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A Guide to Characterizing

Particle Size and Shape

Remi Trottier

Shrikant Dhodapkar

Dow Chemical Co.

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.

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.

36

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

Projected Area

Sphere with Same

Surface Area

Sphere Passing

Through Same

Sieve Aperture

Sphere with

Same Volume

Equivalent diameters can be defined to translate a measured parameter of the

particle (e.g., surface area, volume, perimeter) to a spherical dimension.

or characteristic relevant to the process of interest. Therefore,

it is critically important to understand the relevance of these

definitions, and select wisely.

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

same volume as the particle

ds

Surface Area

Diameter

same external surface area as

the particle

dsv

Surface-Area-toVolume Diameter

same external surface-area-tovolume ratio as the particle

DSt

Stokes Diameter

same terminal velocity and density

as the particle (in laminar flow)

da

Projected Area

Diameter

area as the projected area of the

particle (in random orientation)

dc

Perimeter

Diameter

perimeter as the projected outline

of the particle

dA

Sieve Diameter

aperture through which the

particle will pass

dF

Feret Diameter

parallel lines tangent to the

projected outline of the particle

dM

Martins

Diameter

projected outline of the particle in

two equal halves

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.

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

CEP July 2014 www.aiche.org/cep

37

Instrumentation

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

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)

diameter) is used when the volume (or mass) of the particles

is important. Referred to as D[3,0], it is the mean diameter

ni di3

d m = dv =

ni

( 4)

d n < ds < dv

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).

38

(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)

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 )

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, %

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

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

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.

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

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

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

40

Particles

Multi-Element

Detector

Focusing Lens

Scattered

Light

Laser

Laser

Light Source

Particle

Dispersion

Obscuration

Detector

Collimator

Photon

Detector

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

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

in a suspension. With this technique, the size of the particles is deduced from

the random motions of the particles undergoing Browning diffusion.

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

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 )

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.

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.

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

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

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.

Sample Flow

Camera

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.

43

Instrumentation

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

Anode

Cathode

Aperture

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

Dendritic

Fibrous

Thread-like

Granular

Lamellar

Plate-like

Crystalline

Spherical

Globular-shaped

Irregular

Modular

Source: (3).

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

of particle shape.

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

sphericity, roundness, roughness, and dimensional ratios of length (L),

breadth (B), and thickness (T).

d

= v

dS

( 9)

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

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)

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

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.

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=

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

(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.

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).

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