PARTICLE SIZE MEASUREMENT USING

LASER DIFFRACTION

Abstract:
Laser-based techniques for particle-size measurement have become increasingly important in

combustion research and many other disciplines. Instruments are continually being

developed and improved to meet the demanding geometric, accuracy and other

requirements associated with current research and industrial applications. The operating

principles of particle-size instrumentation using laser-based techniques, as well as difficulties

associated with applying these methods, are discussed. Light diffraction is one of the

most widely used techniques for measuring the size of a wide range of particles from

very fine to very coarse. The method is popular because it is quick and easy to use,

flexible, and it can be adapted to measure samples presented in various physical forms.

The method depends on the analysis of the diffraction pattern produced when particles are

exposed to a collimated beam of light . As the patterns are characteristic of the

particle size, mathematical analysis can produce an accurate, repeatable picture of the

size distribution.

Abbreviations:

DCW Dual Cylindrical Wave

DLS Dynamic Light Scattering
PCS Photon Correlation Spectroscopy
LALLS Low Angle Laser Light Scattering

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 TABLE OF CONTENTS

1. Introduction vii

1.1. Purpose and Description vii

1.2. Importance of particle-size measurements vii

1.3. Important elements in particle-size measurement ix

1.4. Description of particle diameter and shape ix

2. Light diffraction measurement of particle size xii

2.1. Principle xiii

2.2. Apparatus xiii

2.3. Preparation of the sample xv

2.3.1. Concentration of sample xv

2.3.2. Dispersion liquids xvi

2.4. Measurement of the scattering of dispersed samples xvi

2.5. Selection of an appropriate optical model xvi

2.6. Conversion of Scattering Pattern into Particle Size Distribution xviii

2.7. Replicates xviii

2.8. System Suitability xix

2.9. Accuracy and Repeatability xix

3. Comparison of Fraunhofer and Mie scattering xxi

4. The Future xxiii

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 LIST OF TABLES

Table1 Application of particle sizing technology. vii

Table 2 Definition of individual particle diameter. ix

Table 3 Definitions and descriptions of mean particles. x

Table 4 Common size distributions and their associated parameters. xi

LIST OF FIGURES

Fig.1 Various methods of particle-size analysis. viii

Fig.2 Typical set up for a laser diffraction instrument. xiii

Fig.3 Fraunhofer diffraction: Effect of particle size. xxi

Fig 4.Mie scattering: Effect of particle size. xxi

Fig.5 Effect of imaginary part of the refractive index. xxii

Fig.6 Effect of real part of the refractive index. xxii

Fig 6.Size distribution for slurry. xxiii

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1. Introduction:

1.1 Purpose and Description

Laser-based techniques for particle-size measurement are important in a variety of

industries and to researchers in many different fields. Examples include combustion of
pulverized coal and liquid fuels, spray characterizations, analysis and control of particulate
emissions, industrial process control, manufacture of metallic powders and the production of
pharmaceuticals. In response to different situations encountered in sizing particles, many
techniques have been and are being proposed and developed to size particles accurately.
Often these techniques are capable of measuring particle velocity as well. Use of the laser has
become increasingly popular in particle-sizing applications. This has occurred because the
laser's distinctive property of nearly planar waves, mono-chromatic nature, coherence, and
high spectral power makes it an extremely useful tool for particle sizing.

1.2 Importance of particle-size measurements

Particle-size measurements are important to researchers, scientists and engineers in both

the research and development and industrial communities working in a broad range of

disciplines. Table 1 describes some of the many fields in which particle-size analysis is

essential and lists some of the primary uses of particle-sizing methods in these areas

For example, particle size and number density are critical parameters in two-phase
combustion experiments and modelling, since the particles or droplets represent the energy
source in reacting two-phase flows. Thus, knowledge of the particle size distribution is a key
parameter in modelling radiative heat transfer, as well as in characterizing other properties,

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such as droplet evaporation rates and total droplet/particle burnout. The particles and the
associated heat release also have a large impact on the flow field in the combustion
region. Laboratory work with laser-based sizing instrumentation includes work on the
characterization of all types of two-phase flows, measurements of droplet size
distributions in clouds, quality control of injection fluids for medical use and studies of
respiratory illness caused by particle inhalation. Laser-based methods of particle-size
analysis are used extensively in spray characterization and have seen industrial
applications in such diverse fields as pulverized coal combustion, spray combustion,
powder metallurgy, pharmaceuticals manufacturing, agriculture, powder and liquid paint
production and pollution monitoring.

