are trapped in the

hairs of the throat and do not reach the lungs

• Too small and they go into the lungs but are

exhaled again

– In either case, drug is wasted but more

importantly the dosage cannot be controlled

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 Example: Particle size and coffee

• Percolator
– Water refluxed many times, long contact
time, coarse grind
• Cafetiere
– No reflux, single contact, finer grind
• Filter
– Single short contact, even finer grind
• Espresso
– Contact time between steam and coffee
very short, finest of all particle size
distributions

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Sampling for particle size
measurements

• Must be representative
• Must not change during the period of measurement:
– Must not sediment
– Must not cream
– Must be stable to dissolution or aggregation

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Basic principles

The Particle size problem.

• I give you a matchbox and a ruler and ask

you to tell me what size it is.

• What will your reply be ?

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Basic principles

You may reply

“20x10x5mm”
which is correct

• It is not possible to describe the 3-dimensional

matchbox with one unique number
• There is only one shape that can be described by
one unique number and that is a sphere

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 Basic principles

All particle sizing techniques measure

some 1-D property of our particle
By assuming that this property refers to a
sphere, it provides us with one unique
number to work with.
This is known as
‘The Equivalent Sphere Theory’
Basic principles
Equivalent sphere in
terms of volume:

= 2X

4
v = X 3

v =   r 2  h = 10000 Equivalent sphere in terms

of surface area: 47 mm
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Basic principles

What size
are they ?

“For irregularly shaped

particles, characterization
on particle size must
include information on
particle shape”

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Basic principles

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 Basic principles

• Depending upon which property we take to

use in our calculation may make a
significant difference to our answer (max
length, min. length, volume, surface area, etc…)

• Different techniques use different

properties of the particle to calculate their
size.

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 Basic principles
- The problem with Means -

• Imagine we have 3 spheres with

diameters of 1,2,3 units.
• What would be their average size using
different techniques?

1
2 3
 Basic principles

– Add all (measured) diameters up and divide by

the number of particles:

(1+2+3)/3= 2.00
Number-Length mean: D [1,0]
Microscopy

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Basic principles
1+ 2 + 3 Number length mean
X nl = D[1,0] = = 2.00
3

1+ 4 + 9 Number surface mean

X ns = D[2,0] = = 2.16
3

1 + 8 + 27 Number volume or
Xnv = D[3,0] = 3 = 2.29
3 number weight mean

1 + 8 + 27 Surface area mean

X sv = D[3, 2] = = 2.57
1+ 4 + 9 diameter
1 + 16 + 81
X vm = D[ 4 ,3] = = 2 .72 Volume mean diameter
1 + 8 + 27

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Different techniques: different means

• Number-length mean or D[1,0]- Microscopy

• Number-surface area mean or D[2,0]- Image

analysis

• Number- volume mean D[3,0]- Electrozone

sensing

• Volume mean diameter D[4,3] and surface area

mean diameter D[3,2]- Laser diffraction

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Different techniques: different means

Microscopy
• Usually measure the diameters with a
graticule,add them up and divide by the
number of particles to get an average.
• This generates Number-length mean or
D[1,0]
Image analysis
• Usually measures the area of each particle
and divide by the number of particles.
• This generates the Number-surface area
mean or D[2,0]
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Different techniques: different means

Electrozone sensing
• Measures the volume and counts the
number of particles and generates
number- volume mean D[3,0]
Laser diffraction
• Ensemble technique generating a
distribution proportional to volume -
volume moment mean D[4,3] - numbers of
particles not needed

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Basic principles

• Each technique is liable to generate a different mean

diameter as well as measuring different properties of our
particle.

• Be aware of the great dangers of interconversion between

number, length, and volume/mass means: i.e microscopy

•Particle counting vs. particle sizing

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Basic principles

• “Number means” when the number of particles is important

(i.e contamination in rivers, air clean enough?…)= particle
counting (dust, etc…)

• Particle sizing = particle size distributions

– % > 50 mm
– % < 2 mm
– Average size
– How much coarse/fine material?

