Particle size distribution

• A particle population which consists of spheres

or equivalent spheres with uniform dimensions is
monosized and its characteristics can be
described by a single diameter or equivalent
diameter.

• it is unusual for particles to be completely

monosized, most powders contain particles with
a large number of different equivalent diameters.
• to be able to define a size distribution or
compare the characteristics of two or more
powders consisting of particles with many
different diameters, the size distribution can be
broken down into different size ranges, which
can be presented in the form of a histogram
• a histogram presents an interpretation of the
particle size distribution and enables the
percentage of particles having a given
equivalent diameter to be determined.

• A histogram representation allows different

particle size distributions to be compared;
• for example, the size distribution shown in Fig.
(b) contains a larger proportion of fine particles
than the powder in (a) in which the particles are
normally distributed.

• The peak frequency value, known as the mode,

separates the normal curve into two identical
halves, because the size distribution is fully
symmetrical.
• A frequency curve with an elongated tail towards
higher size ranges is positively skewed (Fig.
(b)); the reverse case exhibits negative
skewness.

• These skewed distributions can sometimes be

normalized by replotting the equivalent particle
diameters using a logarithmic scale, and are
thus usually referred to as log normal
distributions.
• In some size distributions more than one mode
occurs: Figure (c) shows bimodal frequency
distribution for a powder which has been
subjected to milling.

• Some of the coarser particles from the unmilled

population remain unbroken and produce a
mode towards the highest particle size, whereas
the fractured particles have a new mode which
appears lower down the size range.
Frequency distribution curves corresponding to (a)
a normal distribution, (b) a positively skewed
distribution and (c) a bimodal distribution.
• An alternative to the histogram representation of
a particle size distribution is obtained by
sequentially adding the percent frequency
values as shown in Table 10.2 to produce a
cumulative percent frequency distribution.

• If the addition sequence begins with the coarsest

particles, the values obtained will be cumulative
percent frequency oversize; the reverse case
produces a cumulative percent undersize.
• The median particle diameter corresponds to the
point that separates the cumulative frequency
curve into two equal halves, above and below
which 50% of the particles lie (point a in Fig.
10.5(a)).

• the lower and upper quartile points at 25% and

75% divide the upper and lower ranges of a
symmetrical curve into equal parts (points b and
c, respectively, in Fig. 10.5(a)).
• it is possible to compare two or more particle
populations using the cumulative distribution
representation.

• For example, the size distribution in Fig. (a)

shows that this powder has a larger range or
spread of equivalent diameters than the powder
represented in Figure (b).
 Cumulative frequency distribution curves

• Point a corresponds to the median

diameter.

• b is the lower quartile point.

• c is the upper quartile point.

 Statistics
• to quantify the degree of skewness of a particle
population:
• the interquartile coefficient of skewness (IQCS):
• Where:
• a is the median diameter
• b is the lower quartile point
• c is upper quartile point

• The IQCS can take any value between -1 and

+1.
• If the IQCS is zero then the size distribution is
practically symmetrical between the quartile
points.
• To quantify the degree of symmetry of a particle
size distribution a property known as kurtosis
can be determined.

• The symmetry of a distribution is based on a

comparison of the height or thickness of the tails
and the 'sharpness' of the peaks with those of a
normal distribution.
• 'Thick'-tailed 'sharp‘ peaked curves are
described as leptokurtic

• 'thin'-tailed 'blunt' peaked curves are platykurtic

• the normal distribution is mesokurtic.

• The coefficient of kurtosis, k:

• where
• x is any particle diameter
• x is mean particle diameter
• n is number of particles.
• The coefficient of kurtosis has:

• a value of 0 for a normal curve.

• a negative value for curves showing

platykurtosis.

• positive values for leptokurtic size distributions.

• The mean of the particle population, the median
and the mode are all measures of central
tendency and provide a single value near the
middle of the size distribution, which represents
a central particle diameter.

• It is also possible to define and determine the

mean in several ways and, for log-normal
distributions, a series of relationships known as
Hatch- Choate equations link the different mean
diameters of a size distribution.
 Influence of particle shape
• The techniques for representing particle size
distribution are all based on the assumption that
particles could be adequately represented by an
equivalent circle or sphere.