Fig.1 shows a diagram outlining several broad methods of particle-size analysis, including
those based on optical techniques and those mechanical in nature.

Fig.1 various methods of particle-size analysis (Barth, 1993)

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1.3 Important elements in particle-size measurement

Laser-based methods of particle-size analysis have several common elements that must be
addressed and understood before a method can accurately be used for particle-size
analysis. A knowledge of particle-sizing terminology and particle size distribution
functions is essential to understand the measurements from the various systems. Issues
to resolve when applying a technique include that of a Gaussian intensity profile
across the laser beam diameter, the scattering characteristics of the particle, and the
measurement environment. Problems related to the Gaussian beam profile must be
resolved for all types of laser-based systems.

1.4 Description of particle diameter and shape

A number of terms have specific meanings related to the description of the shape and
size of the particles. Table 2 lists some of the more common terms related to aspects of
particle shape, along with their associated meanings

Table 2. Definitions of individual particle diameters (Barth, 1993)

Most descriptions of the particle diameter involve relating some aspect of the particle
to a particle having an equivalent spherical diameter. If the particle under consideration is
spherical, then all diameters become equal. The wide variation in particle shape leads to
terms such as the volume diameter (where the diameter is that of a sphere having the same
volume as the actual particle), the surface diameter (where the diameter is that of a
sphere having the same surface area as the actual particle) and others, as defined in
Table 3.

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 Table 3. Definitions and descriptions of mean particle (Barth, 1993)

Each of these diameter definitions stems from application of one or more methods of
size analysis. Diameter definitions, such as the projected area diameter, Martin's diameter
and Feret's diameter, come from analyses using microscopy where these diameters are
easily measured. Others, such as the drag diameter, come from sedimentation methods of
particle-size analysis. All laser-based methods of particle sizing measure an equivalent
spherical diameter.

Laser-based particle analyzers generally determine the distribution of the equivalent spherical
particle sizes. The mean particle size of the distribution can then be defined in different
ways. Some of the most common are the arithmetic mean (d10), the surface mean (d20),
the volume mean (d30) and the Sauter mean (d32). Each mean diameter is defined to be
the most useful or convenient measure to use given the phenomena under investigation.
For example, d32 is used in combustion related fields, d43 is used in the field of
chemical kinetics and d30 is common, since diffraction- based instrumentation typically
report this parameter. f (di) is the value of the particle size distribution function at the
discrete values of the particle size.

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 Table 4. Common size distributions and their associated parameters (Barth, 1993)

Particle size distribution functions are mathematical expressions that relate some aspect of
the particulates in the flow, such as the volume or concentration, with the particle diameter.
These distributions functions, given the symbol rid), are a simple mathematical method
of characterizing particulates without the need for detailed plotting of the experimental
distribution. They allow communication of detailed information about the particles in a
concise manner. The use of size distribution functions also provides a way to
extrapolate information about particle sizes outside the measured range of values,
makes calculation of relevant information simple (such as the average particle diameters
and parameters describing the distribution shape), and provides insight into the
processes involving the particles. Distribution functions of particles and droplets can be of
several types, depending on the nature of the particles and the environment in which
they are used.

Some of the most common distribution functions for powders and sprays are the
normal, log-normal and Rosin-Rammler distributions, The mathematical formulas of the
normal, log-normal and Rosin- Rammler distributions along with the equations for the
mean and standard deviation for each distribution are shown in Table 4.

