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36 Powder and Bulk Engineering, February 1995
Measuring nanometer-sized particleswith
dynamic light-scatteringtechniques
Philip E. Plantz and Paul J. Freud Leeds+Northmp
The developmentof dynamic light-scatteringtechnology
is providing accurate sizing of ultrafine particles from 3
to 6,000nanometers.After discussingthe growing popu-
larity of nanosized particles, this article describes chal-
lenges in measuring such small particles and how two
methods of dynamic light scattering overcome these
challenges.The final section covers applicationsfor these
sizingtechniques.
I
t may be a well-worn phrase, but good things do come in
small packages. The ultrafine particle sizes of todays ad-
vanced materials signal a revolution in controlling material
characteristics and performance.
How small are the particles? Ultrafine powders contain nano-
sized particles that are measured in billionths of a meter (typi-
cally from 1 to 1,000nanometers, or 0.001 to 1 micron). The
particles improve products by giving processors better control
of a materials properties and how the material works.
For instance, a drug containing nanosized particles can be in-
jected into the bloodstream without blocking capillaries.
Adding nanosized particles to cast steel creates a stronger steel
with a finer grain. Nanosized particles make extremely dense,
highly pliable ceramic materials for heat-tolerant engine parts
and other components. The particles also produce stronger al-
loys and plastics. Even entirely new materials can be tailor-
made for specific applications by sandwiching the nanosized
particles with other metals and ceramics and blending proper-
ties of each.
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While a nanosized particle of a given material shares the same
chemical composition as a larger particle, the tiny particles
size and surface-area-to-volume ratio improve the materials
performance and reactivity. Thus, because most of a nanosized
particles atoms -and hence, energy -are on its surface, just
a few nanosized particles are needed to initiate some solid-
phase reactions. This performance improvement has spurred
the application of nanosized particles as sintering aids and
composite additives, among other products.
Theres no doubt the trend toward smaller particles promises
great things for advanced materials processing. For those of us
who must characterize the materials, however, this trend begs
the question: How can I accurately measure particles just a few
billionths of a meter in size?
Two decades ago, laser light-scattering systemswere devel-
oped that could measure particle size from a few microns to
hundreds of microns. Such a system directed fluid- or air-
suspendedparticlesthrough a laser beam, producing a scattered-
light pattern. The system measured the pattern to determine the
particle size distribution.
While advances in this static light-scattering technology have
extended the limits of measurable size, nanosized particles
from a few nanometers to a few microns have remained difficult
to measure. Another recently developed technique, dynamic
light scattering, is ideally suited to measuring nanosized parti-
cles.
Dynamic light scattering
Particles in the submicron and near-submicron range (called
colloids) exhibit movement because theyre bombarded by the
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Powder and Bulk Engineering, February 1995 37 73
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suspending mediums molecules. This process, called Brown- causes the collected light to fluctuate. Analyzing the intensity 5
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ian motion, displaces the particles and causes them to migrate fluctuations shows that theyre not random, but exhibit a well-
or diffuse. Measuring the particles migration can determine defined buildup and decay lifetime. This lifetime is inversely 0
the particles diffusion coefficient, D. Using the Stokes-Ein- proportional to the diffusion coefficient, D,which is used to cn
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stein relation, determine the particle size from the above Stokes-Einstein
relation.

D = kT/67rq R

(where kis the Boltzmanns constant, Tis the absolute tempera- Figure 1
ture, and q is the viscosity) can determine the particle size R.
The dynamic light-scattering technique determines the diffu- Photon correlation spectroscopy
sion coefficient by analyzing the laser light scattered from the
moving particles.

How photon correlation spectroscopyworks

One dynamic light-scattering variation is photon correlation
spectroscopy. In this technique, a photomultiplier collects the
light scattered from laser-irradiated particles suspended in a
sample cell, as shown in Figure 1. The laser light travels through
a centimeter or more of the cell. As Brownian motion causes
each particle to change position, the scattered light wave pre-
sents a changing phase relative to the scattered light from other
particles in the suspension. Because all the particles are in mo-
tion, the total light collected has many different phases, which

Figure 2

Controlled reference method system

Three-port
surface wavequide -- - -

-
\
Sample cell

Photodetector-

I Port 3 \--\
\
L7 Optical probe P O L

I Personol
Analog-to-digital
converter

Fast-Fourier-
-I computer

Frequency-shifted
scattered light\
transform digital
signal processor
I
Incoming I
\ laser beam Reference
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Powder and Bulk Engineering, February 1995 39 73