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Practical example: Barium Titanate
(believed size around 70 nm)
Size by laser Size by volume: 0.55 mm
diffraction

Convert to number: 0.076 mm = 76 nm

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Different distributions depending we are looking at
volume/mass or at number distributions

Number and volume: “Words should be weighed and not counted”

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Particle Sizing Techniques
Sieves

• Very old technique but has the advantage that it

is cheap and is readily usable for large particles
such as are found in the mining industries.
• Allows separation of materials.
• For grain milling, sugar particles…

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Sieves. Disadvantages…

• Low resolution and low precision (materials as small as

1mm impossible to resolve)

• Measurement of dry powders below 45mm very difficult

• Cohesive, agglomerated material are difficult to measure

• The longer you measure the smaller is your answer

(measuring times and operating procedure need to be
standardised)

• Second smallest dimension is measured (a true weight

distribution is not produced)

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 Sieving - a common question

“I sieved my material to 110mm but Laser diffraction tells me I

still have particles larger than 110mm.”

How can this be so?”

Diameter of sphere with equivalent

volume = 124mm approx
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Sieving...
The situation gets worse as the shape of the particle
changes

Volume of particle is now 2x106 mm3

Diameter of sphere with same volume is now 156mm

 Sieving - a common question

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.
Sieves mix shape and size in an unpredictable
manner - diffraction measures the volume of the
particles.
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Sedimentation Techniques

• Particle size is determined by measuring the

velocity at which particles sediment (or cream)
in a gravitational or centrifugal field

• Simple equipment (Andreasen pipette) or more

complicated involving the use of centrifuges or
X-rays

• Gravitational sedimentation / Centrifugation

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 Gravitational sedimentation

• The traditional method for paint and ceramics

industry. Range 2-50mm
• The principal of measurement is based on:

Stokes’ Law ( )
d 2 = diameter of particle m 2
 kg 
 p = density of particle 3 

d ( p − m )
2 m 
 kg 
V= •g  m = density of medium  3 
m 
18  = viscosity of medium 
 kg 
 m • s


m
g = acceleration due to gravity 9.8 2 
s 

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Andreasen Pipette - Gravitational Sedimentation

The concentration changes at the bottom of a vessel

are measured, as suspended particles settle in the
dispersing liquid. A 10 ml sample is drawn from the
pipette, generally at 20 sec intervals. The sample is
drained, dried, and weighed or otherwise analyzed for
concentration.
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Gravitational Sedimentation

• Stokes’ Law is only valid for spheres which possess the

unique feature of being the most compact shape for the
volume or surface area they possess.

• Irregular shaped (or normal) particles will possess more

surface area than the sphere and will thus fall more
slowly because of the increased drag than their
equivalent spherical diameters.

Approx Settling
Particle Diameter (mm) Order of Size Time (1 metre)
10
Gravel 0.9s
1
Coarse sand 9s
0.1
Fine silt 110s
0.02
0.001
Silt 1.5 hrs
0.000001
Colloids 2.5 yrs
Color Particles 200 yrs

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Gravitational Sedimentation

Disadvantages

• Speed of measurement - 25min to 1 hour

• Need to control temperature accurately (1oC change in
temp. will change viscosity by 2%)
• Inability to handle mixtures of different densities
• Limited range: below 2mm system is very inaccurate as
Brownian motion exceeds gravitational settling.
Verification issues.
• Disc-shaped particles “flutter” and do not settle in a
straight line as required by Stokes’ Law

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Centrifugal •Micro-spheres
sedimentation •Starch/flour particles

•
The CPS Disc Centrifuge separates particles by size using centrifugal
sedimentation in a liquid medium. The sedimentation is stabilized by a slight
density gradient within the liquid.
The particles sediment within an optically clear, rotating disc. When
particles approach the outside edge of the rotating disc, they block/scatter
a portion of a light beam that passes through the disc. The change in light
intensity is continuously recorded, and converted by the operating software
into a particle size distribution.

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Electrozone Sensing
(Coulter Counter)

• Developed in the 1950’s for

counting blood cells, which
are monodisperse
suspensions in a weak
electrolyte.

• Good technique for blood cells

• High resolution for very narrow
distributions

https://www.youtube.com/watch?v=auQznEZnMw0
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Electrical Pulse counting

•Typically particles between 4 and 40% of the diameter of the

hole can be reliably analyzed
•To cover a whole range of sizes is necessary to use glass tubes
with different sized holes
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Electrical Pulse counting

• Particles with diameters 0.6-400 mm

• Particles are made to flow through a small orifice in a

glass tube which has a voltage applied across it.

• As particles pass through the orifice the voltage changes,

this is measured by using an electrical pulse height
analyser. The height of the pulse is proportional to the
size of the particle.

