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Instrumentation

A Guide to Characterizing
Particle Size and Shape
Remi Trottier
Shrikant Dhodapkar
Dow Chemical Co.

Knowledge of particle properties is essential for


understanding how the particles will impact your
process. Learn how to identify the relevant properties
for a particular application, select the best
measurement technique, and analyze the data
to extract meaningful information.

article science and technology is relevant to a broad


range of chemical processes, including those for
manufacturing paints and coatings, pharmaceuticals,
catalysts, fertilizers, food products, and cosmetics. For
processes that have particles as a raw material, intermediate, or final product, the ability to measure, monitor, and
characterize fundamental particle properties, such as size,
size distribution, shape, density, and surface texture, is
essential.
A particle can be defined as a solid with well-defined
boundaries; its linear dimensions can range from nanometers (colloids) to millions of meters (extraterrestrial
objects). Whether for an industrial process or a natural
process, measuring particle properties (e.g., size and shape)
is a means to an end the ultimate objective is to understand the effect of morphological parameters on particle
behavior. Particle properties can affect absorption, agglomeration, aggregation, bioavailability, compressibility, combustibility, entrainment, fluid-particle interactions, packing,
particle trajectories, permeability, reactivity, segregation,
separation, settling, and toxicity.
This article reviews different ways to define particle
size and explains how to decide which size variable is
appropriate for a particular process and objective. It
describes techniques for measuring particle size and provides key advantages and disadvantages of each. Finally,
it discusses particle shape, as it is difficult to separate the
effect of particle size and particle shape on the macroscopic response of a complex particulate process.

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The many ways to define particle size


The size of a spherical particle is unambiguously defined
by its diameter. This diameter, which can be considered the
particles characteristic dimension, can be directly measured.
However, particles encountered in most industrial processes
are rarely spheres, and very rarely of the same size.
For particles that deviate from the spherical shape, relevant characteristic dimensions (e.g., length, width, diameter)
or derived dimensions (e.g., aspect ratio) that relate to a
size-dependent property must be identified. These so-called
equivalent spherical diameters are often used to translate a
certain property (e.g., surface area, volume, perimeter) of an
irregular particle to a spherical dimension (Figure 1, Table 1).
Sphere with Same
Maximum Length

Sphere with Same


Projected Area
Sphere with Same
Surface Area

Sphere Passing
Through Same
Sieve Aperture

Sphere with
Same Volume

p Figure 1. Most particles of interest in industrial processes are not spherical.


Equivalent diameters can be defined to translate a measured parameter of the
particle (e.g., surface area, volume, perimeter) to a spherical dimension.

Copyright 2014 American Institute of Chemical Engineers (AIChE)

Each derived equivalent diameter represents a mechanism


or characteristic relevant to the process of interest. Therefore,
it is critically important to understand the relevance of these
definitions, and select wisely.

Particle size data


If every particle in the population were identical in size
and shape, only one particle would need to be analyzed.
However, that is extremely rare, so to get a full, accurate,
and statistically representative profile of the size or shape
distribution of a sample, a large number of particles, often
as many as hundreds of thousands, must be analyzed. The
data are then typically sorted into a series of successive size
intervals characterized by the number of particles, surface
area, or mass of each interval. The entire size range, which
can span up to several orders of magnitude, can be covered
with a relatively small number of intervals.
For samples with a narrow size distribution, it may be
appropriate to group the data into linear intervals, such as
01 m, 12 m, 23 m, etc., and express the contents of
each interval as a percentage of the whole population. One
disadvantage of grouping into linear intervals is that the
resolution (i.e., the ratio of the interval width to the mean
Table 1. Equivalent diameters can be used to characterize
the size of nonspherical particles.
Symbol

Name

Definition

dv

Volume Diameter

Diameter of a sphere with the


same volume as the particle

ds

Surface Area
Diameter

Diameter of a sphere with the


same external surface area as
the particle

dsv

Surface-Area-toVolume Diameter

Diameter of a sphere with the


same external surface-area-tovolume ratio as the particle

DSt

Stokes Diameter

Diameter of a sphere with the


same terminal velocity and density
as the particle (in laminar flow)

da

Projected Area
Diameter

Diameter of a circle with the same


area as the projected area of the
particle (in random orientation)

dc

Perimeter
Diameter

Diameter of a circle with the same


perimeter as the projected outline
of the particle

dA

Sieve Diameter

Width of the minimum square


aperture through which the
particle will pass

dF

Feret Diameter

Distance between a pair of


parallel lines tangent to the
projected outline of the particle

dM

Martins
Diameter

Length of the chord dividing the


projected outline of the particle in
two equal halves

Copyright 2014 American Institute of Chemical Engineers (AIChE)

size of that interval) is not constant across the entire size distribution. For example, if the particles are classified into ten
intervals from 0 m to 10 m with each interval 1 m wide,
the resolution of the first interval (01 m) is 2, while for the
last interval (910 m) the resolution is 0.1.
The data can also be organized on a geometric basis,
with the interval widths increasing by the same factor
(e.g., 12 m, 24 m, 48 m, 816 m). Grouping the
particles in this way maintains a constant resolution over
the entire distribution.
Table 2 summarizes a population of particles whose size
intervals are a geometric progression increasing by a factor
of 1.5. The fourth column shows the number of particles
in each interval. The remaining columns show the proportion of the total population in each interval, which can be
expressed in terms of the number of particles, surface area,
volume, or any other basis upon which data are acquired.
Once the data have been collected and grouped into
the appropriate size intervals, they are usually tabulated
and then transformed into a graphical representation. The
size data can be plotted as a differential frequency plot (the
percentage of the total relevant quantity, e.g., number of
particles, surface area, or mass, in each interval) or a cumulative frequency plot, as illustrated in Figure 2.
Differential frequency plots allow for the direct comparison of different distributions, provided the intervals
of the distributions are identical. Cumulative distributions
are useful for comparing several distributions that have
intervals of different widths.