How the controlled referencemethod works (port 3) to a photodetector. A beam is also reflected from the
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A different approach to determining particle size based on dy- probe-to-sample interface; its frequency remains unshifted,en- d

namic light scattering is the controlled reference method, abling the beam to act as a controlled reference. This reference 0
which measures the Doppler frequency shifts of light scattered beam is combined with the collected scattered beam and deliv- cn
ered (through port 3) to the photodetector.
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from the moving particles. While similar to measuring fluctua- 77
tion lifetimes, measuring the frequency shift distribution has
major advantages: the higher optical signal it produces and the
ability to measure particles at higher sample concentrations. A The optical signal created by combining the reference beams
closer look at how the controlled reference method works unshifted light with the scattered, frequency-shifted light varies
helps to explain these advantages. at the two beams beat frequency. This produces a very high -0
optical signal because the reference beam is much stronger than 0
the weaker scattered light beam. d
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As the particles move, the optical frequency of their scattered
light is shifted,which is the familiar Doppler effect. By measur-
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P,
ing the frequency shifts of light scattered from all the particles 3
as they interact with a laser beam, the controlled reference As shown in Figure 2, the beam emerging from the optical Q

method determines a frequency power spectrum, which it ana-
lyzes to yield the diffusioncoefficient and the particle size.
As shown in Figure 2,a three-port surface waveguide built into
an optical probe delivers laser light (through port 1)to the sam-
ple cell (through port 2), collects the back-scattered light
(through port 2), and delivers it through a Y optical splitter
probes tip scatters from the suspended particles located only m
a short distance from the tip -about 50 to 100 microns. This r_
7i
short path permits measuring highly concentrated samples
without concern for high signal attenuation (in which the opti-
cal signals amplitude decreases as it travels over distance) or
multiple scattering. The longer, through-the-sample measure-
ment provided by photon correlation spectroscopy is limited
to low concentrations because of the high optical attenuation
and multiple scattering that occur at high concentrations.
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Powder and Bulk Engineering, February 1995 73
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The particle size measurements of both techniques have been 5
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compared at various solids concentrations - from parts per
million to a few percent. Figure 3 shows results3of measuring a 0
well-characterized sample of 460-nanometer spherical poly-
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styrene particles as a function of concentration (from 1to 1,000 77
ppm). The controlled reference method -with its short path -
shows a constant measured size, consistent with the samples
specified size, over a wide concentration range. In contrast, the
photon correlation spectroscopy method -with the longer
path - shows a measured size over the same concentration
range that depends strongly on the concentration. -0
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Applications of dynamic light scattering 3
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Both dynamic light-scattering techniques -photon correla- m
tion spectroscopy and the controlled reference method -can r_
measure many materials from 3 to 6,000 nanometers (0.003to 7i
6 microns). Examples of nanosized particles measured with
these techniques are industrial polymers, resins, and other
chemicals; abrasives and industrial oxides: advanced ceram-
ics; pharmaceuticals; liposomes; and food.
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42 Powder and Bulk Engineering, February 1995 73
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Measuring the particle size distribution of nanosized industrial Figure 5 reports dynamic light-scattering measurements of 5
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polymers and other nanosized chemicals allows you to study polystyrene at a 25 percent (production-level)solids concentra-
their stability, shelf-life, and end-use applications. Because tion. The trace represents the cumulative volume and the solid 0
these materials are manufactured in large process quantities for area represents the differential volume. The data reported for
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use as adhesives or paints, several effects - such as coagula- such concentrated samples is reliable because, generally, the
tion, interference with chemical reactions, and temperature more concentrated the particle sample, the easier it is to avoid
fluctuations-can create particle size distributions that lead to dilution effects. Such effects include destabilization, such as
unsatisfactory product. The following application data3de- settling and coagulation (particles attaching to each other to
scribes dynamic light-scattering size measurements for evalu- create larger particles).For instance, if the particle sample is di-
ating the desirable and undesirable traits of various materials. luted, it would be hard to determine whether coagulation is a
property of the material itself or an artifact caused by diluting -0
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the material for the sample. d
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In Figure 4, a resin emulsion is measured at 1percent solids con- %
centration. Trace A represents the differentialvolume -that is, P,
the volume of particles (in percent of total) between one size and Measuring nanosized abrasives and industrial oxides can be 3
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another; trace B represents the cumulative volume (in percent) subject to suspension and dispersion problems because their m
of particle size (that is, the cumulative informationabout particle specific gravity causes the materials to settle. Figure 6 shows r_
size computed from the differentialvolume data). For example, dynamic light-scattering measurements of six sizes of dia- 71
on trace B, the data indicates that 90 percent of the samples par- mond dust abrasive between about 100and 2,000 nanometers.
ticles are smaller than 1micron, while on trace A, the data indi- While the finer particles typically wont settle before the size
cates that 2 to 3 percent of the particles fall between 0.9 and 1.O measurements are complete, the coarser particles can. To avoid
micron and that the median particle size is about 0.65 micron. such settling effects, each dust sample was stabilized by sus-
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44 Powder and Bulk Engineering, February 1995 73
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pending it in 60 percent glycerol.The dusts concentration was somes are used in drug targeting (formulating drug delivery 5
increased to 1percent to enhance the scattered light signal and systems that will target a specific body tissue). If a long-term d