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Electrical Pulse counting

Disadvantages
Difficult to measure emulsions (they have to be diluted first
considerably, so one particle passes through the hole at a
time). Cannot measure sprays
Must measure in an ELECTROLYTE
Requires regular calibration with expensive standards
Slow method as orifices have to be changed
Lowest size set by orifice selected - around
2 microns
Porous particles give problems

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Microscopy

• Excellent technique as it allows the user

to look at the particles in question.
• We can look at shape, dispersion or
agglomeration/aggregation
• But “seeing is not believing” in a
quantitative sense

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Shape is important!

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Microscopy

• 1g of 10mm particles contains 750x106 particles.

• 1g of 1mm particles contains 750x109 particles !
Missing or ignoring ONE 10mm particle has the same effect as
ignoring ONE THOUSAND 1 mm particles !

• Must be very careful to examine a representative sample

• Good for Qualitative not for Quantitative

• In combination with other techniques, microscopy becomes a

very valuable aid to particle size analysis

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 Microscopy Techniques

• Conventional optical microscopy

• Electron microscopy:
• Scanning and Transmission (SEM, TEM)

• Atomic force microscopy (AFM)

• Confocal laser scanning microscopy (CSLM)

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 Microscopy
(atomic and
(limit AFM molecular
CSLM 0.2 mm) level)

A probe is scanned over the

A laser beam is scanned surface of a material, and its
across a x-y plane within the displacement is measured using
sample. It is possible to an accurate laser detection
create a 3D-image. system. The force required to
keep the probe in the same
location, or the deflection of the
probe, is measured
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 Confocal microscopy

Protein bar structure

Red is fat (nile red stain)

Green is protein (fast green stain)

45 µm

Loveday et al. Food Research International 2009, 2010

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 Milk Gelation Research
(a)

0 mm 50

(b)

0 mm 50
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Atomic Force Microscopy

Phase image Height image and height profile

3D height image

Loveday and Gunning

(2016)
M assey University - Bachelor of Food Tech nology (Honours)

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 TEM

Electron
microscopy limit
0.2 nm (in
practice 1 nm)

Electron Microscopy
has elaborate sample
preparation methods.
Few particles are
An electron beam is directed measured (maybe
through the sample and the intensity 2000 a day by a good
of the transmitted beam is measured operator.)

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 Microscopy
Comparison of electron micrographs
of emulsions produced by:
(a) SEM (of butter) and
(b) TEM (of margarine)

TEM normally produces a two-

dimensional image of a sample,
whereas SEM produces a more
three-dimensional image.

The SEM of butter: g = fat droplet,

f = fat crystals.
The TEM of margarine: W = water
droplets, F = fat continuous matrix,
c = fat crystals. © Massey University
Light Scattering techniques
 What is light scattering?

• When electromagnetic radiation passes through matter, most of

the radiation continues in its original direction but a small fraction
is scattered in other directions

Incident Scattered
beam light

Blue sky, red sunsets..

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The scattering intensity is dependent upon a
number of factors :

• (1) the wavelength and polarization of the

incident beam (scattering intensity increases
with decreasing wavelength)

• (2) the size and shape of the particles

• (3) the difference in refractive index between

continuous and dispersed phases (i.e emulsions)

• (4) the concentration and structure of the

dispersion.

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INTERACTION OF LIGHT WITH MATTER:
Rayleigh Approximation

• For small particles (R< 10 nm) scattering is isotropic

(i.e. equal in all directions)
• Rayleigh approximation tells us that
I a d6 and

I a 1/ l4
• where I = intensity of scattered light, d = particle
diameter and l = laser wavelength

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Blue Sky—Rayleigh scattering

The blue color of the sky is caused by the scattering of sunlight off the
molecules of the atmosphere. This scattering, called Rayleigh scattering,
is more effective at short wavelengths (the blue end of the visible
spectrum). Therefore the light scattered down to the earth at a large
angle with respect to the direction of the sun's light is predominantly in
the blue end of the spectrum

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 Mie Scattering

The scattering from molecules and very tiny particles (R< 10 nm) is
predominantly Rayleigh scattering. For particle sizes larger than a
wavelength, Mie scattering predominates. This scattering produces a
pattern like an antenna lobe, with a sharper and more intense forward lobe
for larger particles.