• In some cases particles deviate markedly from

circularity and sphericity.
• For example, a powder consisting of monosized
fibrous particles would appear to have a wider
size distribution according to statistical diameter
measurements.
• Thus,
• the breadth of the fibre could be obtained using
a projected circle inscribed within the fibre di
• the fibre length could be measured using a
projected circle circumscribed around the fibre dc

• The ratio of inscribed circle to circumscribed

circle diameters can also be used as a simple
shape factor to provide information about the
circularity of a particle.
• The ratio di /dc will be 1 for a circle and diminish
as the particle becomes more acicular.
 PARTICLE SIZE ANALYSIS
METHODS
• Particle-size analysis methods can be divided
into different categories based on several
different criteria:

• size range of analysis;

• wet or dry methods;
• manual or automatic methods;
• speed of analysis.
1. Sieve methods
2. Microscope methods
3. Electrical stream sensing zone method
(Coulter counter)
4. Laser light scattering methods
5. Sedimentation methods
 Sieve methods
• Equivalent diameter:
• Sieve diameter, ds (the particle dimension that
passes through a square aperture (length = x)).
• Range of analysis
• In practice sieves can be obtained for size
analysis over a range from 5 to 125 000 µm.
• Principle of measurement:
• Sieve analysis utilizes a woven, punched or
electroformed mesh, often in brass or stainless
steel, with known aperture diameters which form
a physical barrier to particles.

• Most sieve analyses utilize a series, stack or

'nest' of sieves, which has the smallest mesh
above a collector tray followed by meshes that
become progressively coarser towards the top of
the series.
• A sieve stack usually comprises 6-8 sieves with
an aperture progression based on a √2 or 2√2
change in diameter between adjacent sieves.

• Powder is loaded on to the coarsest sieve of the

assembled stack and the nest is subjected to
mechanical vibration.
• After a suitable time the particles are considered
to be retained on the sieve mesh with an
aperture corresponding to the sieve diameter.

• Sieving times should not be arbitrary and it is

recommended that sieving be continued until
less than 0.2% of material passes a given sieve
aperture in any 5-minute interval.
• Alternative techniques:
• Another form of sieve analysis, called air-jet
sieving,
• uses individual sieves rather than a complete
nest of sieves.
• Starting with the finest-aperture sieve and
progressively removing the undersize particle
fraction by sequentially increasing the apertures
of each sieve.
• Particles are encouraged to pass through each
aperture under the influence of a partial vacuum
applied below the sieve mesh.
• A reverse air jet circulates beneath the sieve
mesh, blowing oversize particles away from the
mesh to prevent blocking.
• Air-jet sieving is often more efficient and
reproducible than using mechanically vibrated
sieve analysis, although with finer particles
agglomeration can become a problem.
• Automatic methods:
• Sieve analysis is still largely a non-automated
process, although an automated wet sieving
technique has been described.
 Microscope methods
(microscopy)
• Equivalent diameters:

• Projected area diameter, da

• projected perimeter diameter dp
• Feret's diameter dF
• Martin's diameter dM
• Range of analysis:
• Sample preparation and analysis conditions:
• Specimens prepared for light microscopy must
be adequately dispersed on a microscope slide
to avoid analysis of agglomerated particles
• Specimens for scanning electron microscopy are
prepared by fixing to aluminium stubs before
sputter coating with a film of gold a few nm in
thickness.
• Specimens for transmission electron microscopy
are often set in resin, sectioned by microtome
and supported on a metal grid before metallic
coating.
• Principle of measurement:

• Size analysis by light microscopy is carried out

on the two-dimensional images of particles
oriented in three dimensions.

• for dendrites, fibres or flakes it is very

improbable that the particles will orient with their
minimum dimensions in the plane of
measurement.
• Under such conditions, size analysis is carried
out accepting that they are viewed in their most
stable orientation.

• This will lead to an overestimation of size, as the

largest dimensions of the particle will be
observed.
• The two-dimensional images are analysed
according to the desired equivalent diameter.

• Using a conventional light microscope, particle-

size analysis can be carried out using a
projection screen with screen distances related
to particle dimensions by a previously derived
calibration factor using a graticule.
• A graticule can also be used which has a series
of opaque and transparent circles of different
diameters, usually in a √2 progression.

• Particles are compared with the two sets of

circles and are sized according to the circle that
corresponds most closely to the equivalent
particle diameter being measured.

• The field of view is divided into segments to

facilitate measurement of different numbers of
particles.
• Alternative techniques:

• scanning electron microscopy (SEM).

• transmission electron microscopy (TEM).

• Scanning electron microscopy is particularly
appropriate when a three dimensional particle
image is required; in addition.

• Both SEM and TEM analysis allow the lower

particle-sizing limit to be greatly extended over
that possible with a light microscope.
• Automatic methods:
• Semiautomatic methods use some form of
precalibrated variable distance to split particles
into different size ranges.

• One technique, called a particle comparator,

utilizes a variable diameter light spot projected
on to a photomicrograph or electron
photomicrograph of a particle under analysis.
• The variable iris controlling the light spot
diameter is linked electronically to a series of
counter memories, each corresponding to a
different size range.

• Alteration of the iris diameter causes the particle

count to be directed into the appropriate counter
memory following activation of a switch by the
operator.
Particle comparator
• A second technique uses a double-prism
arrangement mounted in place of the light
microscope eyepiece.

