Chapter 3 Hunter

Determination of Particle Size
Contents
Reference
Hunter, R. J.
Introduction to Modern Colloid Science
Oxford SCIENCE PUBLICATIONS
OXFORD NEWYORK MELBOURNE
OXFORD UNIVERSITY PRESS
Contents
1. General considerations
2. Microscopy
3. Sedimentation methods
4. Electrical pulse counting
5. Light scattering methods
6. Hydrodynamic methods
7. Electroacoustics
8. Summary of sizing methods
3.1 General considerations
The size and shape of colloidal particles are amongst their
most important characteristics because they determine many
other features of the behavior of colloidal suspensions.
The rate of settling
The ease with which they can be filtered
Their flow properties when poured or pumped through a
pipe, all depend on particle size.
So too does their capacity to adsorb contaminants
The case of catalysts, their capacity per unit mass which
normally depends on the available surface area, onto which
reacting molecules must be adsorbed.
Colloidal suspension often exhibit a wide range of particle
sizes. For some purpose it may be enough to know the
minimum size, or the maximum, or some sort of average
value, but in many cases it is necessary to have a more or less
complete knowledge of the distribution, that is the number of
particles in each size range.
Colloidal particles in a sample often vary widely in shape. Unless

special care has been taken to produce monodisperse, and or
spherical particles, the particles may be disc or rod shaped or they
may be highly irregular, varying from particle to particle and from
sample to sample.
In all of our theoretical analysis we will be forced to deal only with
the simplest shape, a sphere of a certain size. More sophisticated
treatments can partially extend the treatment to more complicated
shape like discs and rods provided one can specify the ratio of the
major to the minor axis (Figure 3.1)
Figure 3.1
(a) An oblate spheroid,
obtained by rotating an
ellipse around its short
axis. The cross section in
the plane where a is
measured is circular.
(sometimes described as
‘lozenge shaped’.)
(b) A prolate spheroid,
obtained by rotating an
ellipse around its long
axis (like a rugby or
gridiron football, or a
cigar). Sections parallel
to b are circular.
(c) A disc may be
approximated as an
oblate sheroid, a
cylinder, or a flat plate.
The important point to note is that different sizing methods
can be expected to give different results because they are
measuring different aspects of the size distribution.
3.1.1 Size distributions

Whenever we are confronted with a problem of describing the
particle size of a system that is heterodisperse or polydisperse
(that is, contains many different sizes of particles) we resort to
breaking the range of sizes up into convenient steps or classes, and
recording the number of particles in each class.
Table 3.1 represent the diameters of a sample of particles
produced by a precipitation reaction. If the observed particle sizes
ranged from 65 nm to 0.6 µm one might choose to break the range
up into 11 steps of 50 nm,as shown, and to record the number of
particles in each class. The resulting data can then be plotted as a
histogram or as a smoth curve (Figure 3.2) or as a curve showing
the cumulative percentage equal to or smaller than a given size
(Figure 3.3, called the ‘per cent undersize’).
Table 3.1
Specimen size distribution for a precipitate: ∑ ni = 2500 = N , ∑ f i = ni / ∑ ni
Figure 3.2
the frequency histogram can be replaced by a smoothed curve. Note that
the model size is the most common one.
Figure 3.3
The cumulative frequency
curve showing the
median size dM which
divides the distribution
evenly (50 per cent of
the material has di ≤ dM)
Rather than going to the trouble of plotting the data each time, it
is often sufficient to specify the main features of the
distribution using a few numbers.
1. The mean and standard deviation
1/ 2
 ∑ ni (d i − d ) 2 
σ = 
N
 (
= ∑ f i (d i − d ) 2 )
1/ 2
 
Then can be written (

σ = d − (d ) 2 2
)
1/ 2
2. Other mean values if the colloidal suspension is polydisperseThe

total surface area, As, of a polydisperse sample of spherical
particles. We can write A = ∑ n πd 2 s i i
The number-area mean diameter, dNA is defined as the diameter

