Introduction to Particle Size Analysis

Ian Treviranus
[email protected]
www.horiba.com/us/particle

© 2013HORIBA, Ltd. All rights reserved.

What we’ll talk about
 Featured technologies

 Defining particle size

 Understanding size metrics

 Differences between techniques

 Q&A

© 2013 HORIBA, Ltd. All rights reserved.

Featured technologies
LA-950
Laser Diffraction

SZ-100
Dynamic Light Scattering & Zeta Potential

CAMSIZER & CAMSIZER XT

Dynamic Image Analysis

PSA300
Static Image Analysis

SA-9600
Flowing Gas BET Surface Area

© 2013 HORIBA, Ltd. All rights reserved.

LA-950: Laser Diffraction
Particle size performance leader
Ninth generation
Ultra durable
Lowest total cost of ownership
Suspension, emulsion, powder,
paste, gel
10 nanometer – 3 mm

© 2013 HORIBA, Ltd. All rights reserved.

SZ-100: Dynamic Light Scattering
Particle size: 0.3 nm – 8 µm
Zeta potential: -200 – +200 mV
Molecular weight: 1x103 – 2x107 Da
Patented ultra long-life
graphite electrodes
Lowest total cost of
ownership
Optional autotitrator

© 2013 HORIBA, Ltd. All rights reserved.

Image Analysis
Dynamic: Static:
particles flow past camera particles fixed on slide,
stage moves slide

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CAMSIZER Series
High resolution size & shape
Intelligent sieve correlation
Patented dual capture
CAMSIZER
30 µm – 30 mm
Free-flowing powders
CAMSIZER XT
1 µm – 3 mm
Cohesive or free flowing

© 2013 HORIBA, Ltd. All rights reserved.

PSA300
High resolution size & shape
Referee technique for micronized powders
Turnkey, automated image analysis
1 µm – 1,000 µm
Cohesive or free flowing
powders
Optional Powder
Disperser accessory

© 2013 HORIBA, Ltd. All rights reserved.

More Information
 Best Practices/Training
 Understanding Laser Diffraction PSA Results TR008
 Troubleshooting Laser Diffraction Data TR010
 Understanding Dynamic Light Scattering Results TR012
 Help! How Can I Trust My Size Results? TR015
 Refractive index selection, sampling, dispersion, system
verification, method development and more
 Technology
 Intro to CAMSIZER TE002
 Find the Best Analyzer for Your Application TE006
 Intro to Static Image Analysis TE008
 Intro to Dynamic Image Analysis TE009
 Intro to Laser Diffraction TE010
 Intro to Dynamic Light Scattering TE012
 Intro to CAMSIZER XT TE015
© 2013 HORIBA, Ltd. All rights reserved.
Who Cares About Particle Size?

 Minerals Grinding 10
Pharmaceutical
 Portland Cement 5 25
Chemical

 Glass Beads 5 Ceramics

Cement

 Abrasives 5 Food
Abrasives

 Foods 5 Cosmetics
Mining

 Cosmetics 5 Powder Metals

University
 Pharmaceuticals 5
5
25
Other

5
 Paint and Coatings
 Metals and Ceramics
 Explosives and Fireworks

© 2013 HORIBA, Ltd. All rights reserved.

What we’ll talk about
 Featured technologies

 Defining particle size

 Understanding size metrics

 Differences between techniques

 Q&A

© 2013 HORIBA, Ltd. All rights reserved.

Size Terminology
0.1µm 1.0µm 10µm 100µm

10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 10-0
100 nm

nanometer micrometer millimeter meter

nm Micron or µm mm m

Angstrom
(Å)

The most common designation is micrometers or

microns. When very small, in colloid region,
measured in nanometers, with electron
microscopes or by dynamic light scattering.

© 2013 HORIBA, Ltd. All rights reserved.

 Poll!

Which size ranges do you measure?

© 2013HORIBA, Ltd. All rights reserved.

 Particle Diameter (m)
0.01 0.1 1 10 100 1000

Ultrafine Fine Coarse

Size Ranges
Inhalable

Tobacco Smoke Spores Beach Sand

Relative Size
of Common Viruses Bacteria
Material
Carbon Black Paint Pigment Human Hair

Electron Microscope
Optical Microscope

Common Static Angular Light Scattering

Methods Dynamic Light Scattering
for Particle Electrozone Sensing
Size Analysis
Sedimentation Methods
Field Flow Fractionation Light Obscuration
Ultrasonic Spectroscopy

© 2013 HORIBA, Ltd. All rights reserved.

