Sampling and Dispersion

The Key to Precision

Jeffrey Bodycomb, Ph.D.

[email protected]
www.horiba.com/particle

© 2012 HORIBA, Ltd. All rights reserved.

 What we’ll talk about

Sampling techniques

Particle wetting, surfactant use

Dispersing agglomerates

Tips for HORIBA size analyzers

© 2012 HORIBA, Ltd. All rights reserved.

 Particle Sizing Workflow

Today’s subject area

From: NIST Recommended Practice Guide

Special Publication 960-1
Particle Size Characterization
Ajit Jillavenkatesa
Stanley J. Dapkunas
Lin-Sien H. Lum
Materials Science and
Engineering Laboratory
January 2001

© 2012 HORIBA, Ltd. All rights reserved.

 Measurement Error Sources
 SMALL PARTICLES
 POTENTIALLY SMALL C SAMPLE PREPARATION SAMPLE EXTRACTION
EXTRACTION ERRORS (A)
%
 POTENTIALLY LARGE B
E
SAMPLE PREP ERRORS (C)
R
 LARGE PARTICLES R

 POTENTIALLY LARGE O
EXTRACTION ERRORS (B) R A D
 POTENTIALLY SMALL INSTRUMENT ERROR
SAMPLE PREP ERRORS (D)

PARTICLE SIZE

 INSTRUMENT ERROR IS SMALL AND

RELATIVELY CONSTANT

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 Question?

What size particles do you analyze?

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 Section Overview

Sampling from bulk

Sub-sample for measurement
Disperse sample
Wet powders, apply air pressure or
ultrasound
Sometimes second sub-sampling
From beaker to instrument
Perform measurement

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 Sampling from Flowing Powder

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 Sampling from Flowing Powder

Cross-cut sampling: w = L W b = Wb
 L 
 = sampling speed (m/s) Cross-cut sampler
W = sample mass
L = width of powder stream *Masuda, H, Powder Technology Handbook, CRC
b = sample cutter width* Press, p 771

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 Sampling from Drums

Powder Thief

www.samplingsystems.com

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 Sampling from Drums

www.samplingsystems.com

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 Sub-sampling for Measurement

Not all of sample brought to lab is

analyzed
Must sub-divide sample
How to introduce representative sample
into instrument

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 Technique: Grab Sampling

 PLACE SPATULA INTO POWDER

 EXTRACT SMALL AMOUNT FOR ANALYSIS
 ACCEPTABLE FOR NARROW DISTRIBUTIONS

 SEGREGATE LARGE AND SMALL WHEN POLYDISPERSE

 LARGE PARTICLES PERCOLATE UPWARD
 SMALL PARTICLES GRAVITATE DOWNWARD
 EASY METHOD
 MOST USED METHOD

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 Grab Sampling from Bottle

 When a powder is stored in a

container, it can be mixed by rolling
and tumbling the container. The
container should not be more than
half to two-thirds full. It is important
to perform this action before
“grabbing” a sample with a spatula.

 Then pull sample with a spatula…..

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 Technique: Coning & Quartering
Pile of powder is divided into 4
sections.
Two diagonal sections are
discarded, and two are retained
and mixed together.
Mixture is again divided into 4
sections, and two diagonal
sections are mixed.
Process is repeated until
remaining sample is correct
amount for analysis.
Can be carried out with very
small sample amount or very large
samples.

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 Technique: Chute Riffling

Chute splitting allows sample to

vibrate down a chute to vanes
which separate the mass into two
portions. Each portion moves
further where they each are
divided into two parts, now giving
four parts. This may be continued
until usually 8 or 16 portions are
obtained.

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 Technique: Rotary Riffling
 The best method of representative
splitting of powders is the ROTARY
RIFFLER. The complete sample to be
split is directed down a chute into open
containers. Each container will receive a
sample which is representative of the
original bulk material because the
distribution of material is averaged over
time. The complete amount of the
original bulk sample must be consumed.

 These splitters are commercially available from companies that market

various types of sample splitters.
 See: www.retsch.com
 www.quantachrome.com
 www.microscal.com

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 Sample Dividers

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 Sampling Technique Error Levels

 Standard Deviation () in % Sugar-Sand Mixture

 SCOOP SAMPLING 6.31
 TABLE SAMPLING 2.11
 CHUTE RIFFLER 1.10
 SPINNING RIFFLER 0.27
 Density of sand and sugar respectively 2.65 and 1.64 g/ml
 Reference: Allen, T. and Khan, A.A. (1934), Chem Eng, 238, CE 108-112

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 Technique: Sampling from Beaker

Liquid should be in motion

vertically and horizontally
to insure good mixing.
Pipette should be about
one-third of the way from
the bottom when
extracting sample.
Alternative: When mixing IMPELLER PIPETTE

powders into a slurry:

make paste, pipette from
paste
© 2012 HORIBA, Ltd. All rights reserved.
 Summary

From: NIST Recommended Practice Guide

Special Publication 960-1
Particle Size Characterization
Ajit Jillavenkatesa
Stanley J. Dapkunas
Lin-Sien H. Lum
Materials Science and
Engineering Laboratory
January 2001

© 2012 HORIBA, Ltd. All rights reserved.

