Light scattering

and nanoparticles
Metal oxide nanoparticles are finding increasing application in the
preparation of new nanocrystalline materials, with metal oxide
composites being used to confer new electronic, magnetic and
optical properties into material structures. Often these materials are
formulated and processed as slurries or aqueous suspensions. One key
parameter in controlling the properties of such colloidal nanoparticle
systems is their particle size. Light scattering techniques are widely
used for its determination.

Ulf Nobbmann and Ana Morfesis

Malvern Instruments Ltd, Enigma Business Park, Grovewood Road, Malvern, Worcestershire, WR14 1XZ, UK
www.malvern.com

Comparing results from different methods must be approached
with caution: particle size distributions reported in terms of
volume, number or scattering intensity usually produce vastly
differing results, despite the data having been derived from exactly
the same physical material. Alongside particle size, another
fundamental colloidal characteristic is zeta potential, which can
also be measured rapidly using light scattering techniques. This
effectively quantifies the parameter controlling electrostatic
stabilization, and can be used in formulation development to avoid
the instability that can result from particle-particle attraction.
The potential uses for metal oxide nanoparticles are often size
dependent. For example, the UV absorption power of TiO2 particles1
or the use of iron oxide as contrast agents for magnetic resonance
imaging (MRI) scans2 are a function of their particle size. Rather than
a single size, most ‘real world’ samples contain a range of sizes, and
the challenge is to characterize and understand the effects of this
size distribution on the application in question. When selecting a size
measurement technique, it is important to appreciate that for non-
spherical materials containing a range of particle sizes, the likelihood
is that each will produce different results. We seek to explain why
this is the case using the following example of a TiO2 dispersion.
Experiment
TiO2 was obtained from Nanophase Technology Corporation, prepared
in Di-H2O adjusted to pH 3.1 at a concentration of 0.01 wt% and
sonicated in a bath for 30 sec. The sample serves as a model system
for metal oxides and was chosen here because of its availability and
ease of use. The sample labelled “Nanotek” was filtered through a
Whatman Anodisk filter (Whatman plc, Maidstone, UK) with pore size
of 0.2 μm to remove undispersed aggregates.
Size measurements were performed using dynamic light scattering
(DLS) on a Malvern Zetasizer Nano-ZS (Malvern Instruments,
Malvern, UK). Samples were irradiated with red light (HeNe laser,

52 MAY 2009 | VOLUME 12 | NUMBER 5 ISSN:1369 7021 © Elsevier Ltd 2009

 Light scattering and nanoparticles APPLICATIONS

Size Distribution by Intensity

20

15
Intensity (%)

10

0
0.1 1 10 100 1000 10000
Size (nm)

Record 47: TiO2 Nanotek, pH3, 1 Record 48: TiO2 Nanotek, pH3, 2
Record 49: TiO2 Nanotek, pH3, 3

Fig. 1 The intensity size distribution of Nanotek TiO2 versus particle diameter in nanometers is characterized by a peak mean of 85.6 nm. The different colors represent
repeat measurements of the same sample.