The Basics

Which is the most meaningful size?

different different
size definitions results

© 2013 HORIBA, Ltd. All rights reserved.

The Basics

What sizes can be measured?

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Size Definitions
 Martins’s Diameter: The distance between opposite
sides of a particle measured on a line bisecting the
projected area. To ensure statistical significance all
measurements are made in the same direction
regardless of particle orientation. Equivalent Spherical
 Feret’s Diameter: The distance between parallel Diameter
tangents on opposite sides of the particle profile.
Again to insure statistical significance, all
measurements are made in the same direction
regardless of particle orientation. Martin’s
Diameter
 Note: Both Martin’s and Feret’s diameters are
generally used for particle size analysis by optical and
electron microscopy.
 Equivalent Circle Diameter: The diameter of a circle
having an area equal to the projected area of the
particle in random orientation. This diameter is usually
determined subjectively and measured by oracular
micrometers called graticules.
 Equivalent Spherical Diameter: The diameter of a
sphere that has the same volume as the irregular Feret’s Diameter
particle being examined.

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Particle Orientation

Equivalent Spherical
Equivalent Spherical
Diameter
 Martin’s and Diameter
Martin’s
Feret’s Diameter’s Diameter
will vary as
Martin’s particles are
Diameter
viewed in different
orientations. The
result will be a
DISTRIBUTION
from smallest to
largest.
Feret’s Diameter Feret’s Diameter

© 2013 HORIBA, Ltd. All rights reserved.

The Basics
Particle Particle Distribution

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The Basics
Particle Size Particle Size Distribution

4 µm

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 Monodisperse vs. Polydisperse

Monodisperse Polydisperse
VOLUME

VOLUME
Particle Size Particle Size

 Monodisperse Distribution:  Wide Distribution:

 All particles are the same size  Particles of Many Sizes
 Latex standards  Everything else

© 2013 HORIBA, Ltd. All rights reserved.

 Logarithmic vs. Linear Scale
 Logarithmic X-Axis  Linear X-Axis
Distribution Distribution
VOLUME

VOLUME

0 10 100 0 10 20 30 40 50 60 70 80 90 100
Particle Size Particle Size

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Distribution Display

Cumulative Distribution
Histogram
VOLUME

Differential
Distribution

Particle Size
 Represented by series of segments or channels known as
histogram.
 Number of channels based on design, practicality and
aesthetics

© 2013 HORIBA, Ltd. All rights reserved.

Your Analyzer’s Displays

Frequency Frequency + cumulative (undersize)

Histogram Multiple frequency + cumulative (undersize)

© 2013 HORIBA, Ltd. All rights reserved.

What we’ll talk about
 Featured technologies

 Defining particle size

 Understanding size metrics

 Differences between techniques

 Q&A

© 2013 HORIBA, Ltd. All rights reserved.

Central Values

Mean
Weighted Average Mean
Center of Gravity Median
and
Mode
Median
50% Point

Mode
Peak of the distribution
Most common value

Size

© 2013 HORIBA, Ltd. All rights reserved.

What does “Mean” mean?
Three spheres of diameters 1,2,3 units

1
2
3

What is the average size of these spheres?

Average size = (1+2+3) ÷ 3 =2.00
This is called the D[1,0] - the number mean

© 2013 HORIBA, Ltd. All rights reserved.

Many possible Mean values
1 2  3
X nl  D[1,0]   2.00
3
1 4  9 None of the answers
X ns  D[ 2,0]   2.16
3 are wrong they have just
been calculated using
1  8  27 different techniques
X nv  D[ 3,0]  3  2.29
3

1  8  27
X sv  D[ 3,2]   2.57
1 2  3

1  16  81
X vm  D[ 4,3]   2.72
1  8  27

© 2013 HORIBA, Ltd. All rights reserved.

Volume-based Mean diameter
D[4,3] which is often referred to as the Volume Mean Diameter [ VMD ]

D [4,3] =
D n 4
i i

D n 3
i i

Monitoring the D[4,3] value in your specification

will emphasize the detection of large particles

© 2013 HORIBA, Ltd. All rights reserved.

Central Values revisited
Mean
Weighted Average
Mode
Center of Gravity
Median

Mean Median
50% Point
D[4,3]

Mode
Peak of the distribution
Most common value

Size

Remember: D[4,3] is sensitive to large particles

© 2013 HORIBA, Ltd. All rights reserved.