of the sphere for which
πd 2
NA
A
= s
N
and (
d NA = ∑ f i d i )
2 1/ 2
= d ( )
2
1/ 2
Note that a system of N uniform spheres of diameter d NA has the
same surface area as he original sample, S. in a similar way one
can define a series of different average sizes, many of which are
directly measurable.
Important one is the volume average particle size which happens to
be the one most easily extracted form light scattering methods
and is closely related to the mass average size determined from
ultrasonic measurements using the ESA technique ( see Exercise
3.1.3) it is defined as 1/ 3 3 1/ 3
 ∑ niVi   ∑ ni d i 
d NV =   = K 
 N   N 
3. The continuous distribution function. Figure 3.2 shows that the
histogram can be replaced by a smooth curve but it is important
to note that this is not a plot of ni against di. For the continuous
curve, F(di)ddi, the number of particles dni in the range di to ddi
is given by dn = F (d )ddi
i i
Figure 3.4. The continuous distribution function, F(di), and its
relation to the frequency histogram.
4. The theoretical distribution functions. The most commonly used
and important of the theoretical functions is the normal or
Gaussian distribution
In fact , the distribution of sizes obtained from grinding a solid
down to form small particles is often very far from’normal’ or
Gaussian (Figure 3.5).
Figure 3.5. A possible size distribution produced by grinding or

crushing.
In that case it often helps to transform the data by looking at the
distribution of log d which look more like a normal distribution
(Figure 3.6.)
Figure 3.6. The relative percentage frequency distribution

function plotted gainst ln (di / nm). Data from figure 3.5
Another common complication comes in the form shown in (Figure
3.7) which shows a bimodal distribution. Such distributions can
occur in the preparation ofa sol using the condensation
procedure if there are two different nucleation periods
separated by a significant time interval.
Figure 3.7. A bimodal distribution resulting from the overlap of

two ‘normal distribution having modes dM1 and dM2.
3.2 Microscopy
1. Optical (light) Microscopy
For observation of the presence and the motion of particles
If ultramicroscopic the shape is possible
The limit of resolution of the optical microscope is a little
below 1µm
An intense beam of light from an arc lamp, or a laser is
focused on the particles.
The most of light scattered by the particles depends on
their volume and refractive index, wavelength
2. Electron microscopy
The most significant development in microscopy has, of course,
been the Transmission Electron Microscope (TEM) and, more
recently, the Scanning Electron Microscope (SEM)
Transmission Electron Microscope
Two dimensional representation of the actual structure. The
electron beam is produced by thermionic emission from a tungsten
cathode and is accelerated toward anode
Electron are observed or scattered depend on its local electron
density, and the remainder are transmitted
An electromagnetic objective lens collects the transmitted
electrons and magnifies the image of the specie 10-20 time.
Additional lens 50-400 times.
Scanning Electron Microscope

Provide quite remarkable images, which are interpreted by the eye
as truly three-dimensional
Electron beam is forced o about 5-10 nm and deflected in a
regular manner across the surface of he sample.
Beam is used to scan the surface
Results are reconstructed image or TV. Image
3.3 Sedimentation methods
1. Sedimentation under gravity
Very dense particle
Particle size distribution can be built up.
2. Sedimentation under gravity
Increase sedimentation rte by subjecting the particles to

centrifugation
The concentration of particles of a particular level
measured by determining the optical density
First remove large particle , then medium, and then small
3.5 Light scattering methods
1. Intensity method
A. Rayleigh scattering
Measuring the amount of light scattering at an angle 90°
to the incident beam allows one, in principle, to estimate
the molar mass of a polymer in very dilute solution.
Amount of light (measure amount light scattered)
lo / l / α particle size
Alternative procedure, used for more concentrated system, is
o measure the turbidity, T, of the sample, due to the scattering
process.
B. Rayleigh-Gas Debye
Measured radius of monodispersed spherical particle (10 – 100
nm) RD = I o / I o
45 135
C. Mei scattering
Particle size > light wavelength
D. Fraunhofer diffraction
Larger particles >10nm) laser beam/ collected diffracted light
with lens then detection
Best for particle above colloidal size large.
2. Dynamic QELS
Spectrum analyzer to determine the certain angle asa
function of frequency

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Determination of Particle Size

Colloidal particles in a sample often vary widely in shape. Unless

3.1.1 Size distributions

Then can be written (

2. Other mean values if the colloidal suspension is polydisperseThe

The number-area mean diameter, dNA is defined as the diameter

Figure 3.5. A possible size distribution produced by grinding or

Figure 3.6. The relative percentage frequency distribution

Figure 3.7. A bimodal distribution resulting from the overlap of

Scanning Electron Microscope

Increase sedimentation rte by subjecting the particles to

Particle size > light wavelength

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