 What we’ll talk about

Sampling techniques

Particle wetting, surfactant use

Dispersing agglomerates

Tips for HORIBA size analyzers

© 2012 HORIBA, Ltd. All rights reserved.

 Dispersion Strategies
 Powders
 When measuring powder as suspension
 Choose solvent (avoid dissolution)
 Wet powder (surfactant)
 Dispersing aid to avoid re-agglomeration
 Energy to break agglomerates into primary
particles
– Pump & stirrer or ultrasound
 Suspensions
 Dilute
 Energy

© 2012 HORIBA, Ltd. All rights reserved.

 Measurement Error Sources
 SMALL PARTICLES
 POTENTIALLY SMALL C SAMPLE PREPARATION SAMPLE EXTRACTION
EXTRACTION ERRORS (A)
%
 POTENTIALLY LARGE B
E
SAMPLE PREP ERRORS (C)
R
 LARGE PARTICLES R

 POTENTIALLY LARGE O
EXTRACTION ERRORS (B) R A D
 POTENTIALLY SMALL INSTRUMENT ERROR
SAMPLE PREP ERRORS (D)

PARTICLE SIZE

 INSTRUMENT ERROR IS SMALL AND RELATIVELY

CONSTANT

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 Dispersion Definitions

WELL DISPERSED AGGLOMERATED AGGREGATED

 WELL DISPERSED particles can be easily detected under a
microscope. They are separated from one another and show no
tendency to cling together.
 AGGLOMERATED particles appear in clumps that can be separated
easily by the application of moderate amounts of energy, such as
ultrasonics.
 AGGREGATED particles are tightly bound and must be treated with
higher levels of energy. Usually an ultrasonic probe applied directly to
the sample slurry will disperse the particles. If they are very tightly
bound, they may fracture before they can be separated.

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 Particle Wetting
 MEASUREMENT OF
CONTACT ANGLE (  )

LARGE
 The contact angle is a measure of
how well the liquid drop adheres to (Phobic)
the surface of a solid
 Large angles indicate poor wetting 
ability.
 Small angles indicate good wetting
ability.
 Surfactants reduce surface tension
and thereby are conducive to good
wetting. 
SMALL (Phylic)
 (Instruments are available for
measuring contact angle) DROP OF LIQUID ON A SOLID

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 Particle Wetting
PARTICLE
Surface
Large
Tension must Small Contact
q q
Contact
Angle
be lowered so Angle
Good Wetting Bad Wetting
liquid will LIQUID
GOAL IS TO COMPLETELY COAT
adhere to PARTICLE WITH LIQUID
+
+
particles. +
+
+

+
+
+ +

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 How to check for wetting
 Sprinkle particles on of target dispersant. If the particles float on top and do not
penetrate the water surface, they are not wetted. This is usually a bad sign.
 If the particles break through surface and sink, they are a) wetted or b) so big that
gravity is more important than surface tension. If it is case a, you are in luck.

Plume of sinking particles

Particles floating on top

© 2012 HORIBA, Ltd. All rights reserved.

 Don’t forget changing solvents

Working with aqueous systems is

usually easier for many reasons.
But don’t forget to try a less polar
solvent such as isopropyl alcohol.
And, don’t forget that organic solvents
are more difficult to handle due to fire
and health hazards.

© 2012 HORIBA, Ltd. All rights reserved.

 If the going gets tough…
 Check the literature and the web and see
what other people use.
 Here I use Google to get the idea to use MEK
with lead.

© 2012 HORIBA, Ltd. All rights reserved.

 If the going gets tough…
Try a series of options.
Here I make a series of suspensions
and check them by eye, then measure.

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 Effect of Surfactant Addition

 Addition of surfactant to a sample MEAN

will disperse the particles so a PARTICLE

proper measurement may be SIZE

made. However, addition of too

much surfactant will cause
agglomeration. SURFACTANT CONCENTRATION

 The graph illustrates that there is an optimum amount of surfactant to effect

optimum dispersion. The Particle Size Analyzer can determine when the
amount of surfactant exceeds the proper concentration.
 As initial surfactant is added, the mean particle size will decrease. It will
reach a minimum as the proper surfactant concentration is reached.
 As additional surfactant is added, the apparent mean particle size will
increase, indicating agglomeration of particles.
 Common concentration: 0.01-0.1%

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 Surfactant Mechanism

EQUILIBRIUM
established between
SURFACTANT ON
PARTICLES and
SURFACTANT IN
SOLUTION.