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Wavelength and particle size

• The interaction between light waves and particles can

be conveniently divided into three regimes, according
to the relationship between the radius (r) and the
wavelength (λ):

– (1) long-wavelength regime (r < λ/20)→ Isometric scattering

– (2) intermediate-wavelength regime (λ/20 < r < 20λ)
– (3) short-wavelength regime (r > 20λ) → Anisometric
scattering

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Basis of light scattering

• Static Light scattering

– Measures the intensity of light scattered off

of a solution at a single time.

• Dynamic light scattering

– Measures the time dependence of the light

scattered from a very small region of solution,
over a time range from tenths of a microsecond
to milliseconds.

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 Static light scattering

• LALLS: Low angle Laser Light Scattering

= LASER DIFRACTION

• MALLS: Multi Angle Laser Light Scattering

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Basis of static light scattering

1. The amount of light scattered is directly proportional

to the product of the molar mass and solute conc.
when there is no absorbance (LS ∝ Mw ∝ c)
2. The angular variation of scattered light is directly
related to the size of the molecule:

Incident light
Small angle scattering

Incident light
Large angle scattering

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 Scattering from particles

Incident light
Small angle scattering

Large particles scatter light mainly in the forward

direction, i.e. at small angles.

Incident light
Large angle scattering

Small particles scatter light at larger angles

but this scattered light is much weaker than forward
scattered light.
MALLS (Multi angle laser light
scattering)

( 10nm-500nm)

– Measure angular dependence of L.S. (18 detectors

at fixed angles, 22.5-147°)

– Parameters obtained:
– Molecular weight Mw,
– Radius of gyration Rg
– Second virial coefficient A2

– To measure proteins, polysaccharides, polymers..

– Can be used on-line with size-exclusion

chromatography

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Basic static light scattering equation

• The Zimm formalism of the Rayleigh-Debye-Gans light scattering

model for dilute polymer solutions:

This model
K *c 1
= + 2 A2 c embodies the
two principles
R () M w P () described

K* is an optical parameter
c is the sample concentration (g/ml)
R(Θ) The Rayleigh ratio-the ratio of scattered light to
incident light of the sample
Mw is the weight-average molecular weight (molar mass)
P(Θ) is the scattering function → rg (radius of gyration)
A2 is a second viral coefficient

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WEBMINAR WYATT

https://www.youtube.com/watch?v=xWp1MTVwIZs

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Laser Diffraction (Mastersizer)

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Laser Diffraction (Mastersizer)

• LALLS (low angle laser light scattering) known as

Laser Diffraction ‹ 20 nm

One of the dominant method of particle size analysis

•Flexibility - ability to measure dry, suspensions, emulsions, even

sprays!
•Wide range - 0.02 – 2000mm
•Rapid measurement - a single measurement is taken in
0.001seconds = 1ms (MS2000)
•Excellent repeatability
•No calibration - is a fundamental measurement - but easy
verification of performance
•Accepted technique with international norms (ISO13320)

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Laser diffraction particle sizing

• Laser light scattering can be used for sub-micron to

millimetre particle size ranges
– claim a 0.02 to 2000mm size range

• Can be used for wet or dry systems such as:

– emulsions, powders, fat globules in milk

• Good size distribution information

– as long as optical properties of particles are
known (refractive index)

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Laser diffraction technique
Main components
DILUTE
sample

•Large particles scatter at small/narrow angles and vice versa - Θ ~ 35/d

•Needs laser/s (intense light source of fixed wavelength/s)
•Detectors for scattered light
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Laser diffraction - Mastersizer

Massey University - Bachelor of Food

Technology (Honours)
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 Laser diffraction

• Old instruments use Fraunhofer diffraction theory:

(Assumptions)
– Particles are significantly larger than the wavelength of the laser
– All particles scatter light with equal efficiencies
– Particles are opaque and transmit no light

• Modern laser diffraction instruments use Mie theory:

– Accounts for the interaction of light with matter - solves Maxwell’s
equations exactly
– Assumes transparency of the particles
– Valid for all sizes of particle, wavelengths, and scattering angles
– Gives correct answers and accounts for secondary scattering

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Mie theory Something for nothing?

• To account for the transparency of the

particles we need to know the optical
properties of the material:

– refractive indices for the particle and

medium
– the absorption for the particle needs to
be known.

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What does laser diffraction measure?

