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Selecting In-Process
Particle-Size Analyzers
Paul Barrett,
Lasentec, Inc.,
A Mettler Toledo Company
In-process particle
analysis is key to optimizing
particulate processes and
improving product quality
and performance.
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Increase in
number of fine particles
No change in
number of
coarse particles
Counts, #
100
10
1,000
Dimension, m
Counts, %
Increase in
number of fine particles
Apparent loss
in number of
coarse particles
10
100
1,000
Dimension, m
material has decreased, while the amount of fines has increased (Figure 1b). This is purely a function of the normalization, but without the number-based data, one could easily
draw the wrong conclusion.
Particle-sizing tools
Today, there is an extensive base of commercially available sizing equipment. Perhaps the most common and simplistic of these tools are sieves. With the emergence of computers and ever-improving electronics, several laboratorybased sizing techniques have come to the forefront. Today,
the two most popular offline particle-sizing techniques are
laser diffraction and electrosensing-zone methodology.
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Solids Processing/Analysis
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Laser diffraction instruments are designed for offline particle-size measurement of solids or liquids suspended in another phase (i.e., a solid particle suspended in a liquid, a liquid suspended in another liquid, or a solid particle suspended
in air). These instruments use a light-scattering phenomenon,
coupled with mathematical algorithms, to calculate the volume-based particle-size distribution. The sizes of the particles, regardless of their shape, are typically reported as a volume-based distribution of spherical particles. This reported
distribution has a diffraction pattern similar to that of the
measured sample and ranges from 0.05 m to 2,000 m.
Diffraction involves a change in direction of the light
waves as they pass around an obstacle, in this case, a particle
in their pathway. The angles at which particles diffract light
are related to their sizes. For instance, if the particles are
spherical, large particles will scatter light at narrow angles,
and small particles will scatter light at wide angles.
In contrast to diffraction, the electrosensing-zone technique provides a number-based distribution. In the instrument, the particles are suspended in a weak electrolyte and
drawn through a small aperture. The width of the aperture is
sized for the particle sample in question, but can range from
0.4 m to 1,200 m. Current flows between the two electrodes located on either side of this aperture, creating what is
termed an electrosensing zone. As particles pass through
this charged aperture, their presence produces a current that
is proportional to their size. In this manner, the electrosensing-zone technique counts each particle.
The popularity of these instruments for laboratory-based
sample analysis is countered by their less-useful role in particle systems where knowledge of the rate or particle-system
dynamics are desired. Many attempts have been made to utilize offline tools for the characterization of high-concentration, dynamic particle systems that occur in industry. However, offline tools can only do so much.
It is often difficult, and sometimes hazardous, to take a
sample from an elevated-solids-concentration process (either
laboratory or production scale). A primary concern is whether
that slurry sample is representative of the process as a whole.
There have been several studies highlighting the impact of
sampling on the reliability of particle-size measurement (2).
Particles can change after they have been taken from the process, but before they are actually measured offline.
For instance, changes in temperature or pressure could
alter the particle system, thereby impacting how particles interact; fine particles could dissolve or aggregate. A typical example of this would be a crystallization process where, after
taking a sample, a temperature change causes additional crystal growth. Furthermore, most offline sizing techniques require low solids concentrations (typically, less than 2% by
wt., depending on the size and shape of particles), often demanding that the sample be diluted. Dilution can again
change the particle sample, rendering it non-representative of
what is occurring in the process. Sometimes, the samples are
filtered and dried in order to prepare them for measurement.
300
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m
Figures 2a and 2b. These images are taken in-process using a particle
vision and measurement (PVM) analyzer equipped with an in-process
video microscope. Images taken during a flocculation process indicate that
a large number of fine particles agglomerate to form a large particle (a).
Well-formed single hexagonal platelets can crystallize in a variety of forms
forms, depending on the solvent, the nature of the solute and
crystallization conditions (b).
The result is a poor portrayal of what actually occurred in the
elevated-concentration conditions of the production process.
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Figure 2c and 2d. This image of paper fibers was taken in-process.
Papermaking is a complex process where interaction between the fibers
and fillers is extremely important (c). This crystal exhibits dendritic growth
that would be difficult to characterize offline, as crystals would break
apart in sample handling (d).
shown in Figures 2a2d, particles often exist in-process as irregularly shaped entities. But how do particles that are not
spherical affect measurement results?
Consider the simple sieve. Sieving will size a particle
based on its second largest dimension (2). Envision a 100m-dia. sphere vs. a 100-m-dia. 400-m long cylinder.
Although the rod has the greater mass, they will both fall
through the same size sieve aperture. The sieve data will be
incorrect if one does not account for shape. This example can
be extended to the majority of sizing techniques.