What does mean diameter mean?


Size distributions can be reduced to a single average
diameter, such as the mean, median, or mode. Distribution
averages are often a source of confusion when data from
different instruments that may have calculated the average diameter differently are being compared. An average
particle diameter is meaningless without specifying how it
was calculated.
The mean diameter is a calculated statistic that represents the size of the entire particle population. Several
definitions of the mean are commonly used for various
types of comparisons. The most appropriate mean diameter
for a particular application is the one that corresponds most
closely to the relevant property of the particle system.
The simplest mean is the arithmetic mean, which is the
sum of all of the diameters in the population divided by the
total number of particles:
ni di
dn =
(1)
ni
where ni is the number of particles in group i and di is the
midpoint diameter of the particles in group i. This diameter
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Instrumentation

Table 2. Particle size data should be grouped into appropriate intervals.


The sample data shown here are grouped into geometric intervals with widths that increase by a factor of 1.5.
Diameter

Particles

Number Basis

Surface-Area Basis

Volume Basis

Min

Max

Mid

Count

Diff %

Cum %

Diff %

Cum %

Diff %

Cum %

1.00

1.50

1.25

22

0.044

0.044

0.00

0.00

0.00

0.00

1.50

2.25

1.88

710

1.42

1.464

0.03

0.03

0.00

0.00

2.25

3.38

2.81

2,520

5.04

6.504

0.27

0.31

0.03

0.04

3.38

5.06

4.22

5,500

11

17.504

1.33

1.63

0.26

0.29

5.06

7.59

6.33

10,000

20

37.504

5.44

7.07

1.58

1.87

7.59

11.4

9.49

16,000

32

69.504

19.57

26.65

8.51

10.38

11.4

17.1

14.2

11,000

22

91.504

30.28

56.92

19.74

30.12

17.1

25.6

21.4

3,000

97.504

18.58

75.50

18.17

48.29

25.6

38.4

32.0

1,000

99.504

13.94

89.44

20.44

68.73

38.4

57.7

48.1

2,00

0.4

99.904

6.27

95.71

13.80

82.53

57.7

86.5

72.1

40

0.08

99.984

2.82

98.53

9.31

91.85

86.5

130

108

0.014

99.998

1.11

99.64

5.50

97.35

130

195

162

0.002

100

0.36

100.00

2.65

100.00

is commonly referred to as D[1,0] because the diameter


term in the numerator of the equation is of the power 1 and
the diameter term in the denominator is of the power 0.
The mean surface-area diameter and volume (or mass)
diameter reflect the fact that surface area is proportional
to the square of the diameter and the volume and mass are
proportional to the cube of the diameter.
The mean surface-area diameter is used when the particle surface behavior is important. It is referred to as D[2,0]
and is the arithmetic mean of the particle surface areas:

ni di2

ds =
ni

1/ 2

( 2)

Similarly, the mean volume diameter (or mean mass


diameter) is used when the volume (or mass) of the particles
is important. Referred to as D[3,0], it is the mean diameter

of the particle volumes or masses within the population:

ni di3

d m = dv =
ni

( 4)

d n < ds < dv

Equations 13 are based on the number of particles


being measured, and therefore are limited to particle-sizing
techniques that provide information on individual particles.
The most common techniques measure particle parameters

10
100
Particle Diameter, m

1,000

rea

Vol
um
e

20

ce A

Volume

Surfa

20

Num

Cumulative Frequency, %

Number

ber

40
Surface Area

Differential Frequency, %

(3)

It is not unusual for a population with a wide size distribution to have a mean mass diameter that is one or two
orders of magnitude larger than the arithmetic mean diameter based on the number of particles. In any polydisperse
system, the diameters always follow this relationship:

40

1/3

10
100
Particle Diameter, m

1,000

p Figure 2. The particle size data of Table 2 can be plotted in terms of differential frequency (left) and cumulative frequency (right).

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Copyright 2014 American Institute of Chemical Engineers (AIChE)

where si is the total surface area of the particles in group i


(si = nidi2) and S is the total surface area of the entire population. The Sauter mean diameter can be defined as the diameter
of a sphere having the same surface-area-to-volume ratio as
the entire particle population.
In the calculation of the mean, most particle-size analyzers assume that the particles are smooth spheres, which
may lead to significant errors for populations of highly
irregular particles. In such cases, the Brunauer-EmmettTellet (BET) gas adsorption technique, which estimates
the total surface area from the number of gas molecules
required to cover the surface of the particles, can be used to
measure the surface area; this surface area can then be used
to calculate the Sauter mean diameter:
6
dsv =

(6)

where p is the density of the particles, M is the total mass,


and S is the surface area measured by the BET technique.
The De Brouckere diameter (also referred to as the
mass mean diameter) is:
d mm =

mi di
M

ni di
ni di3
4

(7 )

where mi is the total mass of the particles in group i and


M is the total mass of the entire population.