Variation of scattering angle

• Particle Size Distribution?
with particle size No!
• At least not directly
• An Intensity-Angle plot is
measured and this is
converted (“mapped”) to a
particle size distribution
given certain assumptions
 Scattering Intensity Vs. Angle.
Remember, to measure a wide range of particles, clearly, we need to be able
to measure over as wide an angular range as possible.

Scattering
Intensity
0.3 micron
3 micron
30 micron

0 10 20 30 40 50 60 7

Angle / degree
 Laser diffraction (Mastersizer)

Mie
Guess Mie theory

Size distribution •Refractive index of particle (oil droplet)

Scattering •Refractive index of dispersant (water)
Volume % •Absorption of particle

Comparison
Particle diameter ( mm)
 ni di 4
i
d43=
 ni di 3
i

Mean diameter
 ni di
i
3
Oil droplets d32=
 ni di
Equivalent spheres 2
i
Example: following an emulsion
destabilization process

Particle Size Distribution

8
Volume (%)

6 T= 0h
T= 3h
4
T= 2h
2
T= 1h
0
0.01 0.1 1 10 100 1000 3000
Particle Size (µm)

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Dynamic light Scattering or
Photon Correlation Spectroscopy (PCS)
Nano range (Zetasizer)

http://www.malvern.co.uk/labeng/products/zetasizer/demo/demo_flash.html
DLS and BROWNIAN MOTION

Dynamic Light Scattering or

Photon Correlation Spectroscopy or

Quasi-Elastic Light Scattering

measures Brownian motion

and relates it to size

© Massey University
Photon Correlation Spectroscopy

• PCS is ideal for sub-micron particle sizing

– 0.5nm to ~5mm
– perfect for casein micelles in milk
– can be used for liposomes, latex particles

• Dispersion must be DILUTE to ensure single

scattering conditions ( < 0.1%)

• Can measure very small changes in average size

– can measure average size differences of 2% or less,

i.e. can measure nm scale changes in size

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Brownian motion: diffusion of
molecules in solution

The velocity of the

Brownian motion is
defined by the
translational diffusion
coefficient ‘D’

Gravitation Brownian motion

(10 mm) (0.1 mm)

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 Browning Motion

• Random movement of colloidal particles due to the bombardment by the

solvent molecules that surround them

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© Massey University
Photon Correlation Spectroscopy

intensity
time (micro-seconds)

intensity

The small particles cause the intensity

to fluctuate more rapidly than the time (micro seconds)
large ones.
What does a Conventional DLS
Instrument consist of ?
Sample
containing particles
Laser
Scattered
light
Pinhole

Detector
(Photomultiplier/
Avalanche
Computer Photo Diode)
Correlator

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Basis of Dynamic Light Scattering

• ‘DLS measures Brownian motion and relates this to

the size of the particles’.

• Because of Brownian motion, scattered light

intensity fluctuates. The intensity fluctuations are
analysed by passing the scattered light through a
correlator, this is why dynamic light-scattering is
also named photon correlation spectroscopy.

• These fluctuations in the intensity of the

scattered light are related to the rate of
diffusion of molecules in and out of the region
being studied (Brownian motion), and the data can
be analyzed to directly give the diffusion
coefficients of the particles doing the scattering.
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Basis of Dynamic Light Scattering

© Massey University
Basis of Dynamic Light Scattering

• D, in the case of spherical particles, is related to the particle

size by the Stokes–Einstein relationship:

DT is diffusion coefficient
kb is Boltzmann’s constant
T is absolute temperature
η is the viscosity of the
suspending liquid

Rh= The hydrodynamic radius of a nonspherical

particle is the diameter of a
sphere that has the same translational
diffusion speed as the particle.
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Steps in measuring Size by DLS

Particles move due to Measure Fluctuations in

Brownian Motion Intensity of Scattered Light

Apply Stokes- Calculate Translational

Einstein Equation Diffusion Coefficient

Hydrodynamic Apply algorithm to

Diameter determine size
(Z-Average size) distribution

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Hydrodynamic Diameter

• The diameter which is measured in DLS is a value

that refers to how a particle moves within a liquid

• It is called the HYDRODYNAMIC DIAMETER

• Various factors can affect movement of particles in

liquid (surface charge, shape, surface coatings)

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HYDRODYNAMIC DIAMETER:
Effect of Ionic Strength

Surface charge on particle will

create an electrical double layer
when dispersed in a liquid.

