PARTICLE SIZE ANALYSIS

LabPlus international - November 2000 28

Laser diffraction for particle size analysis - why use Mie theory?
The most rigorous and comprehensive prediction of the light scattering behaviour of particles is embodied in Mie theory whose application requires a large amount of computing power When laser diffraction systems were introduced in the late 1970s, the lack of readily available computing power meant that widespread use of Mie theory was limited and the less- demanding Fraunhofer approximation used instead. With the current plethora of powerful and cheap PC's there is no longer any good reason for the adoption of the Fraunhofer approximation.
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Introduction The recent publication of ISO 13320, a new international standard relating to particle size analysis by laser diffraction, has been a welcome advance. Laser diffraction methods have been around for many years, but the development of this standard demonstrates that the technique is now a fully accepted and mature technology. One of the key recommendations in the new standard is the choice of the correct optical model for the material being measured, in order to ensure reliable particle size measurement. Laser diffraction operates as a sizing technique by predicting the light scattering behaviour of particles, and the quality of this prediction determines the accuracy of the size determination performed. The most rigorous and comprehensive prediction of the light scattering behaviour of particles is embodied in Mie theory. H o w e v e r, w h e n l a s e r d i f f r a c t i o n instruments were first introduced in the late 1970s, computer power was at a premium and the first PCs were limited to 8K of RAM. Since at the time the use of Mie theory demanded a considerable amount of computing power, manufacturers used an approximation comprehensive prediction of the light scattering behaviour of particles is embodied in Mie theory. However, when laser diffraction instruments were first introduced in the late 1970s, computer power was at a premium and the first PCs were limited to 8K of RAM. Since at the time the use of Mie theory demanded a considerable amount of computing power, manufacturers used an approximation of Mie theory known as the Fraunhofer approximation. Now that the average PC has a Pentium and 32 Megabytes of RAM, there is no longer any good reason for its continued adoption. The new ISO standard states that although Fraunhofer can still be used for the measurement of particles greater than 50 m, Mie theory is recommended for those below 50m and it is applicable across the full measurement range. Instruments designed to measure in the size range

below 50m should therefore uniformly support Mie theory. In the past, the need to input the refractive indices of the materials being measured may have deterred some people from using Mie theory. To simplify this procedure the Malvern Instruments Mastersizer 2000, for example, has a database containing the refractive indices of most common materials, making the implementation of Mie theory very straightforward. The advances in computer power referred to above make its adoption transparent to the user. Practical applications The examples that follow demonstrate why the use of Mie theory is so important. Example 1 The sample is a synthetic diamond powder that has been fractionated in such a way as to have a limited size distribution and a tight specification of median size. Such fractions are used in the grinding and polishing industries. The real part of the refractive index (R1) of synthetic diamond is well known and has a value of 2.41-0.0. The material is suspended in water (Refractive Index 1.31) The results of measuring this material applying both Fraunhofer and Mie theories are shown in Fig 1. Using the Fraunhofer approximation, the results indicate a bimodal distribution, but it is known from electron microscope evaluation that this is incorrect. The curve produced by the use of Mie theory, where the appropriate refractive index values were input into the software, provides the correct result. Again, this has been confirmed by detailed electron microscopy. Example 2 The second example is a measurement of calcium carbonate. This material is used as a filler that is laid down on the cellulose fibres in papermaking to give a smooth printing surface. The particle size distribution is important since the whiteness of the final paper surface is considerably enhanced by the increase in optical scattering efficiency (extinction) of the particles, which occurs within a particularly narrow particle size band. In

Fig. 1: Measurement of synthetic diamond powder using both Mie and Fraunhofer (example 1)

this instance, Fraunhofer interprets the size distribution as being too large, can be seen in Fig 2. This error stems from Fraunhofer being unable to predict the true extinction
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Fig. 2: Measurement of calcium carbonate using Mie and Fraunhofer (example 2)

behaviour of the particles. The Fraunhofer approximation assumes that the extinction efficiency of all sizes of particle is 2. In practice, for most commonly found materials, this approximation is only correct for particles greater than about 10 microns. In fact a graph of the scattering efficiency of calcium carbonate as a function of particle size shows that the scattering power actually falls off rapidly below 2 microns. The amount of light scattered from the 0.3-micron contribution for example is very small. Therefore, Fraunhofer assumes that there must be very little of this size present. Mie theory however predicts this fall off and therefore continues to weight the fine sizes correctly. Conclusions These examples demonstrate how Mie Theory correctly anticipates the effect on light scattering behaviour caused by differences in Refractive Index, the relative transparencies of particles and the extinction efficiencies of particles. The Fraunhofer approximation is unable to consider these variations and is thus is in error in each case described.
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