The normal distribution is rare, usually applicable only when the range of particle sizes is
narrow. Most distributions of powders in manufacturing processes, pulverized coal, fly
ash and any powders produced by grinding processes fit a log-normal distribution. The
log-normal distribution is similar to the normal distribution and is given by letting z =
ln(d). Fine powders and sprays can be described in terms of the Rosin-Rammler

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distribution, written in terms of the percentage undersized R; and the particle diameter
d. The variables b and n are a measure of the spread in the particle size and a
characteristic of the particle material, respectively.

2. Light diffraction measurement of particle size

Light diffraction is one of the most widely used techniques for measuring the size of
a wide range of particles from very fine to very coarse. The method is popular
because it is quick and easy to use, flexible, and it can be adapted to measure samples
presented in various physical forms. The method depends on the analysis of the
diffraction pattern produced when particles are exposed to a collimated beam of light .
As the patterns are characteristic of the particle size, mathematical analysis can produce
an accurate, repeatable picture of the size distribution.

This provides guidance on the measurement of size distributions of particles in any

phase system (e. g. powders, sprays, aerosols, suspensions, emulsions, and gas bubbles in
liquids) through analysis of their angular light -scattering patterns. Traditionally, the
measurement of particle size using laser diffraction has been limited to particles in the
range 0.1 µm to 3mm. Due to recent advances in optics and lens and equipment design
and construction, newer instruments are routinely capable of exceeding this range (e. g.
,0. 1µm to 8mm). It is the responsibility of the user to demonstrate the applicability
of the instrument for its intended use and to validate any method prior to its adoption
for routine use.

For non-spherical particles, an equivalent -sphere size distribution is obtained because

the technique uses the assumption of spherical particles in it s optical model. The
resulting particle size distribution may be different from those obtained by methods based
on other physical principles (such as sediment at ion or sieving). The laser diffraction
technique is based on the phenomenon that particles scatter light in all direct ions with
an intensity pattern that is dependent on particle size. All present instruments assume a
spherical shape for the particles. Historically, the early laser diffraction instruments used
only scattering at small angles and, thus, has been known by the following names:
Fraunhofer diffract ion, near forward light scattering, and low angle laser light
scattering (LALLS).

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However, the technique since has been broadened t o include light scattering in a
wider angular range by application of the Mie theory, in addition to the Fraunhofer
approximation and anomalous diffract ion. The measurement of particle size is an
import ant aspect in the characterization of raw materials and drug formulations. To
monitor production and particle stability, efficient and rapid methods for particle sizing are
needed. The electronic measurement of samples offers a convenient solution to this
problem. However, the electronic measurement will often have to be accompanied by
microscopical investigation to determine the type of particles being investigated.
Modern drug formulations may also be particulate formulations where the particle size
will be below 100 µm, and reliable and reproducible methods are needed for the
quality control of these drug products.

2.1 Principle

A representative sample, dispersed at an adequate concentration in a suitable liquid or

gas, is passed through the beam of a monochromatic light source, usually from a laser. The
light scattered by the particles at various angles is measured by a multi element detector,
and numerical values relating to the scattering pattern are then recorded for subsequent
analysis. These numerical scattering values are then transformed, using an appropriate
optical model and mathematical procedure to yield the proportion of total volume to a
discrete number of size classes forming a volumetric particle size distribution.

2.2 Apparatus

A typical set up for a laser diffraction instrument is shown in Figure1.

Fig.2 Typical set up for a laser diffraction instrument (Barth,1993)

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A representative sample, dispersed at an adequate concentration, is passed through the
light beam in a measuring zone by a transporting fluid ; This measuring zone should be
within the working distance of the lens used. In some cases the particle stream in a process is
illuminated directly by the laser beam for measurement, as in the case of sprays, aerosols, and
air bubbles in liquids. In other cases (such as emulsions, pastes, and powders), representative
samples can be dispersed in suitable liquids. Often dispersants (such as wetting agents or
stabilizers) or mechanical forces (such as agitation ) is applied to deagglomerate particles
and to stabilize the dispersion. For these liquid dispersions, a recirculating system is
most commonly used, consisting of an optical measurement cell, a dispersion bath
(usually equipped with stirrer and ultrasonic element s), a pump, and tubing.

