Brookhaven Instruments Corporation White Paper

What Is Particle Size?

By Bruce B. Weiner Ph.D., November 2010

Keywords: particle, particle size, ESD, image analysis,

hydrodynamic radius, Rh, radius of gyration, Rg
Introduction: The short answer is this: diameter or radius. But what type of diameter or radius, and what to do about non-spherical particles? The following introduces some ideas for
those who have never done particle sizing.
Length vs. Mass: If you are a particle technologist, then the only answer is length. But at a recent biochemistry national meeting, a group of
protein chemists continually referred to the molecular weight of a globular protein, a relative
molar mass, as the proteins size. Over hearing this, our group was surprised because we refer to the size of a globular protein in nanometers. With the exception of these protein chemists, the rest of us will mean a length in nanometers or microns when we refer to particle size.
To Be or Not To Be a Sphere: Of all the threedimensional particles, the sphere is by far the
most important in particle sizing. Why is that?
Is it because most particles are spheres? No,
though many come close to it (unaggregated latex, monoclonal antibodies, oil-in-water and water-in-oil emulsions, spherical micelles, liposomes, etc.). And still more are nearly so, especially if measurements are averaged over rotationally diffusing particles1. Over the timescales
of many types of measurements, we are measuring a rotationally averaged size and thus a
sphere represents, often, a reasonable approximation. In addition, if highly irregular particles
are broken down due abrasion, long ones are
broken down into shorter ones and they become
more globular rather than less. Think of wind
and water action forming smooth, globular
rocks from the jagged shards of volcanic debris.
Think of irregular and/or jagged particles
rounded off as they are mixed or stirred on their
way to final product status.

According to the 1st law of thermodynamics, a

liquid body with no external forces will form a
sphere in order to minimize its surface area for a
given volume of material. Thus, liquid droplets,
ignoring external forces, form spheres. This explains why even cooling planets formed, to 1st
order, spherical objects.
But perhaps the most important reason is that
many 2nd-order differential equations that describe the physics of the automated methods
used for measuring particle size are exactly soluble for spheres. Yes, we are fitting nature into
what is conveniently achievable. The good news
is that it works most of the time, most especially
for quality control purposes.

A Quick Tour of Spherical Geometry: The

volume is either 4r3/3 or d3/6 where twice the
radius r equals the diameter d. If you cant easily recall these simple formulas, consult an introductory math book as your first step in learning
about particle sizing. For completion, the surface area of a sphere is either 4r2 or d2. The
Greeks knew these things 2,500 years ago and
many of them still do.
The simple factor of two that relates radius to
diameter is sometimes the cause for a 100% error. If a specification for size does not list it as
radius or diameter, or if a result (mean size, for
example) does not say which it is, or a graph is
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not labeled, then sometimes one is left to guess.

A claim of being able to measure up to 5 micron
in radius is the same as the claim of 10 micron
in diameter. Look for this error. It occurs quite
often and sometimes for purposes of deception,
especially in advertising brochures.
The Equivalent Spherical Diameter, ESD:
There are two types, geometric equivalent and
technique equivalent.
Geometric ESDs: Consider a static, 2-D image
of a particle. First, it is two, not three dimensional. So what looks like a circle might correspond to a thin disc-like particle and not a
sphere, unless shadows reveal a more spacefilling structure. When the image was taken, assuming it was not a 3-D holographic image, one
assumes that as the particles settle they do so, so
as to become stable on a flat surface. Thus, most
discs if they did not land on their faces would
topple over if they landed on an edge. Try it.
Throw coins into the air and see how they land.
There are many different geometrically defined
ESDs that could be assigned to an irregular particle. One way to determine the ESD of an arbitrarily shaped particle is to draw circles around
the actual image until it is just completely enclosed. Assign the diameter of the enclosing circle to that of the particle (de). Alternatively, find
a circle whose area equals that of the measured
particle area. This is easily done by counting
pixels and computer programs that allow ever
increasing accuracy with smaller and smaller
pixels. Given the area of the drawn circle, assign
its diameter to that of the particle (d2/4). This
ESD should be labeled dA. Or, one could trace
the images perimeter and assign that to the diameter of the circle with the same perimeter
(dP).
These are all geometric equivalent diameters.
There are lots more choices based on parallel
tangents (Ferets diameter, dF) and chords

