DRY POWDER METHOD DEVELOPMENT
FOR LASER DIFFRACTION PARTICLE SIZE
MEASUREMENTS
Particle size measurements of
materials in the dry dispersed
state are increasingly being used
as an alternative to wet or liquid
dispersion methods. There are
several advantages to using dry
powder dispersion for laser
diffraction measurements:
If a material is processed in the
dry state then measuring the
particle size in the same state may
be more representative than wet
dispersion.
For some materials dry
measurement may be the only
option, due to dissolution in
common dispersants or changes
in the size of the particles in wet
dispersion (due to hydration).
In general, measurements in dry dispersion are quicker than wet, enabling you to
measure a larger mass of material in a short time. This is particularly useful for
achieving reproducible results for coarse or polydisperse materials.
However, not every sample is suitable for dry dispersion. Very fine or cohesive
materials may be more suited to wet measurement, as surfactants and additives
may be required to achieve full and reproducible dispersion. Dry dispersion may not
be suitable for extremely fragile materials due to the more aggressive nature of the
dispersion mechanisms. Finally, while it is possible to measure very small sample
masses using a dry system, improved result reproducibility is often achieved using
wet dispersion.
Achieving reproducible results from any kind of particle characterization system
depends upon three factors:
 Representative sampling,
 The correct state of dispersion
 Appropriate measurement conditions.
The relative importance of each of these factors depends on the size of the particles
being measured. Figure 1 shows the relative risk factors associated with
measurements of fine or coarse particles in dry dispersion.
Figure 1: Risk factors for coarse and fine particles in dry dispersion
Therefore, if you are measuring fine particles then the air pressure will have the
greatest influence on the results as it affects the samples state of dispersion.
However, if you are measuring coarse particles, the greatest possible source of
error will be sub sampling of the material.
©2013 Malvern Instruments Limited MRK1903-01 1
Air pressure and dispersion
Achieving reproducible results from a particle size measurement relies on the sample being in a stable state of dispersion. The
ease with which particles can be dispersed depends on the particle size, as the relative forces of adhesion between particles
increase as the particle size decreases. This is why air pressure, and dispersion, is at the top of the list of risk factors for
measurements of fine particles.
Samples in the dry state are dispersed using a venturi driven by compressed air. For each venturi, the amount of energy
available to disperse the sample will depend on the pressure of the compressed air. The state of dispersion for a dry sample is
assessed by carrying out a pressure titration and comparing the results to a well dispersed wet measurement. A pressure
titration generally shows a decrease in particle size with increasing pressure as agglomerates are dispersed. However, the
particle size can also decrease due to particle attrition and these two processes can overlap. The results of a pressure titration
are compared to a well dispersed wet measurement to determine the pressure at which the agglomerates are dispersed but
the primary particles are not being broken. A pressure titration for a milk powder sample is shown in Figure 2.

Figure 2: Milk powder pressure titration, standard venturi.

The dry result showing the closest agreement to the well dispersed wet result will indicate the appropriate pressure. If the
results of a dry measurement are finer than the wet measurement this indicates that the primary particles are being broken at
that pressure. Figure 3 shows a dispersed wet result for the milk powder sample, compared to dry results measured at 0.5 bar
and 3 bar. The 0.5 bar measurement shows a larger size compared to the wet measurement, indicating that the sample is not
fully dispersed at 0.5 bar. However, the 3 bar measurement shows excellent comparability to the wet measurement. Therefore,
for this material the appropriate pressure to disperse the sample to its primary particle size is 3 bar.

Figure 3: Comparison of dispersed wet result and dry results at 0.5 bar and 3 bar

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The pressure titration shown in Figure 2 was carried out using the standard venturi supplied with the Mastersizer 3000 dry
powder disperser the Aero S. This venturi makes use of two of the mechanisms available for dry powder dispersion, as
shown in Figure 4: (a) velocity gradients caused by shear stress and (b) particle-to-particle collisions.

Figure 4: Dispersion mechanisms for dry powder dispersion

For the majority of materials these two mechanisms are sufficient to disperse the sample. However, some highly agglomerated
and robust samples may require the additional higher energy dispersion mechanism of particle-to-wall collisions, Figure 4 (c).
As the standard venturi is applicable to the vast majority of samples then this will be your starting point for developing a dry
method. However if full dispersion is not achieved for a robust material then the Aero’s high energy venturi , which makes use
of all three dispersion mechanisms, may be required.
If we measure the milk powder sample using the high energy venturi then we see a different pressure titration. Full dispersion
is achieved at a lower pressure, due to the higher energy dispersion mechanism. Figure 5 shows that the dry result at 1 bar
using the high energy venturi shows good agreement to wet result, whereas the dry result at 4 bar shows a smaller particle
size which indicates particle attrition.

Figure 5: Comparison of dispersed wet result and high energy venturi dry results at 1 bar and 4 bar

Figure 6 shows the Dv50 vs. pressure measured using both the standard venturi and high energy venturi, with the Dv50 from
the wet result added as a dashed line for comparison. This shows that results comparable to the wet measurement are
achieved at between 3 bar and 4 bar using the standard venturi and at 1 bar using the high energy venturi. In this case the
standard venturi would be recommended, as the dry results are comparable to the wet dispersion over a wider range of
pressure which improves the robustness of the method.