Dry powders can also be converted into aerosols through the use of dry powder
dispersers, which apply mechanical forces for deagglomeration. In this case, a dosing device
feeds the disperser with a constant mass flow of sample. The disperser uses the energy of
compressed gas or the differential pressure to a vacuum to disperse the particles. It
outputs an aerosol that is blown through the measuring zone, usually into the inlet of a
vacuum pipe that collects the particles.

There are two posit ions in which the particles can enter the laser beam. In the conventional
case, the particles enter the parallel beam before and within the working distance of the
collecting lens. In the so-called reversed Fourier optics case, the particles enter behind
the collecting lens, and thus in a converging beam.

The advantage of the conventional set up is that a reasonable path length for the sample
is allowed within the working distance of the lens. The second set up allows only small
path lengths but enables measurement of scattered light at larger angles, which is useful
when submicron particles are present .

The interact ion of the incident light beam with the dispersed particles results in a
scattering pattern with different light intensities at various angles. The total angular
intensity distribution, consisting of both direct and scattered light , is then focused by a
positive lens or an assembly of lenses onto a multi element detector. The lens (es) provide(s)
for a scattering pattern which, within limits, is not dependent upon the location of the
particles in the light beam. Thus the continuous angular intensity distribution is
converted into a discrete spatial intensity distribution on a set of detect or elements.

It is assumed that the recorded scattering pattern of the particle ensemble is identical to
the sum of the patterns from all individual single scattering particles presented in

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random relative posit ions. Note that only a limited angular range of scattered light is
collected by the lens (es), and thus by the detector.

2.3 Preparation of the sample

Prepare a representative sample of suitable volume for the measurement by an

adequate sample splitting technique.

Sprays, aerosols, and gas bubbles in liquid should be measured directly, provided that
their concentration is at an appropriate level, since sampling or dilution is generally
impossible without altering the particle size distribution.

The dispersion procedure is adjusted t o the purpose of the measurement : for example,
whether agglomerates should be detected or broken down to primary particles.

For the development of a method, it is necessary to check that comminution of the

primary particles does not occur, and conversely that a good dispersion of the
agglomerates has been achieved. The dry particles may be examined microscopically
before and after the addition and dispersion of aliquots of the dispersing liquid to
determine if the particle size has changed, and if the agglomerates are dispersed but
t he primary particles are not fractured. The effect of the dispersion process can
usually be checked by changing the dispersing energy and monitoring the change of
the size distribution. The measured size distribution does not change significantly if the
sample is well dispersed and the particles are neither fragile no soluble. Microscopy may
also be use to investigate primary particle comminution and adequacy of dispersion.

2.3.1 Concentration of sample

The particle concentration in the dispersion should be above a minimum level, which
for many instruments will correspond to about 5% obscuration, in order to produce an
acceptable signal - to - noise ratio in the detector. Likewise, it should be below a
maximum level in order to avoid multiple scattering.

2.3.2 Dispersion liquids

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A variety of liquids are available for the dispersion of powders and must have the
following characteristics:

 be transparent at the laser wavelength and free from air bubbles or other
particles
 be compatible with the materials used in the instrument
 not dissolve or alter the size of the particulate materials
 favour easy and stable dispersion of the particulate material
 have suitable viscosity to enable calculation
 have a refractive index that differs from that of the material (for the Mie
calculation), and
 not be hazardous to health and meet safety requirements

2.4 Measurement of the scattering of dispersed sample(s)

Generally, a large number of detector scans or sweeps at short time intervals is

used (typically some 2 second or 1000 sweeps). For each detector element an average
signal is calculated, sometimes together with its standard deviation. Data are stored in the
computer memory. The magnitude of the signal from each detect or element depends
upon the detection area and the light intensity. The coordinates (size and position) of
the detect or elements, together with the focal distance of the lens, determine the
region of scattering angles for each element .These factors are factory determined and
stored in the computer.