(Martins diameter, dM). Note the fact that the

same particle can have several different types of
geometric ESDs, and if properly labeled, they
should not be equal the more irregular the particle shape. And the ratio of two such geometric
ESDs for the same particle says something
about shape and space filling.
The more irregular the particle shape, the more
difficult it is to describe it with just one parameter. Because of this, the interpretation of size
determined by image analysis is more difficult
than an automated machine based on an ESD
determined by the technique. What is meant by
this type of ESD?
Technique ESDs: Picture a stack of sieve
plates. The mass of all the particles that remain
on a particular plate (after suitable shaking)
whose hole size2 is dS are said to represent the
cumulative increment by mass larger than diameter dS. Think of a particle falling under gravity
or moving radially outward in a centrifuge. Its
velocity is measured and then set equal to that
of a sphere that would have moved in the same
way. The resulting diameter is called the Stokes
diameter, dSt, because the motion is described
by Stokes Law. Imagine a rotating, tumbling
particle whose diffraction pattern is registered
on a detector. Then the pattern is set equal to
that of a sphere that would give the closest diffraction pattern. This is the so-called laser or laser diffraction particle size and should be labeled dLD. Finally, consider using dynamic light
scattering to determine the translational diffusion coefficient of a submicron particle. Then
calculate the so-called hydrodynamic diameter
or radius corresponding to the measured diffusion coefficient. There should be two subscripts
here: H for hydrodynamic and DLS for the
technique (dH,DLS). In practice, double subscripts
like this are rarely seen, though if they were, it
would become more obvious what was actually
measured.

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In all these cases, and many more, the size of

the sphere is assigned such that it would give
the same result as the actual particle. These are
so-called technique ESDs (or ESRs). But what
you see in practice is either d or r and this leads
to confusion when comparing results. For
spheres, if techniques were equally accurate,
then a subscript would not be necessary. But for
irregular shapes, using subscripts one would understand that the sizes should not be equal.
And, as with geometric ESDs, ratios of technique ESDs yield information on shape.
Unlike image analysis, there is only one definition for a given technique (ignoring specialized
flow orientation techniques). Therein lays the
weakness of image analysis: Which ones to
choose to characterize the particle size? There
are no generally applicable, easy guidelines to
consult.
The Promise and Heart Break of Image
Analysis: For very long rods, the aspect ratio,
AR, is defined as the length divided by the diameter, L/d, and sometimes the reciprocal is
called the AR. For more irregular particles, the
longest dimension divided by the shortest dimension is the aspect ratio, or its reciprocal is.
Given the L and d for each particle in a distribution, the aspect ratio can be calculated. A particles performance could be correlated with L, d
or perhaps with AR. There are only three choices here.

There are other difficulties with image analysis

and these are addressed in more detail in another
section of this series entitled A Guide to
Choosing a Particle Sizer.
Three Types of Radii: First, there is the one we
all picture, the hard-sphere, geometric radius,
Rs. This radius is most easily obtained using image analysis. Second, as mentioned, in dynamic
light scattering (DLS), we obtain the hydrodynamic radius, Rh. This radius is the one we get
from comparing a sphere to the translational diffusion coefficient actually measured. Imagine a
solid, hard-core particle whose surface is coated
with long-chain polymers or surfactants that
stick far out into the liquid. Sometimes called
hairy particles, their radii are significantly
larger than that of their cores. Finally, there is
the radius of gyration, Rg, obtained from static
light scattering (SLS). Interestingly, the Rg obtained from SLS measurements is independent
of shape assumptions; whereas, any Rh value assumes a sphere.
Ratios of Rg/Rh suggest shape: 0.77 a sphere;
1.54 a random-coil polymer.

But imagine a more highly irregular particle,

smooth or jagged. There are many possible statistical descriptors of shape and size. Most modern software offers dozens of choices that can be
used. And that is the problem.
Which size parameter or subset of size parameters will correlate with particle performance? In
some disciplines, answers are known. But in
many they are not. Image analysis results in
large amounts of data, but it does not necessarily result in useful information.

Summary: After first determining that particle

size is indeed a length and not the mass of a protein, determine if the results are given for a single statistical parameter or are multiple parameters involved using image analysis. If it is a single statistical parameter, is it a true diameter or
an ESD determined geometrically (image analy-

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sis) or by comparison against what a sphere

would yield using an automated technique (laser
diffraction, centrifugation, sieving, zone counters, etc.). And, finally, is it a radius or a diameter (a true one or ESD/ESR) that is being discussed? With answers to these questions, you
will be in a better position to compare numerical
results more effectively. And that is the subject
of the next application note in this series.
1

The rotational diffusion coefficient, DR, for a sphere of radius

1 micron in water at 25 C is 0.18 s-1 and it varies inversely with
the cube of radius. Thus, a 100 nm radius particle is diffusing
(rotating) 180 times per second. If the measurement time is a second or longer, the results are rotationally averaged.
2

Sieve sizes are a complete topic in themselves. Often, they are

not circular holes. Abraded holes as well as particles broken by
abrasion may be problems. Sifting long enough to ensure all
smaller particles made it through is an issue. Finally, for highly
irregular shapes, if the particle can be oriented by sifting, then it
is the smaller dimension that is determined Think of a distribution of long rods of varying lengths and varying, but much
smaller diameters. Although unlikely, you would be determining
the size distribution of the rod diameters and learn nothing about
the distribution of rod lengths if you could sift them such that
they all stood on end when passing through the sieves holes.

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