 Most Common Statistics
half are smaller than this diameter half are larger than this diameter
D(v,0.5)
median

10% of the particles lie 90% of the particles lie

below this diameter below this diameter
D(v,0.1) D(v,0.9)
D(v,1.0)
Never use
the D100!
Size µm
D(4,3) sensitive to large particles
D(3,2) sensitive to small particles
© 2013 HORIBA, Ltd. All rights reserved.
Standard Deviation

 Normal (Gaussian)
Distribution Curve
-1 STD DEV +1 STD DEV   = distribution mean
68.27%
  = standard deviation
 Exp = base of natural
logarithms

-2 STD DEV +2 STD DEV

95.45%

Mean

1 - (x - )2
Y=  2 Exp [ ]
22
© 2013 HORIBA, Ltd. All rights reserved.
Distribution Width

 Polydispersity Index
(PI, PDI)
 Span
 Geometric Std. Dev.
 Variance
 Etc…

© 2013 HORIBA, Ltd. All rights reserved.

For Your Reference

Note: Span typically = (d90 – d10)/ d50

© 2013 HORIBA, Ltd. All rights reserved.

For Your Reference

© 2013 HORIBA, Ltd. All rights reserved.

For Your Reference
Error Calculations in LA-950 only

© 2013 HORIBA, Ltd. All rights reserved.

Skewness

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Kurtosis (Peakedness)

From highest to lowest peak:

red, kurtosis 3
orange, kurtosis 2
green, kurtosis 1.2
black, kurtosis 0,
cyan, kurtosis −0.593762…
blue, kurtosis −1
magenta, kurtosis −1.2

© 2013 HORIBA, Ltd. All rights reserved.

 Number vs. Volume Distributions
r = 1 µm r =2 µm r = 3 µm
v=4 = 32 = 108
V = 4  r3
3

V*3 = 12 96 324 Total = 12+96+324 = 432

12/432=2.8% 96/432=22.2% 324/432=75%

© 2013 HORIBA, Ltd. All rights reserved.

Beans!

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Equivalent Volume Distributions

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Equivalent Volume Distributions

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Equivalent Volume Distributions

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Equivalent Volume Distributions

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 Comparing Distribution Bases
 Same material shown as volume, number and area
distribution
12
Number
Volume Distribution
10
Percent in Channel

Volume Mean = 12.65µm

Area Median=11.58 µm
8 SA=13467 cm2/cm3
Std Dev.=8.29
6
Number Distribution
Mean = 0.38µm
4
Median=0.30 µm
SA=13467 cm2/cm3
2
Std Dev.=0.40

0
0.58

2.27

8.82

34.25
0.34

1.15

4.47

Particle Size 17.38

© 2013 HORIBA, Ltd. All rights reserved.

Statistical Issues with Distributions

 L Neumann, E T White, T Howes (Univ.

Queensland) “What does a mean size
mean?” 2003 AIChE presentation at Session
39 Characterization of Engineered particles
November 16 - 21 San Francisco

Other references:
 L Neumann, T Howes, E T White (2003) Breakage can cause mean
size to increase Dev. Chem. Eng. Mineral Proc. J.
 White E T, Lawrence J. (1970), Variation of volume surface mean for
growing particles, Powder Technology,4, 104 - 107

© 2013 HORIBA, Ltd. All rights reserved.

Does the Mean Match the Process?

 Particle size measurements often made to

monitor a process
Size reduction (milling)
Size growth (agglomeration)
 Does the measured/calculated mean
diameter describe the change due to the
process?
 It depends on which mean used…

© 2013 HORIBA, Ltd. All rights reserved.

Size Reduction Scenario

10 x1 m 10 x 1 m

79.4 m

79.4 m
100 m
breaks into two smaller particles

© 2013 HORIBA, Ltd. All rights reserved.

Size Reduction: Number Mean

Ten particles of size 1; one of size 100 units

Number mean = D[1, 0] = (10*1 + 1*100)/11 = 10 units
..

Largest particle (100) breaks into two of 79.37

(conserves volume/mass: 2 @ 79.373 = 1 @ 1003)
Have broken one
What happens to the number mean?

Mean = (10*1+2*79.37)/12 = 14.06 units

Surprise, surprise a 40.6% increase!

© 2013 HORIBA, Ltd. All rights reserved.

Size Reduction: Volume Mean

Ten particles of size 1; one of size 100 units

Volume Moment Mean
D[4, 3] = (10*14 + 1*1004)/(10*13 + 1*1003) ~ 100 units
..
Largest particle (100) breaks into two of 79.37
(conserves volume/mass: 2 @ 79.373 = 1 @ 1003)
Have broken one
What happens to the D[4, 3]?
New D[4, 3] = (10*14+2*79.374)/(10*13 +2*79.373) ~ 79.37 units

This shows the expected behavior

© 2013 HORIBA, Ltd. All rights reserved.