2.5 Selection of an appropriate optical model

Most often either the Fraunhofer approximation or the Mie theory is used, though
other approximations are sometimes applied for calculation of the scattering matrix.
Below approximately 25 µm, the differences between the optical models become more
significant. In this size range, the proper application of the Mie theory (assuming
accurate real and imaginary refractive index values) provides the greatest accuracy.

When using the Mie theory, the refractive indices of particulate and medium, or their ratio,
are entered into the instrument to allow calculation of the model matrix. Often, small values
of the imaginary part of the refractive index (about 0. 01–0. 1) are applied to cope with
the surface roughness of the particles. In order to obtain traceable results, it is essential that
the refractive index values used are reported.

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The scattered intensity can be calculated by replacing the particle by a disc of same shape and
size as the projected area of the particle in the direction of propagation of the incident light.
Therefore, far field intensity distribution in the forward direction is independent of refractive
index and only a function of particle size, shape and the properties of the incident wave. For a
spherical cross section and small scattering angles (sinθ = θ), the Fraunhofer Diffraction
pattern is given by

Where

Io = scattered intensity in the direction forward direction (θ= 0o)

Iinc =Intensity of the incident plane wave with wavelength ʎ

dp = diameter of the particle

x = Mie parameter

C = a proportionality constant which depends distance of the screen

J1= first order Bessel function.

This angular intensity structure contains side lobes, which decrease in maximum intensity
with increasing scattering angle. For larger particles, the overall intensity decreases with
scattering angle.

When an ensemble of particles in a finite volume is illuminated, all the diffraction pattern of
the individual particles overlap in the far field. For a time varying particle ensemble and a
finite illumination time, interference effects are averaged and the resulting intensity s the
summation over the intensities of all contributing particles.

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Where p(x) is the probability density function of the Mie parameter, i.e., of the size
distribution. Therefore, this equation represents a relation between particle size distribution
and far field distribution of scattered light from these illuminated particles.

2.6 Conversion of Scattering Pattern into Particle Size Distribution

This deconvolution step is the inverse of the calculation of a scattering pattern for a
given particle size distribution. The fact that rapidly measured data always contain some
random and systematic errors may cause erroneous size distribution results. Several
mathematical procedures have been developed for use in the different instruments
available. They allow for some weighting of deviations between measured and calculated
scattering patterns (such as least squares), some constraints (such as non negativity for
amounts of particles), or (or in combination with) some smoothing of the size
distribution curve. A new procedure uses the observed fluctuations of the detect or
signals to introduce proper weighting of these data and to calculate confidence intervals
for the particle size distribution.

The algorithms used are specific to each make and model of equipment and are
proprietary. The differences in the algorithms between different instruments can give rise
to differences in the particle size statistics. For this reason, when reporting the particle
size distribution and statistics for a given material, also report the cell type, sample state
and preparation, together with the make and model of the equipment .

2.7 Replicates

The required precision of the method is dependent on the characteristics of the material
(milled versus not milled, robust versus fragile), and also on the requirements of the
application (formulation type and technique). Appropriate measurement conditions are
established experimentally, in relation to the desired precision. In general, at least three
different representative samples from the same batch are measured. The repeatability of the
particle size distribution parameter is as follows: for any central value of the
distribution, for example the median (x50), the coefficient of variation is less than 10%.
For values away from the centre of the distribution, for example x10 and x90, the coefficient of
variation cannot exceed 15%. Below 10µm, these maximum values are doubled.

2.8 System Suitability

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The system suitability test is used to verify that the precision and accuracy are adequate
for the analysis to be done. The test is based on the concept that the equipment ,
electronics, and analytical operations constitute an integral system that can be evaluated
as such. This can be done by measuring at regular time intervals a control material
of known size distribution. In general, unless otherwise specified in the individual
monograph, the mean values of three measurements must deviate from the established
value by less than 10% for x50, and by less than 15% for x10 and x90. Below 10µm,
these maximum values are doubled.