measure the median particle diameter to an accuracy within 4
percent.
With some nanosized materials, particularly advanced ceram-
ics, you can use dynamic light-scattering methods to find ex-
cessively large particles or agglomerates. Such materials
include very fine particles from 50 to 1,000 nanometers and
can contain individual coarse particles up to several microns.
Such large particles can cause faults in specialized ceramic
products, such as engine parts.
In pharmaceutical and food sciences, you can use dynamic
light-scattering techniques to obtain data about several materi-
als. For instance, the technology can measure proteins molecu-
lar weight, provide data for substrate interaction studies of
enzymes, and provide stability and quality control data for
emulsions. It can also measure the stability of phospholipid
vesicles (liposomes) to help determine their shelf-life. Lipo-
study of a liposome indicates that its particle size is increasing, 0
the emulsion may become unstable and lose efficacy. One such cn
study over a 3-week period is shown in Figure 7. As you can 0
see, each weeks differential and cumulative volume traces
closely match those for the other weeks. This indicates the me-
dian particle size didnt increase during the three weeks, which
suggests the material has long-term stability.
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Such studies of particle size stability are also important for 0
other drugs, such as progesterone for veterinary applications.
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For this drug, a stable particle size is particularly important be- %
cause the drug is injected and must pass through the animals P,
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system without blocking capillaries. Blocked capillaries could Q
cause blood starvation and eventual tissue death. m
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Like pharmaceutical suspensions, many foods are suspensions
of oil mixed with water. Such emulsions contain nanosized par-
ticles and must be stable to maintain the foods aesthetic ap-

Measuring six sizes of diamond dust

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Powder and Bulk Engineering, February 1995 45 73
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Measuringa liposome over three weeks cn
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Particle size (microns]

I I 1
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Particle size (nanometers]

pearance, texture, and flavor response. Accurately measuring
the emulsions size distributiondetermines whether the mixture
is homogeneous, which is critical to ensuring the foods stabil-
PBE
ity, flavor profile, and shelf-life.
2. Microtrac Ultrafine Particle Analyzer (WA), Leeds+Northrup, St. Petersburg,
F1a.
3. Data from tests conducted at Leeds+Northrup, St. Petersburg, Fla., with the
companys Microtrac UPA, which uses the controlled reference method. Figure
3 provides results of tests using photon correlation spectroscopy, as well.

Editors note
For more information and additional dynamic light-scattering
test results, contact the authors.
References
1. E.L. Weiss and H.N. Frock, Rapid analysis of particle size distributions by
laser light scattering,Powder Technology, Vol. 14, 1976, pages 287-293.
Philip E. Plantz is manager of theparticle size technology lab-
oratory at Leeds+Northrup (a unit of General Signal), 3000
Old Roosevelt Boulevard, St. Petersburg, FL 33716; 813/573-
4073. He holds a PhD in biochemistry and food science from
Pennsylvania State University in State College, Pa. Paul J.
Freud is principal scientist at Leeds+Northrup, 795 Horsham
Road, Horsham, PA 19044; 215/442-8000. He holds a phD in
physicsfrom Rutgers University in New Brunswick, N.J.