Can You See the Problem?

Number mean = 10 Number mean = 14

Volume mean = 100 Volume mean = 79

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Size Growth Scenario

10 1 m 10 1 m

10 46.4 m

1 100 m

Ten 46.4 m particles agglomerate into one 100 m particle

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Growth: Number Mean

Ten particles of size 1; ten of size 46.42

D[1, 0] = (10*1 + 10*46.42)/20 = 23.71 units
.

Ten of 46.42 agglomerate into one of 100

(conserves volume/mass: 10 @ 46.423 = 1 @ 1003)
Have agglomerated half; does mean increase?

Mean = (10*1+1*100)/11 = 10 units

Over a 50% decrease!

© 2013 HORIBA, Ltd. All rights reserved.

Growth: Volume Mean

Ten particles of size 1; ten of size 46.42

D[4, 3] = (10*14 + 10*46.424)/(10*13 + 10*46.423)
~ 46.4 units
(Note again the volume moment mean is dominated by the large
particles)
.

Ten of 46.42 agglomerate into one of 100

(conserves volume/mass: 10 @ 46.423 = 1 @ 1003)
Have agglomerated half; does mean increase?

D[4, 3] = (10*14+1*1004)/10*13 + 1*1003 ~ 100 units

This shows the expected behavior
© 2013 HORIBA, Ltd. All rights reserved.
Can You See the Problem?

Number mean = 24 Number mean = 10

Volume mean = 46 Volume mean = 100

© 2013 HORIBA, Ltd. All rights reserved.

Practical Implications

 Not just a “party trick” topic!

“Do you know you can break particles and
the mean will increase?”

 Serious. “Did an experiment. I thought I

broke particles but the mean has increased”
(REAL experience)

 Should be aware it can happen!

 Analyse whole size distribution, not mean

alone.
© 2013 HORIBA, Ltd. All rights reserved.
What we’ll talk about
 Featured technologies

 Defining particle size

 Understanding size metrics

 Differences between techniques

 Q&A

© 2013 HORIBA, Ltd. All rights reserved.

 PSA Method is Important
Why should one consider various
methods of particle size analysis?

Material suppliers and users employ many

different types of instruments

Use a different technique = get a different

answer

It is important to understand how analysis

methods differ in order to know how to
compare data

© 2013 HORIBA, Ltd. All rights reserved.

Size Range by Technique

ELECTROFORMED MESH SIEVES

CENTRIFUGAL SEDIMENTATION

ACOUSTIC SPECTROSCOPY

OPTICAL MICROSCOPY / IMAGE ANALYSIS

ELECTRICAL CONDUCTIVITY

LIGHT OBSCURATION / ELECTRICAL SENSING ZONE

DYNAMIC LIGHT SCATTERING

LASER DIFFRACTION

10 nm 100 nm 1 µm 10 µm 100 µm 1 mm

© 2013 HORIBA, Ltd. All rights reserved.

What Size is Measured?

Laser Diffraction
Equivalent Spherical Diameter

Dynamic Light Scattering

Hydrodynamic Radius

Image Analysis
Lengths, Widths, Equivalent Spherical

Acoustic Spectroscopy
Equivalent Spherical Diameter

© 2013 HORIBA, Ltd. All rights reserved.

Particle Shape Definitions

Acicular: Needle-shaped, rigid

Angular: Edgy, hard angles
Fibrous: Thread-like, non-rigid
Granular/Blocky: Irregular-shaped, low aspect-ratio
Spherical: Regular-shaped, unity aspect ratio

Aspect ratio: Breadth / length OR Length / breadth

Sphericity: How spherical is the particle?
Roundness: How round is the particle?

© 2013 HORIBA, Ltd. All rights reserved.

 Poll!

What are the shapes of your particles?

© 2013HORIBA, Ltd. All rights reserved.

 Poll!

Do you use multiple sizing techniques?

© 2013HORIBA, Ltd. All rights reserved.

Hegman Gauge
 Used in paint and coatings industry
Device has tapered center
channel
Slurry is placed in
channel, then straight
edge is drawn across it
“Hegman Number” is
where particles disturb
smooth surface of slurry
Information from largest
particles only – no
distribution

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Sieves
Weigh % sample caught
on known screen sizes
Solid particles 30 m – 30
mm (and larger)
Advantages: Disadvantages:
Low equipment Limited lower
cost range
Direct Time
measurement Consuming
method High Labor Cost
No practical upper Need Large
limit Sample
Available through www.retsch.com

© 2013 HORIBA, Ltd. All rights reserved.