The distribution statistics are usually reported by the instrument data system. Most
common parameters are calculated from the cumulative distribution by interpolation.
Percentile sizes, xm, represent the particle size in relation to which m percent of the
distribution is smaller. (The notation dm is also used and is equivalent to xm.) Qy
represents the percent smaller than y microns. Mean sizes, such as D4,3, the arithmetic
volume mean diameter, can also be calculated by representing the distribution as a
collection of spherical particles with diameters of the size band midpoints. Unless
otherwise stated, parameters are calculated on the volume or mass basis.

2.9 Accuracy and Repeatability

Primarily, qualification validation can be made with any certified or standard reference
material, accept able for use in the particular industry. Here, the total measurement
procedure is being examined, including sampling, sample dispersion, sample transport
through the measuring zone, measurement , and the deconvolution procedure. It is
essential that the total operational procedure is adequately described in full detail.

Certified or standard reference materials consisting of a known distribution having a

range of spherical particles over one decade of size are preferred. They are certified to
mass percentage by an absolute technique, if available, and used in conjunction with an
agreed, detailed operational procedure. It is essential that the real and imaginary part of
the complex refractive index are precisely specified for the material if the Mie theory
is applied in data analysis.

The response of a laser diffraction instrument is considered adequate if the mean

value of x50 obtained from at least three independent measurements does not exceed
the certified range of values of the certified or standard reference material by more

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than 3%. The mean values for x10 and x90 must not exceed the certified range of
values by more than 5%. For repeatability, the coefficient of variation must be less than
3% for x50 and less than 5% for x10 and x90. Below 10 µm, these maximum values are
doubled.

Although the use of spherical materials is preferable, non spherical ones may also be used.
Preferably, these have certified or typical values coming from laser diffraction analyses
according to an agreed, detailed operational procedure. If the reference values come
from methods other than laser diffraction, a significant bias may result . The reason for
this bias is that the different principles applied in the various methods may lead to
different responses to the particles, and thus to different equivalent -sphere diameters for
the same non spherical particle.

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3. Comparison of Fraunhofer and Mie scattering

Fig.3 Fraunhofer diffraction: Effect of particle size (Hirleman, E., 1988)

As diameter increases, intensity per particle increases and the location of first peak shifts left
i.e. to the smaller angle.

Fig 4. Mie scattering: Effect of particle size (Hirleman, E., 1988)

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 Fig.5 Effect of imaginary part of the refractive index (Hirleman, E., 1988)

In general, refractive index is expressed as m= n-ik, where the real part n is the refractive
index of the particle and the imaginary part k is the absorptivity of the particle.

Fig.6 Effect of real part of the refractive index (Hirleman, E., 1988)

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Practical application:

Fig 6. Size distribution for slurry (Hirleman, E., 1988)

THE FUTURE
Laser diffraction systems are presently perceived ass productive, flexible workhorses – a
reliable part of company’s analytical armoury. However, there are challenges remaining as
industries evolve. One main issue for laser diffraction instrument manufacturers is to make
sure the performance gains over the last decade are fully exploited by the users.

Laser is complementary to, and complemented by, these newer techniques. It is highly
effective to exploit them in combination. The benefit of laser diffraction suggests that the
technique will retain its place as the preferred choice for particle size measurement.

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REFERENCES

Barth, H. G. and Sun, S (1993)., Particle size analysis, Anal. Chem. 65, 55R-66R.

Farmer (1972), W. M., Measurement of particle size, number density and velocity using a
laser interferometer, Appl. Opt. 11, 2603-2612.

Hirleman, E. (1988), Modeling of multiple scattering effects in Fraunhofer diffraction

particle-size analysis, Part. Syst. Charact. 5, 57-65.

Holve (1991), D. J., Using ensemble diffraction to measure particle size distribution, Powder
Bulk Engg 5, 15-19.

Jelinek, Z. K. (1970), Particle Size Analysis, Wiley, New York 286-299.

Stanley-Wood, N. G. and Lines, R. W., (1992) (Eds), Particle Size Analysis, Royal Society of
Chemistry, Cambridge.

Zhang, H. J. and Xu, G. D. (1992), The effect of particle refractive index on size
measurement, Powder TechnoL 70, 189-192.

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