Thickness of the electrical double

layer, 1/K (Debye Length), is
dependent upon the ionic
Particle Diameter 1/K strength of the medium

Hydrodynamic Diameter In low ionic strength media (eg

DI water) the double layer will
be extended

A latex standard diluted in DI

water will give the wrong result
(too high)
HYDRODYNAMIC DIAMETER:
Effect of Ionic Strength

In high ionic strength media the

double layer is suppressed

Latex standards should be

Particle Diameter diluted in 10mM NaCl to
1/K
suppress the double layer and
Hydrodynamic Diameter hence give the correct result
(ISO13321)
HYDRODYNAMIC DIAMETER:
Effect of Surface Coatings

A layer of molecules on the

particle surface will slow the
diffusion speed down
Reported hydrodynamic diameter
The hydrodynamic diameter will
therefore be influenced
DLS examples:
protein-polysaccharide complexation

0.25% whey protein isolate

+ 1.25 % gum arabic

Heated at constant
temperature

Loveday et al. 2013 Food Research International 54:111

© Massey University
 Light scattering techniques

Static Light Scattering:

Laser Diffraction (20nm- 2000 mm)
MALLS ( 10nm-500nm)

Dynamic light scattering (PSC) for particle sizes which are below the
lower limit of detection of laser diffraction techniques (0.5nm- 5mm)

Dynamic light scattering Static light scattering (MALLS)

real-time intensities time-average intensities
Diffusion coefficient DT Molecular weight
Hydrodynamic radius Rh Radius of gyration Rg
Estimation Mw Second virial coefficient
Size distribution Size distribution
© Massey University
Can you measure all the particles
you want to measure?

• e.g. Whole milk

– native whey proteins: ~2 nm
– casein nano-particles ~20 nm
– casein micelles ~200 nm
– fat globules ~2000 nm
• PCS can theoretically measure particles of
these sizes
– but what about when they are mixed
together?
© Massey University
Rayleigh approximation

6
d 
I  
2

Where
I = intensity of scattered light
d = diameter of particles
What does this mean for particle
sizing?
6
d 
I  
2

Approx. Intensity of
Component
Size (nm) scattered light

native whey protein 2 1

casein nano-particles 20 1000000

casein micelles 200 1000000000000

fat globules 2000 1000000000000000000

© Massey University
ULTRASONIC ATTENUATION SPECTROSCOPY

• Ultrasonic spectrometry utilizes interactions between

ultrasonic waves and particles to obtain information about
the particle size distribution

• Particle size between 10 nm and 1000 μm

• Ability to measure particle size at HIGH

CONCENTRATIONS: no need for any dilution

• provides simultaneous measure of volume concentration

• Robust, so is On-line friendly, Expensive

© Massey University
ULTRASONIC ATTENUATION SPECTROSCOPY

• When sound travels through the sample it loses energy

i.e. it is attenuated
c
i
s
t
• The wavelength of ultrasound (10 μm to 10 mm) is much
greater than that of light (0.2 to 1 μm), and so
ultrasonic measurements are usually made in the long-
wavelength regime, whereas light scattering
measurements are made in the intermediate-wavelength
regime.

© Massey University
ULTRASONIC ATTENUATION SPECTROSCOPY

Acoustic attenuation
spectroscopy works by
transmitting sound
waves through a
sample and measuring
the attenuation over
a wide range of
frequencies. Particle
size is then calculated
from the measured
spectra using
software that models
the physical basis of
sound attenuation in
concentrated
systems.

© Massey University
Nuclear magnetic resonance (NMR)
Utilize interactions between radio waves and the nuclei of hydrogen atoms to obtain
information about the properties of materials
http://chem.ch.huji.ac.il/nmr/techniques/other/diff/diff.html

Dr Jason Hindmarsh Massey University

Source: definingNZ.com

© Massey University
 Neutron Scattering
•Neutron scattering techniques utilize interactions between a beam
of neutrons and a sample to determine the droplet size distribution
•http://nanoparticles.org/pdf/41-Kaler.pdf

Dr Elliot
Gilbert
ANSTO

QUOKKA Neutron beam Lucas Heights,

instrument Sydney
Source: www.ansto.gov.au
Massey University - Bachelor of Food Technology (Honours)

© Massey University
• Particle Size Measurement; T. Allen, Chapman
& Hall. 4th Edition, 1992

• http://www.malvern.co.uk/home/index.htm

© Massey University