Instrument selection
To obtain the information required to calculate these
mean diameters, the proper instrument must be selected.
When choosing an instrument, consider the type of data
needed, including the required accuracy and precision.
Consider a fouling problem in a heat exchanger handling the stream characterized by Table 2. Since smallparticle behavior tends to be dominated by surface forces,
fouling is typically associated with small particles sticking
to the surface of the heat exchanger. In this example, the
experimental data show that only the particles with a diameter of <2 m are causing the fouling.
Copyright 2014 American Institute of Chemical Engineers (AIChE)

40

Differential Frequency, %

related to bulk quantities, such as surface area, volume, or


mass, and do not provide information on the number of particles. Thus, other ways to calculate averages must be used.
The two most important means calculated from bulk
quantities are the surface-to-volume mean (i.e., the Sauter
mean diameter, D[3,2]), and the volume mean diameter
(i.e., the De Broukere mean diameter, D[4,3]).
The Sauter mean diameter is:
3
si di ni di
dsv =
=
(5)
S
ni di2

Number

Surface Area

Volume

20

10

100
1,000
Particle Diameter, m

10,000

p Figure 3. It is important to choose the appropriate basis (e.g., number,


surface area, volume) for measuring particle size. Adding a single 820-m
particle to the population in Table 2 skews the volume-based data but does not
affect the number-based data.

However, the surface-area-based particle-size distribution, as well as the volume-based curve (Figure 2), indicate
that 100% of the particles have diameters larger than
2 m which cannot be correct since there is a fouling problem. Instruments that measure particle size on a
number basis are needed to detect those smaller particles.
As a general rule of thumb, when a small percentage of
small particles in a distribution is of interest, single-particle
counting methods should be used.
When a number-based distribution is needed, laser diffraction and dynamic light scattering should not be used.
They should only be used for surface-area- or volume
(mass)-based measurements.
Consider another example in which one 820-m particle is added to the population in Table 2, which is now
represented by Figure 3. This one particle accounts for
roughly 30% of the volume distribution of the population,
but does not effect the number-based distribution.
Surface-area-based measurements should be considered when the surface area of the particulate system plays
an important role, such as in catalysis, fluidization, dust
explosion hazard assessment, or droplet formation. In cases
where the particle shapes are very irregular, the BET technique may be required to accurately determine the surface
area of the particles.
The most common size-measurement basis in the
chemical process industries is mass (or volume). For
example, a wastewater treatment plant is subject to regulations that limit the total mass of suspended solids in the
effluent water, so a distribution or average based on mass
or volume is the relevant quantity of interest.

Particle-sizing instruments
With the exception of imaging technologies, every particle characterization technology provides the measurement
of an equivalent spherical diameter. This equivalent spheriCEP July 2014 www.aiche.org/cep

39

Instrumentation

cal diameter is deduced indirectly from the behavior of the


particles as they pass through restricted volumes or channels
under the influence of gravity or centrifugal force fields, or
from interactions with some form of radiation or ultrasonic
waves (1, 2). Therefore, data for irregular-shaped particles
obtained from different instruments are typically not in good
agreement. Table 3 summarizes some of the advantages and
disadvantages of each of the technologies described in the
following sections.
Particle characterization technologies in use today fall
into one of three categories: ensemble techniques, fractionation techniques, and single-particle counting techniques.

scattered at the same angle to converge at specific locations


on a series of photodetectors. The detectors are strategically positioned to reveal the angular diffraction pattern,
which corresponds to the size of the particles (larger particles diffract light at low angles, smaller particles at higher
angles). While the position of the diffraction pattern provides information on the size of the particles, the intensity
of the diffracted light relates to the total volume of particles
of a particular size. A mathematical model then converts
the diffraction pattern into a particle-size distribution.
The mathematical models are based on the Fraunhofer
and the Mie theories. The Fraunhofer model is a simple
approximation that accounts for the diffraction phenomenon, but ignores reflection, transmission, and refraction,
which may become significant for small particles (<20 m).
The more-sophisticated Mie scattering model takes into
account all light-particle interactions. To use the Mie model,
the refractive index of the particles and of the suspension
medium must be known. The Fraunhofer approximation is
typically used when these optical parameters are not known
and lower accuracy is acceptable.
Over the years, instrument manufacturers have sought
to provide a wider analytical range, the ability to switch
from liquid dispersions to dry-powder dispersions, and
the ability to measure high-concentration dispersions. The

Ensemble techniques
Ensemble techniques, which include laser diffraction,
dynamic light scattering, and ultrasonic spectroscopy, can
measure large numbers of particles simultaneously.
Laser diffraction. These instruments became commercially available in the 1970s, and soon were considered the
workhorse particle analyzer for industrial applications.
As illustrated in Figure 4, light from a laser source is
collimated (i.e., its rays are made parrallel) and transmitted
through the particle dispersion. As the light passes through
the dispersion, it is diffracted by the particles. The diffracted light passes through a Fourier lens that causes rays

Table 3. Each type of particle-sizing instrument has advantages and limitations.