 Electrical Sensing Zone
Coulter Principle
 Based on change in
conductivity of aperture
as particle traverses.
 Requires conducting
liquid.
 Directly measures
particle volume and
counts.
 High resolution
 Used for blood cell
counting more than
industrial applications

© 2013 HORIBA, Ltd. All rights reserved.

Light Obscuration
 Light Obscuration: Liquid Flow

Sensing Zone

Light Source

Light is blocked by single particles as Detector

they traverse the light beam

Advantages: Disadvantages:
 Particle count available  Dilution required for
 USP<788> testing particle size analysis
 High resolution histogram  Prone to cell clogging

© 2013 HORIBA, Ltd. All rights reserved.

 Sedimentation
Sedimentation of same density
Stokes Law material in a viscous medium

18 µ Vp
D=
(A - B) G
Vp = Settling velocity of discrete particle
G = Gravity constant
A = Density of Particle
B = Density of Carrier Fluid
D = Diameter of discrete particle Time
µ = Viscosity of Carrier Fluid

Note: assumes settling of spherical particle

Under-sizes compared to other techniques if non-spherical

© 2013 HORIBA, Ltd. All rights reserved.

Sedimentation Issues
 Comparison of Brownian Motion and
Gravitational Settling
(Movement in 1 second; Particle density of 2.0 grams/cc)

Particle Diameter Movement due to Movement due to

(In micrometers) Brownian Motion Gravitational Settling
0.01 2.36 >> 0.005
0.25 1.49 > 0.0346
0.50 1.052 > 0.1384
1.0 0.745 ~ 0.554
2.5 0.334 < 13.84
10.0 0.236 << 55.4
 Below 1 micrometer, Brownian motion becomes an appreciable factor
in particle dynamics. Gravity sedimentation may not be an appropriate
measurement technique for very small particles.

© 2013 HORIBA, Ltd. All rights reserved.

 Dynamic Light Scattering
Most common technique for sub-micron sizing
Range: 1 nm – 1 m* Frequency Shifted Signal

Frequency-Intensity
Distribution

Particles in suspension undergo Brownian kT

Stokes-Einstein R H 
motion due to bombardment by solvent 6  D
molecules in random thermal motion.
* Density dependent, when does settling become prominent motion?

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Manual Microscopy
 Count particles in a given
field of view
 Use graticule to obtain size
 Repeat this process for a
number of fields
 At least hundreds of particles
must be sized

Advantages: Disadvantages:
Simple Slow
Inexpensive Measures very few particles
Can see shape Very tedious

© 2013 HORIBA, Ltd. All rights reserved.

Automated Microscopy
Static: Dynamic:
Particles fixed on slide, Particles flow past camera(s)
stage moves slide

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 Automated Microscopy
Advantages:
Quick size + shape info
Objective & Image Acquisition
and enhancement
Statistically valid
camera
High resolution
Particle images
Subjective or Thresholding
automatic
Disadvantages:
Expense
Decisions or Image Processing Knowing which
black box numbers are
important
Measurements

© 2013 HORIBA, Ltd. All rights reserved.

Acoustic Spectroscopy
 Acoustic signal sent into
concentrated sample
 Detector measure
attenuation f (frequency,
distance from source)
Signal
Detector source

Signal output

Advantages: Disadvantages:
 Can accommodate high
sample concentrations  Need at least 1 wt% particles
(no dilution)  Need to know wt%
 Rheological properties  Minimum sample = 15 ml
 Also measure zeta potential

© 2013 HORIBA, Ltd. All rights reserved.

Laser Diffraction

•Converts scattered light to

particle size distribution
•Quick, repeatable
•Powders, suspensions
•Most common technique

© 2013 HORIBA, Ltd. All rights reserved.

 Poll!

Which techniques do you use?

© 2013HORIBA, Ltd. All rights reserved.

What we’ll talk about
 Featured technologies

 Defining particle size

 Understanding size metrics

 Differences between techniques

 Q&A

© 2013 HORIBA, Ltd. All rights reserved.

 ありがとうございました
ขอบคุณครับ
谢谢
Gracias
‫ش ْكر‬
ُ ‫ا‬ Grazie
Σας ευχαριστούμε धन्यवाद
Tacka dig நன்ற
Danke
Obrigado
감사합니다 Большое спасибо

© 2013 HORIBA, Ltd. All rights reserved.

www.horiba.com/particle
Ian Treviranus
Product Line Manager
[email protected]

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