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A Guide to Characterizing
Particle Size and Shape
Remi Trottier
Shrikant Dhodapkar
Dow Chemical Co.
36
Sphere Passing
Through Same
Sieve Aperture
Sphere with
Same Volume
Name
Definition
dv
Volume Diameter
ds
Surface Area
Diameter
dsv
Surface-Area-toVolume Diameter
DSt
Stokes Diameter
da
Projected Area
Diameter
dc
Perimeter
Diameter
dA
Sieve Diameter
dF
Feret Diameter
dM
Martins
Diameter
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.
37
Instrumentation
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
ni di2
ds =
ni
1/ 2
( 2)
ni di3
d m = dv =
ni
( 4)
d n < ds < dv
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).
38
(6)
mi di
M
ni di
ni di3
4
(7 )
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, %
Number
Surface Area
Volume
20
10
100
1,000
Particle Diameter, m
10,000
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
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
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
>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
40
Particles
Multi-Element
Detector
Focusing Lens
Scattered
Light
Laser
Laser
Light Source
Particle
Dispersion
Obscuration
Detector
Collimator
Photon
Detector
Intensity
Intensity
Fourier Lens
Diameter
Particle Size
Distribution
Time
Autocorrelator
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
42
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 )
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.
Hydrodynamic
Chromatography
deff
v
Zoom Lens
h
Strobe Light
Flow
vmax
Flow
Sample Flow
Camera
43
Instrumentation
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
Anode
Cathode
Aperture
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
Dendritic
Fibrous
Thread-like
Granular
Lamellar
Plate-like
Crystalline
Spherical
Globular-shaped
Irregular
Modular
Source: (3).
d
= v
dS
( 9)
Roughness
4A
P2
(10)
Roundness =
i=1 ri R
(11)
N
CEP July 2014 www.aiche.org/cep
45
Instrumentation
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=
46
(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.
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).