Range, m

Basis

Analysis
Time

Precision

Accuracy

Resolution

Throughput

Capital
Cost

Skill
Level

0.042,000

Mass

Short

High

High

Low

High

High

Low

Dynamic Light
Scattering

0.0031

Intensity

Short

High

High

Low

High

Medium

Low

Ultrasonic
Spectroscopy

0.011,000

Volume

Short

High

High

Low

High

High

Low

Mass

Medium

High

High

Low

Medium

Low

Low

Technique
Ensemble Techniques
Laser Diffraction

Fractionation Techniques
Wet Sieving
Dry Sieving

>5
>45

Mass

Medium

High

High

Low

Medium

Low

Low

Sedimentation

0.05100

Mass

Medium

High

High

High

Medium

Medium

Medium

Field-Flow
Fractionation

0.0033

Mass

Medium

High

High

High

Medium

Medium

High

Hydrodynamic
Chromatography (HDC)
and Capillary HDC

0.021

Mass

Medium

High

High

High

Medium

Medium

High

Single-Particle Counting Techniques


Dynamic Image
Analysis

>5

Number

Short

High

High

High

High

Medium

Low

Optical Particle
Counting

0.22,500

Number

Short

High

High

High

High

Medium

Medium

Electrozone Counter

0.41,200

Number

Short

High

High

High

High

Medium

Medium

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Copyright 2014 American Institute of Chemical Engineers (AIChE)

Particles

Multi-Element
Detector

Focusing Lens

Scattered
Light

Laser

Laser
Light Source
Particle
Dispersion

Obscuration
Detector

Collimator

Photon
Detector

combination of the Fraunhofer model with Mie theory has


expanded the analytical range to roughly 0.04 m (some
vendors claim as low as 0.02 m) to several millimeters,
although the reliability at both ends of the range is somewhat questionable. Even with the combination of these two
models, the validity of any multimodal distribution with
particle sizes below 2 m should be carefully verified.
Several vendors offer dry-powder dispersion instruments
capable of dispersing particles as small as 10 m (and in
some cases, smaller). It is good practice to validate measurements based on dry dispersion by comparing them to data
obtained by the more-traditional wet-dispersion method.
Some laser-diffraction instruments designed for highconcentration measurements have been used for online
applications. Online applications should be thoroughly
validated. It is also important to note that the measurement
basis for laser diffraction is mass (or volume) and conversions to number-based distributions should never be used
even when offered by instrument vendor software.
Dynamic light scattering. The early particle-size instruments from the 1960s and 70s had limited capabilities and
required expert operators. It took almost two decades of
technical improvements, including major advances in digital autocorrelators, microprocessors, and lasers, to bring
dynamic light-scattering technology to a viable existence in
the marketplace. Today, dynamic light-scattering instruments require a low skill level for operation.
In dynamic light scattering, the size distribution of
sub-micrometer particles dispersed in a liquid medium is
deduced from the random movements of particles under
going Brownian diffusion. Unlike laser diffraction, where
the static intensity of light is measured, a dynamic lightscattering instrument records the fluctuations in scattered
light and processes these data using an autocorrelator, as
illustrated in Figure 5. The smaller particles have a higher
diffusion constant and generate a higher-frequency signal
than the lower-frequency signal of the larger particles. The
autocorrelator analyzes the periodicity of these signals to

Intensity

p Figure 4. In laser diffraction, light from a laser source is collimated and


transmitted through the particle dispersion. Light diffracted by the particles
passes through a Fourier lens and is collected on a series of photodetectors.
The Fourier lens causes all rays scattered at the same angle to converge at
specific locations on the detection plane.

Intensity

Fourier Lens

Diameter

Particle Size
Distribution

Time

Autocorrelator

p Figure 5. Dynamic light scattering also uses a laser to illuminate particles


in a suspension. With this technique, the size of the particles is deduced from
the random motions of the particles undergoing Browning diffusion.

extract the particle-size distribution. The measurement basis


is intensity weighted, which makes the measurement more
sensitive to the larger particles in the population.
This type of instrument is ideal for quality control
applications involving unimodal colloidal dispersions. The
analytical range is about 3 nm1 m. The lower size limit
is reached as the intensity of scattered light gets below the
detection limit, and the upper size limit is reached when the
particles start to settle.
Ultrasonic spectroscopy. This technique uses ultrasound
to probe particles that are homogeneously suspended in a
liquid, thereby exploiting the inherent advantage that sound
waves (unlike light waves) can propagate through opaque
dispersions. It can therefore handle suspensions with much
higher particle concentrations than optical techniques.
In ultrasonic spectroscopy, sound waves are passed
through a suspension. As they travel through the sample and
interact with the particles, the sound waves lose energy via
scattering and absorption. Mathematical models based on
fundamental theory convert this energy loss (or attenuation)
as a function of sound frequency into a size distribution.
A key advantage of ultrasonic spectroscopy over optical
particle analysis is its ability to analyze high-concentration
samples. However, it is generally more difficult to implement because, for both phases, numerous physical constants speed of sound, density, thermal coefficient of
expansion, heat capacity, thermal conductivity, viscosity of
the fluid phase, shear rigidity of the solid phase must be
known for accurate size determination. Thus, this method
is best suited for online applications involving the analysis
of high-concentration samples where other technologies
are not practical.
The analytical range of ultrasonic spectroscopy is
0.011,000 m, with concentrations ranging from a few
volume percent to 80 vol% for emulsions. The concentration limits are highly dependent on the material.
Article continues on next page

Copyright 2014 American Institute of Chemical Engineers (AIChE)