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 140

120

100
Size / m

80

60 Standard Dv50
High energy Dv50
Wet Dv50

40
0 1 2 3 4

Air pressure / bar

Figure 6: Dv50 vs. pressure using standard and high energy venturi compared to wet Dv50

Feed rate
The feed rate controls the rate at which material is fed through the venturi to the measurement cell by vibrating the sample
tray. The amount of material passing through the measurement cell is recorded via the obscuration (the percentage loss of
laser light through the measurement cell). The feed rate must be set so that the obscuration is in range for the majority of the
measurement duration, as illustrated in Figure 7. The obscuration filtering feature in the Mastersizer software ensures that
detector scans where the obscuration is outside the target range are not included in the results. The percentage of the
measurement duration where the obscuration was within range can be checked using the ‘Snap collection percentage’
parameter. The higher this percentage the more scans of the detector were within the obscuration range, and the more
representative and reproducible the results. This is one of the parameters checked by the Mastersizer 3000s data quality
report for dry measurements, which will show a warning when poor obscuration control is detected.

Figure 7: Variation in obscuration vs. time, showing good control of the feed rate in green, and poor control in red.

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The appropriate obscuration range will depend on the size and nature of the sample. Cohesive, fine samples may need to be
measured at a lower obscuration in order to maximize the efficiency of the disperser, whereas coarser materials can be
measured at a higher obscuration. If poor dispersion is observed for fine, or cohesive, materials then the upper obscuration
limit should be reduced to improve the efficiency of the disperser.
On the Aero S dispersion unit, the stability of the sample flow can be optimized by adjusting the set-up of the sample tray and
hopper. For free flowing materials a lower hopper height will prevent material flowing off the tray too quickly. For cohesive
materials an increased hopper height may improve flowability. The basket and ball bearing can also be used to improve the
flow of cohesive materials. If you only have a small amount of sample available then the hopper may not be necessary and the
Macro or Micro sample trays may be more suitable.

Sampling
If you are measuring coarse particles then amount of sample you measure and how you take the sub sample become the
largest possible source of error.
To get a representative result you need to measure a minimum number of particles. For example, to get the Dv90 to within a
5% standard error requires at least 400 particles to be measured during the analysis. Therefore, for a material with a density of
3
1.5g/cm and a Dv90 of 500μm you would need to measure about 0.5g to get the Dv90 to within a 5% standard error. As the
size of the particles increases the mass containing sufficient particles increases, and the minimum mass required to achieve
reproducible results also increases.

90
80
70
Minimum mass / g

60
50
40
30
20
10
0
0 500 1000 1500 2000 2500 3000
Dv90 /μm

Figure 8: Minimum mass for a 5% standard error vs. particle size.

Figure 1 shows the minimum mass required to achieve a 5% standard error as a function of particle size. You can test whether
your sample mass, or technique, is sufficient by measuring several separate sub samples and assessing the variability of the
results.

Measurement duration and robustness

The duration of the sample measurement can also affect the variability of results, as it can become another sampling step. As
the sample tray vibrates it is possible for a sample to become segregated. The larger, more free flowing, particles within a
sample may arrive at the measurement cell before the finer more cohesive particles. Therefore it is important, when making
dry measurement, to ensure that the entire sub sample put onto the tray is measured. During method development it can be
useful to make repeat measurements of shorter duration in order to help optimize parameters, such as the obscuration range.
However, once the measurement conditions have been defined a long measurement, with sufficient duration to measure all of
the material on the tray, should be set.
The mass of the sub sample required to achieve reproducible results will depend on the size and polydispersity of the sample.
Samples containing larger particles or with very polydisperse distributions will require a larger mass of material to be measured
and, therefore, a longer measurement duration.

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Figure 9: Size distributions for repeat 5s measurements of a coarse sample, showing higher variability

For example, Figure 9 shows several 5 second measurements of a sample with a median size of approximately 600μm. The
relative standard deviation of the percentiles shows quite a high variability which can be improved by increasing the
measurement duration and thereby improving the sampling of the material.
For finer, or monodisperse, samples it is possible to measure a very small mass of sample and still get representative results.
Figure 10 shows the results of dry measurements of a baby powder sample from a sub samples with masses between 50mg
and 5mg. The table in Figure 10 contains the resulting percentiles and relative standard deviations which show reproducibility
well within the expected repeatability for a laser diffraction measurement, according to the ISO standard [1].

Figure 10: Size distributions and variability for baby powder samples from 50mg to 5mg.

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Conclusions
Getting reproducible results from dry laser diffraction measurements is dependent on three main factors: taking a
representative sample of the bulk material, using the correct pressure to disperse the sample and setting appropriate
measurement conditions. The relative importance of each of these factors will depend on the particle size of the sample that
you are measuring. For fine particles achieving a reproducible state of dispersion will be the most important factor. Whereas
for coarse particles ensuring that a sufficient mass of material is measured will be the most important factor.
In this application note we have covered the process of setting up a method for dry laser diffraction measurements. We have
also covered some tests that you can carry out to assess the reproducibility and robustness of your method. By following this
process you will be able to increase your understanding of the materials that you measure, and improve the reproducibility of
your particle size results.

References
[1] ISO13320 (2009). Particle Size Analysis - Laser Diffraction Methods, Part 1: General Principles

Measurement precision
The precision of laser diffraction measurements can be assessed using the coefficient of variation.

%
(also referred to as the relative standard deviation)
The ISO standard for laser diffraction [1] recommends that the %COV should be less than 3% for central parameters such
as the Dv50, and less than 5% for parameters at the extremes of the distribution such as the Dv10 and Dv90. The
Mastersizer 3000 has a variability check in its data quality tab to allow you to check the variability of your measurements
against the limits set in the ISO standard.

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