• The image from the prisms is usually displayed

on a video monitor.

• The double-prism arrangement allows light to

pass through to the monitor unaltered, where the
usual single particle image is produced.
• When the prisms are sheared against one
another a double image of each particle is
produced and the separation of the split images
corresponds to the degree of shear between the
prisms.
• Particle-size analysis can be carried out by
shearing the prisms until the two images of a
single particle make touching contact.
• The prism shearing mechanism is linked to a
precalibrated micrometer scale from which the
equivalent diameter can be read directly.
• Alternatively, a complete size distribution can be
obtained more quickly by subjecting the prisms
to a sequentially increased and decreased shear
distance between two preset levels
corresponding to a known size range.
• All particles whose images separate and overlap
sequentially under a given shear range are
considered to fall in this size range, and are
counted by operating a switch which activates
the appropriate counter memory.
Image-shearing eyepiece
• Automatic microscopy is usually associated with
microprocessor-controlled manipulation of an
analogue signal derived from some form of
video monitor used to image particles directly
from a light microscope or from
photomicrographs of particles.
• fully automatic size analysis has the advantage
of:

1. being more objective,

2. very much faster,
3. enables a much wider variety of size and
shape parameters to be processed.
 Electrical stream sensing zone
method (Coulter counter)
• Equivalent diameter:
• Volume diameter, dV.

• Range of analysis:
• Sample preparation and analysis conditions:
• Powder samples are dispersed in an electrolyte
to form a very dilute suspension.

• The suspension is usually subjected to

ultrasonic agitation for a period to break up any
particle agglomerates.

• A dispersant may also be added to aid particle

deagglomeration.
• Principle of measurement:
• The particle suspension is drawn through an
aperture accurately drilled through a sapphire
crystal set into the wall of a hollow glass tube.

• Electrodes situated on either side of the aperture

and surrounded by an electrolyte solution,
monitor the change in electrical signal that
occurs when a particle momentarily occupies the
orifice and displaces its own volume of
electrolyte.
• The volume of suspension drawn through the
orifice is determined by the suction potential
created by a mercury thread rebalancing in a
convoluted U-tube.

• The volume of electrolyte fluid which is displaced

in the orifice by the presence of a particle
causes a change in electrical resistance
between the electrodes that is proportional to
the volume of the particle.
• The change in resistance is converted into a
voltage pulse which is amplified and processed
electronically.

• Pulses falling within precalibrated limits or

thresholds are used to split the particle size
distribution into many different size ranges.
• In order to carry out size analysis over a wide
diameter range it will be necessary to change
the orifice diameter used, to prevent coarser
particles blocking a small-diameter orifice.

• Conversely, finer particles in a large-diameter

orifice will cause too small a relative change in
volume to be accurately quantified.
Particle passing through the measuring aperture of
an electrical stream sensing zone apparatus.
Diagram of electrical stream sensing zone
apparatus
• Alternative techniques:
• use of alternative orifice designs and
hydrodynamic focusing, but in general the
particle detection technique remains the same.

• Another type of stream sensing analyser utilizes

the attenuation of a light beam by particles
drawn through the sensing zone
 Laser light scattering methods
• Equivalent diameters:
• Area diameter, da
• volume diameter dV following computation

• Range of analysis
• Sample preparation and analysis conditions:
• Depending on the type of measurement to be
carried out and the instrument used, particles
can be presented either in liquid or in air
suspension.
• Principles of measurement:
• Both the large-particle and small-particle
analysers are based on the interaction of laser
light with particles.

• Fraunhofer diffraction
• For particles that are much larger than the
wavelength of light, any interaction with particles
causes light to be scattered in a forward
direction with only a small change in angle.
• This phenomenon is known as Fraunhofer
diffraction, and produces light intensity patterns
that occur at regular angular intervals and are
proportional to the particle diameter producing
the scatter.

• The composite diffraction pattern produced by

different diameter particles may be considered to
be the sum of all the individual patterns
produced by each particle in the size
distribution.
Diffraction pattern intensity distribution.
• Light emitted by a helium-neon laser is incident
on the sample of particles and diffraction occurs.

• In some cases the scattered light is focused by a

lens directly on to a photodetector, which
converts the signals into an equivalent area
diameter.
• In other cases the scattered light is directed by a
lens on to a rotating filter, which is used to
convert equivalent area diameters into volume
diameters which are quantified by final focusing
on to a photodetector using a second lens.

• The light flux signals occurring on the

photodetector are converted into electrical
current, which is digitized and processed into
size distribution data using a microprocessor.
• Small particle sizes can be analysed based on
light diffraction or by photon correlation
spectroscopy.
• As particles approach the dimension of the
wavelength of the light, some light is still
scattered in the forward direction, according to
Mie scatter theory, but there is also some side
scatter at different wavelengths and
polarizations.
• In the case of photon-correlation spectroscopy
(PCS) the principle of Brownian motion is used
to measure particle size.