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41

Instrumentation

Fractionation techniques
Fractionation methods which include sieving, sedimentation, field-flow fractionation, hydrodynamic chroma
tography, and capillary hydrodynamic chromatography
separate particles by size prior to detection and measurement. Some fractionation techniques are based on physical
phenomena related to first principles and do not require
calibration (others are not and do need calibration). Both the
analytical range and the resolution of these methods are governed by the efficiency of the separation process they utilize.
Sieving. This technique, which has become the workhorse
method for analyzing coarse particles, is straightforward and
the equipment is simple. There are two types of sieving
dry sieving and wet sieving both of which filter particles
through a series of sieves of different mesh sizes. Dry sieving
is typically carried out by shaking a stack of sieves using a
mechanical vibrator, air pulses of sonic frequency, or rotating
air jets. Dry sieving works well for particles with diameters
larger than about 45 m. Wet sieving, with water or another
liquid facilitating particle passage through the sieves, is used
for finer powders, down to roughly 5 m.
The equivalent diameter obtained from this method
is the sieve diameter, which is defined as the size of the
sieve aperture through which the particle being measured
Nomenclature
A
= projected area of the particles outline
d
= mean diameter
= midpoint diameter of the particles in group i
di
dmm = De Brouckere diameter
= surface-area equivalent diameter
ds
= diameter of a sphere circumscribing the particle
dS
dsv = surface-area-to-volume equivalent diameter
= volume equivalent diameter
dv
g
= gravitational constant
= total mass of particles in group i
mi
M
= total mass of the entire population of particles
= number of particles in group i
ni
P
= perimeter of a particles outline
r
= radius of curvature of a corner of a particles profile
R
= maximum inscribed radius of a particle
= total surface area of particles in group i
si
S
= total surface area of the entire particle population
v
= terminal velocity of a particle
V
= volume of a particle
Greek Letters
s,a = surface-area-projected-area shape coefficient
v,a = volume-area shape coefficient
= viscosity of the liquid

= density of the particles
p
= density of the liquid
l
= circularity shape factor
sf
= sphericity

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just passes (i.e., the particle gets caught by the next sieve,
which has a smaller aperture). Since irregular particles tend
to orient themselves along their smallest dimension to pass
through a two-dimesional aperture, the sieve diameter is
typically related to the second-smallest dimension of the
particle. The data from sieving are mass-based measurements i.e., the mass of the material retained on each
sieve is measured to obtain a mass fraction, which is then
presented in tabular or graphical form.
Sedimentation. This mass-based method measures the settling rate of particles dispersed in a liquid that is subjected to
gravitational or centrifugal forces. At the start of the measurement, the particles may be uniformly distributed throughout the liquid (homogeneous start) or concentrated within
a narrow band at the liquids surface (line start). Particle
movement can be monitored using optical or X-ray detectors.
Regardless of the system configuration (line/homogeneous
start, gravitational/centrifugal force, optical/X-ray detector),
the Stokes equation applies to all sedimentation equipment:
v=

gd 2 p l
18

(8 )

where is the terminal velocity of a particle, g is the


gravitational constant, d is the particle diameter, p is the
particle density, l is the liquid density, and is the liquid
viscosity. For centrifugal sedimentation, the constant g is
replaced with the actual acceleration of the system.
Sedimentation instruments have high resolution
because the separation technique is based on terminal
velocity, which is proportional to the square of the particle
diameter. However, this high resolution comes with a disadvantage: obtaining results for a sample with a wide size
distribution generally takes a long time, thereby reducing
the throughput of the technique.
Field-flow fractionation (FFF). Although field-flow
fractionation methods were first described in 1967, the
technology transfer from an academic laboratory technique
to a viable commercial instrument took more than 20 years,
after which rapid proliferation took place.
The term field-flow fractionation refers to a family of
mass-based techniques in which particles dispersed in a liqApplied Force
Particle
Dispersion
Flow
Diffusion

p Figure 6. Field-flow fractionation subjects particles dispersed in a flowing liquid to forces perpendicular to the flow. The applied force causes the
particles to move toward the bottom of the channel, while the diffusion of
the particles causes them to move against the applied force. Since a parabolic flow profile exists in the channel, the rate at which the particles travel
through the channel depends on their position, and therefore their size.

Copyright 2014 American Institute of Chemical Engineers (AIChE)

uid flow through a narrow channel that is subjected to forces


perpendicular to the flow (Figure 6). The applied forces
(e.g., cross-flow stream, temperature gradient, centrifugal
force) cause the particles to move toward the bottom of the
channel, where diffusion opposes the applied forces. The
opposing forces confine particles of different sizes to specific
regions of the channel smaller particles have higher diffusion coefficients and thus flow near the center of the channel, while larger particles, with lower diffusion coefficients,
travel near the edges. Since a parabolic flow profile exists in
the channel, particles of different sizes are transported at different rates, allowing them to be separated according to size.
These techniques provide a high-resolution separation over
the size range of 3 nm3 m.
Hydrodynamic chromatography (HDC) and capillary
hydrodynamic chromatography (CHDC). In both HDC and
CHDC (Figure 7), the particle-containing liquid travels
through microchannels; in HDC, the microchannels are in
the interstices between beads packed in a column, while
CHDC utilizes straight microchannels. Under laminar conditions, a parabolic flow profile arises, in which the smaller
particles travel closer to the walls in the lower-velocity zones
and the larger particles travel farther away from the walls at
higher velocities. HDC and CHDC provide a high-resolution
separation over the analytical size range of 0.021 m.
The first CHDC instruments became commercially available around 1990, about 30 years after the discovery of this
fractionation technique. Meanwhile, HDC was developed
in an industrial laboratory to fulfill a sub-micron analytical
need; although it provides high-quality sizing data, HDC has
seen limited success in the market, mainly because a high
skill level is required to operate the instrument and the packed
column has a tendency to retain particles and plug over time.