wavelength λ = 632.8 nm) and the intensity fluctuations of the
scattered light (detected at a backscattering angle of 173°) analyzed
to obtain an autocorrelation function. The software (DTS v5.03)
provided both the size mean and polydispersity, using the cumulants
analysis (according to the international standard ISO 13321:19963)
and a size distribution using a regularization scheme by intensity,
volume, and number.
The following assumptions were made in the analysis: the solution
viscosity was assumed to be that of water, corrected for temperature
(η = 0.888 mPa.s); the solution refractive index was that of
water (n = 1.33); the refractive index of the particle was selected to
be nR = 2.4 with an absorption of nI = 0.01. Samples were measured
in disposable polystyrene cuvettes at a temperature of 25°C, and
this temperature was actively maintained within 0.1°C in the sample
chamber. Data were acquired in automatic mode, ensuring enough
photons were accumulated for the result to be statistically relevant.
The software incorporated a ‘data quality report’ that indicated good
quality for all data obtained.
Discussion
The sample gave an overall z-average size of 76.9 nm with a
polydispersity index of 0.10 indicating that the distribution
consisted of a single size mode without aggregates. The result
is an intensity-weighed value and will therefore be sensitive to
any larger size species in the sample. This may be particularly
significant for aggregated or contaminated samples, but is also
of interest for broad, polydisperse non-homogeneous samples.
As a comparison, the polystyrene beads used for size standards
have typical polydispersity index values below 0.05. In order to
understand the sample more completely it can be instructive to
look at the details of the size distribution, to indicate whether a
non-homogeneous sample is a single broad mode or a number
of modes. The direct output is a distribution by intensity, that is
the area of each of the modes is related to the intensity of light
scattered. Mathematically, the intensity distribution may be
rescaled using Mie4 theory to transform the result into a volume
and a number distribution.
Intensity distribution
Figure 1 displays the intensity distribution produced by a typical
algorithm. Here, the contributions in terms of % intensity are shown
as a function of particle diameter. For an ideal monodisperse sample,
the peak in the intensity distribution is expected to be very close
to the z-average size from the cumulant fit. Here, we see a different
situation. As a consequence of the polydispersity of the sample,
the mean size of the peak by intensity is slightly different from the
cumulant size. The mean of three repeat measurements reveals an
intensity peak mean value of 85.6 nm.

MAY 2009 | VOLUME 12 | NUMBER 5 53

APPLICATIONS Light scattering and nanoparticles
Size Distribution by Number
30
Number (%)
20
10
0
0.1 1 10
Size (nm)
Record 47: TiO2 Nanotek, pH3, 1
Record 49: TiO2 Nanotek, pH3, 3
Fig. 2 The number size distribution of Nanotek TiO2 versus particle diameter in nanometers is characterized by a peak mean of 51.9 nm. The different colors represent
repeat measurements of the same sample.
Volume and number distributions
Using Mie theory it is possible to convert the size distribution by
intensity into a size distribution by mass or number. Mie theory
requires information about the optical properties of the dispersing
medium and the dispersed phase (both the real and imaginary part
of the refractive index) sometimes called the absorption, to do this
transformation. The effect is that for particles below about 100 nm,
the volume and number means are smaller than the intensity mean.
Above this size, the change in the mean size reported will depend on
the relative proportions of the different sizes in the distribution. This
is demonstrated in this case where the volume mean for the Nanotek
TiO2 is 65.6 nm. When this light scattering result is compared with
other volume based detection techniques (for example ultraviolet
UV or refractive index RI detection in conjunction with size exclusion
chromatography) it is important to use the volume size distribution
for the comparison.
In a similar way to the transformation from intensity to volume,
it is possible to calculate the result as a number distribution. Here,
the number of particles is displayed as a function of the particle
REFERENCES
1. Morfesis, A., and Fairhurst, D., Nanotech (2005) 1, 800.
2. Chouly, C., et al., J. Microencapsul. (1996) 13(3), 245.
54 MAY 2009 | VOLUME 12 | NUMBER 5
100 1000 10000
Record 48: TiO2 Nanotek, pH3, 2
size. Again, Mie theory is used to perform the rescaling, and thus
the correct material properties (refractive index and absorption) are
needed for accurate results. As displayed in figure 2 the mean size is
significantly smaller, in this case 51.9 nm. Number based metrologies
are typically microscopy techniques, where particle images are
counted and sorted into size bins. Again, when comparing size
results obtained with, for example electron microscopy, it must be
noted that the corresponding size distribution for comparison is the
number distribution.
Conclusions
Using a sample of TiO2 we showed the difference between intensity,
volume, and number distributions. Using the same material, the
size given by an intensity based technique may differ by a factor
two when compared with a number based technique. Neither of
these results is inherently the ‘right’ or ’correct’, but they indicate
why it is important to be clear about the technique being used
and the actual size parameter that is reported when referring to ‘a’
particle size.
3. ISO13321:1996 Particle size analysis – Photon correlation spectroscopy,
International Organization for Standardization (1996).
4. Mie, G., Annalen der Physik (1908) 330(3), 377.