• PCS analyses the constantly changing patterns

of laser light scattered or diffracted by particles
in Brownian motion and monitors the rate of
change of scattered light during diffusion.
Schematic diagram of laser diffraction pattern
particle sizer.
• Alternative techniques:
• based on laser Doppler anemometry or
velocimetry, and diffraction measurements.

• The instruments vary according to their ability to

characterize different particle-size ranges,
produce complete size distributions, measure
both solid and liquid particles, determine
molecular weights, diffusion coefficients, zeta
potential or electrophoretic mobility.
• Automatic methods:

• Most of the instruments based on laser light

scattering produce a full particle-size analysis
automatically.

• The data are often presented in graphical and

tabular form.
 Sedimentation methods
• Equivalent diameters:
1. dfd, frictional drag diameter, a sphere having an
equivalent drag force to a particle of the same
diameter in the same fluid at the same velocity.

2. dst, Stokes diameter, the diameter of a particle

measured during sedimentation at constant
rate in laminar flow conditions.
• Range of analysis:
• Sample preparation and analysis conditions:
• Particle-size distributions can be determined by
examining the powder as it sediments out.

• In cases where the powder is not uniformly

dispersed in a fluid it can be introduced as a thin
layer on the surface of the liquid.
• If the powder is hydrophobic it may be
necessary to add a dispersing agent to aid
wetting.

• In cases where the powder is soluble in water it

will be necessary to use non-aqueous liquids, or
carry out the analysis in a gas.
• Principles of measurement:
• two main categories according to the method
of measurement used.

1. One type is based on measurement of

particles in a retention zone.

2. second type uses a non-retention

measurement zone.
 non-retention zone measurement

• the pipette method.

• known volumes of suspension are drawn off and

the concentration differences are measured with
respect to time.

• The Andreasen fixed-position pipette consists of

a 200 mm graduated cylinder which can hold
about 500 mL of suspension fluid.
• A pipette is located centrally in the cylinder and
is held in position by a ground-glass stopper so
that its tip coincides with the zero level.

• A three-way tap allows fluid to be drawn into a

10 mL reservoir, which can then be emptied into
a beaker or centrifuge tube.
• The amount of powder can be determined by
weight following drying or centrifuging; or
chemical analysis of the particles.

• The largest size present in each sample is then

calculated from Stokes' equation.

• Stokes' law is an expression of the drag factor in

a fluid and is linked to the flow conditions
characterized by a Reynolds number.
• three forces acting on a particle sedimenting in
a gravitational field:

1. A drag force, Fd, acts upwards,

2. A buoyancy force, Fb; acts upwards,
3. Gravity force, Fg, acts as the driving force of
sedimentation.
• Thus for a sphere of diameter d and density ρs,
falling in a fluid of density ρf, sedimentation
height or distance h
• and sedimentation time t, Stoke’s equation is:
Diagram of Andreasen pipette
 retention zone methods

• also use Stokes' law to quantify particle size.

• use a sedimentation balance.

• the amount of sedimented particles falling on to

a balance pan suspended in the fluid is
recorded.

• The continual increase in weight of sediment is

recorded with respect to time.
• Alternative techniques:
• One of the limitations of gravitational
sedimentation is that below a diameter of
approximately 5µ particle settling becomes
prolonged and is subject to interference from
convection, diffusion and Brownian motion.

• These effects can be minimized by increasing

the driving force of sedimentation by replacing
gravitational forces with a larger centrifugal
force.
• sedimentation can be monitored by retention or
non-retention methods.

• Stokes equation requires modification because

particles are subjected to different forces.
• A small quantity of concentrated suspension is
introduced on to the surface of a bulk
sedimentation liquid known as spin fluid.

• Using this technique of disc centrifugation, all

particles of the same size are in the same
position in the centrifugal field and hence move
with the same velocity.
• Automatic methods:
• gravity sedimentation methods tend to be less
automated than those using centrifugal forces.

• a retention zone gravity sedimentation method is

known as a Micromerograph and measures
sedimentation of particles in a gas rather than a
fluid.

• The advantages of this method are that sizing is

carried out relatively rapidly and the analysis is
virtually automatic
 SELECTION OF A PARTICLE
SIZE ANALYSIS METHOD
• governed by:
• The properties of the powder particles
• The type of size information required.
• Analysis requirements such as:
– speed of measurement
– particle size data processing
– the physical separation of different particle-
size powders for subsequent processing.
• For example, size analysis over a very wide
range of particle diameters may preclude the
use of a gravity sedimentation method.