Single-particle counting methods


Particle-counting instruments (also referred to as
stream-counting methods), including dynamic image analysis, optical counters, and electrozone counters, detect and
Capillary Hydrodynamic
Chromatography

Hydrodynamic
Chromatography

count particles one at a time. These methods are not based


on first principles and therefore require calibration.
Particle counters offer the ultimate in resolution, but
can suffer from poor statistical accuracy when the data are
converted from a number-based distribution to a mass- or
volume-based one, especially when the size range is larger
than two orders of magnitude. Because of the inherently
narrow analytical range of these techniques, most counting devices come equipped with several (typically two
or three) distinct sensors or sets of magnifying optics to
increase their analytical ranges.
Dynamic image analysis. The pioneering studies of
particle characterization by imaging technologies were
carried out in the late 1960s and early 1970s. Increasing dataprocessing power coupled with the high performance and
falling costs of video cameras and high-speed frame grabbers
have enabled the development of sophisticated and powerful
image processing and analysis systems. Modern instruments
are capable of acquiring tens or even hundreds of frames per
second with simultaneous image processing to extract size
and shape information. This new breed of instruments has
gained considerable popularity within the past decade.
As illustrated in Figure 8, particles flow through the
sensing zone, where they are illuminated by a light source
(e.g., strobe, laser, or incandescent), magnified, and then
detected by a charge-coupled device (CCD) camera. The
particles are dynamically presented to the instrument as
dry particles carried in a gas stream or falling from a vibratory feeder, or as a liquid dispersion moving through thin
rectangular glass cells.
Dynamic image analysis systems are normally used for
particles larger than roughly 5 m in dia. Several manufacturers have exaggerated claims regarding the lower limit of the
analytical range for these instruments. The smallest particle
measured should be represented by at least 710 pixels
not a single pixel, which would imply a square or rectangular
particle. The measurement basis is the number of particles,
but the data can be converted to a volume-based distribution.
Optical particle counting. The first optical particle

deff
v

Zoom Lens
h

Strobe Light

Flow
vmax
Flow

p Figure 7. In hydrodynamic chromatography and capillary hydrodynamic


chromatography, a particle-containing liquid travels through microchannels
in the interstices between beads packed in a column in HDC, and through
straight capillary tubes in CHDC. A parabolic flow profile forms in which
particle velocity is a function of particle size.

Copyright 2014 American Institute of Chemical Engineers (AIChE)

Sample Flow
Camera

p Figure 8. Dynamic image analyzers consist of a light source to illuminate


the particles in the sensing zone, a zoom lens, a camera to capture images of
the particles, and a processor to quantify the size and/or shape of the particles.

CEP July 2014 www.aiche.org/cep

43

Instrumentation

counters were developed in the late 1950s and early 1960s


to measure the size distribution of aerosols. Instruments for
liquid-based systems were subsequently developed and used
extensively to measure the cleanliness of hydraulic fluids.
Optical particle counters (Figure 9) use the principle
of light blockage to count particles and measure their size.
As a particle passes through the illuminated sensing zone,
it casts a shadow onto the photodetector, which converts
the shadow into an electrical signal, or pulse. The photo
detector sends this pulse to an analyzer, where the height
of the pulse, which is proportional to the cross-section
of the particle, is converted into an equivalent diameter,
referred to as the projected-area diameter (da).
The analytical range of optical particle counting is
roughly 0.22,500 m, depending on the manufacturer;
two or three sensors, each with a limited analytical range,
are required to cover the full analytical range. The numberbased measurement can be converted to a volume-based
distribution.
Electrozone counters. The first electrozone counter was
introduced by Wallace Coulter in 1954 to count blood cells.
Since then, this technology has found a wide range of applications, and after more than half a century, the Coulter counter is
still the preferred technique for obtaining blood counts.
Particles suspended in an electrolyte are drawn through
an orifice situated between two electrodes (Figure 10),
altering the electrical resistance of the electrolyte. The
change in the resistance experienced by the electrolyte is
proportional to the volume of the particle (i.e., the volume
of electrolyte displaced). These instruments measure the
volume equivalent diameter (dv) and provide a numberbased measurement that can be converted to a volumebased distribution. They have an analytical range of
0.41,200 m using multiple sensors.
Particle
Flow
Laser

Particle Diameter
Distribution

Sensing
Zone

Pulse Height
Distribution

p Figure 9. Optical particle counters measure a voltage drop proportional to the cross-section of the particle. As particles pass through the
illuminated sensing zone, they cast shadows onto the photodetector and
reduce the voltage of the detector. The photodetector sends the pulse to an
analyzer, which converts the height of the pulse into an equivalent diameter.

44

www.aiche.org/cep July 2014 CEP

Anode

Cathode

Aperture

p Figure 10. In electrozone counters, particles suspended in an electrolyte


pass through an aperture positioned between two electrodes. The change in
the resistance of the electrolyte is proportional to particle volume.