Most sizing instruments, including the Coulter counter
used during electrosensing, report an SED. However, regardless of the shape of the material under investigation,
most instruments assume that the measured signal comes
from a spherical particle, and in turn derive an SED based
on this assumption. The spherical assumption works fine if
the particles have a spherical shape, but the further a shape
moves away from a sphere, the worse this assumption becomes and the further the reported diameter is from the true
SED (Figure 3).
In fact, the algorithms that drive laser diffraction and
electrosensing-zone techniques do not account for particle
shape. A recent publication from a laser-diffraction instrument manufacturer highlights the limitations of these instruments when non-spherical particles are being measured (3).
Cases are cited in which laser diffraction and the electrosensing-zone techniques both failed to report the true
SED for particles ranging from boulder-shaped particles to
needle-like particles.
At this point, there are no successful correction factors in
commercial software (excluding some image-analysis packages) that account for non-spherical shapes. Most will generally track growth or reduction of shaped particles, but not in
an absolute sense.
The suitability of the SED should be judged bearing in
mind this sensitivity to shape. In addition, for non-spherical
particles, even if a true SED could be measured, it is of little
use this sphere will not represent the surface area of the
non-spherical particle, and it will not have the same flow or
handling characteristics of the non-spherical particle.
Imaging offers the ability to quantify particle shape and to
plot distributions of shape and dimension. Many laboratorybased imaging systems are available, from the simple microscope to automated image-analysis systems. However, when
it comes to sample size, imaging is at a disadvantage. A significant number of particles have to be measured to generate
a robust sample, which can be time consuming. Other shortcomings of imaging include low-end resolution and sensitivity to slight changes in dimension.
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Solids Processing/Analysis
10 m
300
100 m
Calculate diameter of
sphere with same
volume as "needle"
SED = 25.6 m
Dimension, m
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LD Volume-based mean
FBRM Volume-based mean
PVM Analysis
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research firm Frost and Sullivan (San Jose, CA; www.chemicals.frost.com) says that the in-process particle-characterization market is dominated by FBRM and PVM.
phase), viscosity (for the liquid phase) and intrinsic attenuUltrasonics Ultrasonic techniques are split into two
ation. In a dynamic particle system, it can be difficult to
areas: acoustic spectroscopy and electroacoustic speccollect this information. Furthermore, the information can
troscopy. Acoustic spectroscopy is based on the scatterchange over time, making the acoustical techniques diffiing theory, which uses the fundamental equations of mass,
cult to implement.
momentum and energy to describe the
interaction between an ultrasonic wave
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and a suspended particle. The interaction
Little change in volume-based mean
of a particle and wave. also depends on
=> Little change in course materials
the frequency of the wave and the size of
the particle. Therefore, if the fundamen60
tal equations and frequency are known,
Number-based median
the size of the particle can be deterVolume-based mean
mined. On the other hand, electroacoustic techniques use electric impulses to
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stimulate the particles, which then proDrop in number-based median
duce sound waves that are proportional
=> More fine material
to the particle size.
Characterized by a wide measurement
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range, ultrasonic techniques can measure
submicron-sized particles, and in some
cases, be implemented non-invasively.
0
Limitations include the fact that the mea800
0
400
600
200
surement is volume-based, and the partiTime, s
cle is assumed to be spherical. In addition, ultrasonic techniques typically require intricate knowledge about physical Figure 5. In characterizing a particle system, it is important to select the appropriate statistic to
track a change. Here, attrition is tracked with FBRM, revealing an increase in fine particles, but little
properties of the medium being mea- change in the number of large particles. The number-based median drops over time, indicating that
sured, including thermal conductivity, the number of fines has increased. Meanwhile, the volume-based mean is relatively
thermal dilation/expansion, heat capaci- stationary, indicating that this attrition is not breaking the large particles, but rather taking small
ty, shear rigidity/modulus (for the solid chips off their surfaces.
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Counts, #/s
Counts, #/s
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Solids Processing/Analysis
In-process monitoring
Attrition A simple example of the FBRM is shown in
a particle system undergoing attrition (Figure 5). Large
particles are stirred for 10 min. Over time, the distribution
Literature Cited
1. Mota, M., et al., Interference of Coarse and Fine Particles of Different Shape in Mixed Porous Beds and Filter Cakes, Minerals Engineering, 16 (2), pp. 135144 (Feb. 2003).
2. Allen, T., Particle Size Measurement, 4th Ed., Chapman and Hall,
London (1990).
3. Xu, R. and O. A. D. Guida, Particle Size and Particle Count Using
Light Scattering, Coulter Principle, and Image Analysis, World
Congress on Particle Technology 4, Sydney, AU, pp. 2125 (July
2002).