Particle shape
Irregularly shaped particles are much more common than
spherical particles. Two irregular (nonspherical) particles
with the same equivalent spherical diameter can have very
different shapes. British Standard BS 2955 (3) includes a
list of terms related to particle shape, some of which are
shown in Table 4. While these terms may be useful descriptors, their lack of quantification does not lend them to use in
mathematical equations.
Shape factors and shape coefficients provide quantitative information about particle shape and can serve many
purposes, such as:
relating various definitions of derived particle-size
measurements
relating particle volume or surface area to a characteristic dimension (e.g., length, diameter, etc.)
generating a 2D outline of the original particle.
The shape of a large particle can be physically measured
and expressed as linear dimensions on orthogonal axes. For
example, geologists routinely take direct measurements to
define the shapes of rocks and pebbles. However, the study of
microscopic particles must rely on silhouettes or outlines. The
Table 4. These adjectives describe particle shape
in qualitative terms.
Term

Description

Acicular

Needle-shaped

Angular

Sharp-edged or having roughly polyhedral shape

Dendritic

Branched crystalline shape

Fibrous

Thread-like

Granular

Approximately equidimensional but irregular

Lamellar

Plate-like

Crystalline

Freely developed in a medium of geometric shape

Spherical

Globular-shaped

Irregular

Lacking any symmetry

Modular

Having rounded irregular shape

Source: (3).

Copyright 2014 American Institute of Chemical Engineers (AIChE)

orientation of the particles is usually random, so particles of


identical form often have different outlines. Thus, it is necessary to use statistics to obtain a representative characterization
of particle shape.

Common shape factors


References 46 provide excellent reviews on shape measurement. However, clear guidance on the selection of suitable
shape factors for various applications is not available.
The underlying physics of the macroscopic behavior of
interest dictates the appropriate morphological properties for
consideration. Before selecting a shape factor, ask the following questions to narrow the choices:
Is the shape factor independent of size, magnification,
orientation, and rotation?
How does the measurement method affect the shape
factor or shape coefficient?
Does the resolution of the instrument affect the
measurement, especially at the ends of the particle-size
distribution?
Is the measurement based on a 3D measurement or a
2D profile or outline?
Is the shape factor relevant to the macroscopic property under investigation?
Broadly speaking, the quantification of particle shape
falls into four categories (5):
1. dimensional ratios
2. sphericity, which depicts form or overall shape
3. roundness, or circularity, which indicates angularity or
the sharpness of corners
4. roughness, which characterizes surface texture.
Heywood (6) recognized that the definition of shape must
include its form and the relative proportions of its dimensions.
Form refers to the particle's resemblance to a defined geo
metry (e.g., sphere, cube, tetrahedron). He proposed the use of
an elongation ratio and a flakiness ratio as shape factors.
Dimensional ratios. The form of a particle can be defined
Roundness
T
Sphericity

p Figure 11. The shape of a particle can be characterized in terms of


sphericity, roundness, roughness, and dimensional ratios of length (L),
breadth (B), and thickness (T).

Copyright 2014 American Institute of Chemical Engineers (AIChE)

d
= v
dS

( 9)

Riley proposed a quicker method to estimate as the


square of the diameter of the largest inscribed circle divided
by the diameter of the smallest circle circumscribing the particle outline.
Circularity. Circularity () is often used as the shape
factor for 2D planar profiles. The circularity of a particle
can be defined as the circumference of a circle whose area
is equal to that of the particle's projected area divided by
the perimeter of the actual particle.
The circularity shape factor (sf) is defined as:
sf =

Roughness

in terms of ratios of length (L), breadth (B), and thickness (T).


As shown in Figure 11, T is the minimum distance between
two parallel planes that are tangential to the opposite surfaces
of the particle when the particle is in its most stable orientation; B is the minimum distance between two parallel planes
that are tangential to the particle surface and perpendicular
to the planes defining particle thickness; and L is the distance
between two parallel planes that are perpendicular to the
planes defining T and B.
These three dimensions can be expressed as ratios:
elongation ratio = L/B (ranges from 1 to infinity)
flakiness ratio = B/T (ranges from 1 to infinity)
chunkiness ratio = B/L (ranges from 0 to 1).
For a 2D particle outline, the aspect ratio (AR) may be
defined in terms of the minimum distance (Fmin) and the
maximum distance (Fmax) between pairs of tangents to the
particle profile: AR = Fmin/Fmax (ranges from 0 to 1).
Sphericity. This property indicates how closely the
particle resembles a sphere. Wadell defined sphericity () as
the surface area of a sphere having the same volume as the
particle divided by the actual surface area of the particle.
Owing to the difficulty in measuring the surface area
of an irregular particle, Wadell proposed an approximation, in which is the square of the diameter of a sphere
having the same volume as the particle (dv) divided by the
diameter of a circumscribing sphere (dS):

4A
P2

(10)

where A is the projection area of the particle outline and P


is the perimeter of the particle outline. Note that the circularity shape factor and circularity are different.
Roundness. Roundness is a measure of the angularity of
a particle profile, and an indicator of the presence of sharp
corners:
N

Roundness =

i=1 ri R

(11)

N
CEP July 2014 www.aiche.org/cep

45

Instrumentation

where ri is the radius of curvature of a corner, N is the total


number of round corners in the particle profile, and R is the
maximum inscribed radius of the particle.
Convexity. The convex hull perimeter of a particle can
be visualized as the length of an elastic rubber band that fits
around the particle. Convexity is the convex hull perimeter
divided by the perimeter of the particle excluding roughness.
It is a measure of the compactness of a particle profile, and is
affected by surface irregularities, spikes, and concave regions
of the perimeter. Convexity is sometimes measured as the
projected area of the particle divided by the area of the convex
hull, which are easier to measure.
Surface texture. The surface texture of the particle can
be quantified by rugosity, which is the perimeter of the particle outline including roughness divided by the perimeter
of a smooth curve circumscribing the particle profile.

In the same way, the surface-area-projected-area shape


coefficient (s,a) relates the surface-area diameter (ds ) to the
projected-area diameter:

Shape coefficients
Surface area and volume are related to the square and the
cube of the characteristic linear dimension of the particle,
respectively. The shape coefficient expresses this relationship.
The value of the shape coefficient depends on the
definition of particle size (e.g., projected-area diameter,
volume-equivalent diameter, Stokes diameter) and the bulk
property of interest (i.e., volume or surface area). The measurement method must be reported with a shape coefficient.
For example, the volume-area shape coefficient (v,a)
relates the volume diameter to the projected-area diameter:

Literature Cited

3
d = v,a d a3
(12)
6 v
where V is the volume of the particle, dv is the volumeequivalant diameter, and da is the projected-area diameter.
V=

Remi Trottier is a research scientist in the solids processing discipline of


engineering sciences at Dow Chemical (Email: RATrottier@dow.com).
He has over 20 years of industrial experience in particle characterization, aerosol science, air filtration, and solids processing technology.
He has authored roughly 20 papers and has served as an instructor for
several short courses on particle characterization. He received BS and
MS degrees in applied physics from Laurentian Univ., Sudbury, ON,
Canada, and his PhD in chemical engineering from Loughborough Univ.
of Technology, U.K.
Shrikant Dhodapkar is a Fellow in the Process Fundamentals Group,
Performance Plastics Process R&D at Dow Chemical (Email:
SDhodapkar@dow.com). He has been with Dow for 22 years and has
worked closely with the elastomers business for the past 15 years
to develop, design, and implement technologies related to material
handling. He is an expert in the field of solids processing and bulk
solids handling and has extensive industrial experience in powder
characterization, fluidization, pneumatic conveying, silo design, gassolid separation, mixing, coating, computer modeling, and scaleup.
He received his BTech from Indian Institute of Technology in chemical
engineering, and an MS and PhD from the Univ. of Pittsburgh, both in
chemical engineering. He is a senior member of AIChE and past chair
of the Particle Technology Forum. He has authored or co-authored over
35 external publications and four chapters in handbooks. He is also an
adjunct professor of chemical engineering at the Univ. of Pittsburgh.

46

www.aiche.org/cep July 2014 CEP

(13)

S = d a2 = s,a d a2
where S is the surface area of the particle.

Closing thoughts
Knowledge of particle size, size distribution, and shape
is critical for designing and operating complex particulate
processes. While the modern age of electronics and computers made the measurement techniques more robust and less
onerous, the amount of data that can be generated has also
proliferated. Such data can result in misleading conclusions
CEP
unless you clearly understand the fundamentals.

1. Allen, T., Powder Sampling and Particle Size Determination,


Elsevier, Philadelphia, PA (2003).
2. Dalla Valle, J. M., Micromeritics The Technology of Fine
Particles, Pitman Publishing Corp., New York, NY (1943).
3. British Standards Institution, Glossary of Terms Relating to
Particle Technology, BS 2955, BSI, London, U.K. (1993).
4. Hawkins, A. E., The Shape of Powder-Particle Outlines, John
Wiley and Sons, New York, NY (1993).
5. Rodriguez, J. M., Particle Shape Quantities and Measurement
Techniques A Review, Electronic Journal of Geotechnical
Engineering, 18 (A), pp. 169198 (2013).
6. Singh, P., and P. Ramakrishnan, Powder Characterization
by Particle Shape Assessment, KONA Powder and Particle
Journal, 14, pp. 1630 (1996).

Additional Resources
Davies, R., A Simple Feature-Space Representation of
Particle Shape, Powder Technology, 12 (2), pp. 111124
(SeptOct 1975).
Gy, P., Sampling Theory and Sampling Practice: Heterogeneity,
Sampling Correctness, and Statistical Process Control, 2nd ed.,
CRC Press, Boca Raton, FL (1993).
Heywood, H., Symposium on Particle Size Analysis, Institution of
Chemical Engineers, London, U.K. (Feb. 4, 1947).
Jilavenkatesa, A., et al., NIST Recommended Practice Guide:
Particle Size Characterization, U.S. Government Printing Office,
Washington, DC (Jan. 2001).
Kaye, B., and R. A. Trottier, The Many Measures of Fine Particles, Chem. Eng., 102 (4), pp. 7886 (Apr. 1995).
Leschonski, K., Sieve Analysis, the Cinderella of Particle Size
Analysis Methods?, Powder Technology, 24 (2), pp. 115124
(NovDec 1979).
McGlinchey, D., ed., Characterisation of Bulk Solids, WileyBlackwell, Hoboken, NJ (2005).
Trottier, R. A., and S. Dhodapkar, Sampling Particulate Materials
the Right Way, Chem. Eng., 119 (4), pp. 4249 (Apr. 2012).

Copyright 2014 American Institute of Chemical Engineers (AIChE)