4. Barrett, P. and B. Glennon, In-line FBRM Monitoring of Particle
Size in Dilute Agitated Suspensions, Particle and Particle System
Characterization, 16, pp. 207211 (1999).
5. Dunham, A. J., et al., Effects of Dissolved and Colloidal Substances on Flocculation of Mechanical Pulps, Journal of Pulp and
Paper Science, 26 (3), pp. 95101 (2000).
6. Glennon, B., et al., In-Line Monitoring of Biological Systems
Using FBRM, Lasentec Users Forum, Charleston, NC (Feb. 24
27, 2002).
7. Owen, T., et al., The Impact of Polyacrylamide Flocculant Solution
Age on Flocculation Performance, International Journal of Mineral Processing, 67 (14), pp. 123144 (Nov. 2002).
8. Dowding, P. J., et al., Factors Governing Emulsion Droplet and
Solid Particle Size Measurements Performed Using the Focused
Beam Reflectance Technique, Colloids and Surfaces A.: Physicochemical and Engineering Aspects, 192 (13), pp. 513 (Nov. 2001).
9. Barrett, P., and B. Glennon, Characterizing the Metastable Zone
Width and Solubility Curve Using Lasentec FBRM and PVM,
Trans. IChemE, 80 (A), pp. 799805 (Oct. 2002).
10. Ruf, A., et al., Modelling and Experimental Analysis of PSD Measurements Through FBRM, Particle and Particle System Characterization, 17, pp. 167179 (2000).
11. Saranteas, K., Micromixing and Mesomixing Effects on Nucleation,
Agglomeration and De-Agglomeration Kinetics in a Dye Precipitation, Lasentec Users Forum, Orlando, FL (Feb. 28 Mar. 1, 2000).
12. Johnson, B. K., et al., Optimization of Pharmaceutical Batch
Crystallization for Filtration and Scale-Up, American Institute of
Chemical Engineers Annual Meeting, Los Angeles, CA (Nov.
1621, 1997).
13. Fitzsimons, P., Use of Lasentec FBRM in the Regulatory Environment of Bulk API Production, Lasentec Users Forum, New York,
NY (Feb. 2426, 2003).
14. Scott, D. M., et al., In Line Particle Characterization, Particle and
Particle System Characterization, 15, pp. 4750 (1998).
15. Daymo, E. A., et al., Acceptance Testing of the Lasentec Focused
Beam Reflectance Measurement (FBRM) Monitor for Slurry Transfer Applications at Hanford and Oak Ridge, Proceedings of SPIE
The International Society for Optical Engineering, 3536, pp.
8292 (1999).
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of fine particles increases, but the number of coarse particles does not change dramatically. The number-based median decreases over time, but the volume-based statistic remains constant. In this case, using the number-based mean
or the particle count on the fine side of the distribution
would be the appropriate to track this attrition event.
Flocculation To track flocculation in-process, one
needs to examine both sides of the distribution. Initially,
one starts with a high number of small particles, which aggregate through the addition of a flocculation agent (Figure
6a). As a result, the number of fines decreases and the
number of coarse particles increases (Figure 6b). Tracking
a flocculation process in this manner enables one to optimize the amount of flocculent to add, while assessing the
impact of essential process variables, such as agitation, on
the flocculated particles.
Opaque solutions Perhaps one of the greatest challenges
of in-process particle characterization is measurement in challenging process conditions high temperature or pressure, radioactivity (15) or opaque slurries. The use of FBRM for the
characterization of asphaltenes indicates that the naphtha to bitumen ratio has a marked effect on the rate and degree of asphaltenes precipitation and subsequent aggregation. Changes
in temperature, pressure and chemical composition may cause
asphaltenes to precipitate out of crude oil. Consequently, significant difficulties may arise in the production, transportation
and processing of crude oil. For example, precipitation and deposition inside an oil well may partially or completely block
the reservoir, thus damaging the reservoir and thwarting crudeoil recovery; or foul production lines and poison refinery catalysts. The economic impacts of these problems are tremendous. Yet, some of the most fundamental properties and behaviors of asphaltenes remain unresolved. In-process characterization sheds light on the crystallization process and its essential
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process variables.
PAUL BARRETT is the director of applications for Lasentec, Inc. (15224 NE 95th
St.; Redmond, WA 98052; Phone: (425) 881-7117; Fax: (425) 881-8964;
E-mail: paulb@lasentec.com). He is responsible for the implementation of
Lasentecs in-process particle characterization technologies in a variety of
particulate processes. Barrett joined Mettler Toldo Lasentec in 2000 as a
crystallization specialist. He has earned BE and PhD degrees in chemical
engineering from Univ. College in Dublin, Ireland.