NON-POLAR HYDROCARBON
POLAR IONIC DIPOLE

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 Critical Micelle Concentration

- -
- + +
+ -
+ -
+
- + + -
+ + + Cationic Surface
- - +-
+ +
- - Anionic Surfactant
-

MICELLES

 As more surfactant is added, equilibrium shifts. Surfactant leaves

surfaces to start formation of MICELLES. This is called CRITICAL
MICELLE CONCENTRATION (CMC).
 Particle surfaces are no longer repulsed, and energy of the system
favors REAGGLOMORATION.

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 Effect of Surfactant Addition
NO SURFACTANT -
AGGLOMERATED PARTICLES

OPTIMUM CONCENTRATION –
PROPER PARTICLE DISPERSION

EXCESS SURFACTANT -
REAGGLOMERATION
OF PARTICLES

© 2012 HORIBA, Ltd. All rights reserved.

 Common Surfactants
 Nonionic surfactants adsorb to charged and neutral surfaces,
create steric barrier
 Igepal CA630 Ethoxylated octyl phenol Nonionic
 Triton X100 Octylphenoxypolyethoxy ethanol Nonionic
 Tween 20 Polyoxyethylene sorbitan Nonionic
 Aerosol-OT Dioctyl ester Na Sulfo succinic acid Anionic
 Cationic surfactants often used for biological samples,
stringly bonds to negatively charged surfaces
non-polar chain
polar head

Hyrdophobic surface
Polar groups orient to aqueous phase
Anionic surfactant
© 2012 HORIBA, Ltd. All rights reserved.
 Sodium Hexametaphosphate

 Most common stabilizer

 Abbreviated NaHMP
 Keeps particles from re-
agglomerating
 Disperse sample in 0.01 – 1.0%
(NaPO3)6 rather than DI water
 Tetrasodium pyrophosphate
also used (sodium
pyrophosphate, NaPP)

© 2012 HORIBA, Ltd. All rights reserved.

 What we’ll talk about

Sampling techniques

Particle wetting, surfactant use

Dispersing agglomerates

Tips for HORIBA size analyzers

© 2012 HORIBA, Ltd. All rights reserved.

 Particle Interactions
ATTRACTIVE FORCES
(VAN DER WAALS)

REPULSIVE FORCES REPULSIVE FORCES

(CHARGE) (CHARGE)

 Particles are constantly moving with respect to one another. When they
approach close enough to cross the potential barrier (when attractive
forces exceed repulsive forces), they come together (agglomerate).

 The object is to provide repulsive forces strong enough to keep particles

apart, even during close approach. This can be accomplished by
surfactant coating of particle surfaces.

+ + +
+ + +
+ + + +
CHARGE + + CHARGE

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 Particle Interactions
Inter-particle distance is LARGE.
Van der Waals forces WEAK

Decreasing particle distance

Increasing Van der Waals forces

Particle distance very small

If surfactant charge is Van der Waals forces strong
sufficiently high, it will
overcome Van der Waals forces
before the particles approach
+
closely. +
++ ++
+
+

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 Energy of Interaction
 INTERACTION
 Stability of a system depends on
OF TWO forces between particles. Random
CHARGED Electrical forces motion brings them into close
SURFACES cause particles proximity. Whether two particles will
to remain apart. combine depends on potential barrier
between them. Potential energy
Van der Waals consists of two forces, the
Repulsion forces cause ATTRACTIVE one due to Van der
VR particles to Waals, and the REPULSIVE one due to
come together. electrical double layers around
particles.
Potential Energy

Total Potential Energy

VT  If height of the barrier, VT, is lower
Vmax than average thermal energy, KT, then
0 probability is high that two adjacent
Distance Between Surfaces particles will eventually collide. They
VA will probably remain attached to each
other due to strong Van der Waals
Attraction VT = VA + VR forces at very close distances.

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 Dispersion Stability
steric stabilization

electrostatic stabilization

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 Zeta Potential
A double layer exists around
each particle. If a particle is -
negatively charged, a thin layer + Diffuse Layer Stern Layer
of positive charge forms around + +
-
the particle (the Stern Layer). + - -+
Beyond the Stern Layer, there is - - -+ -
-
+ -Particle- + -
a wider layer of mostly opposite
charge known as the DIFFUSE
- REPRESENTATION
Layer. + + + + OF ATTRACTED
The potential at the surface of LAYERS AND ZETA
the particle is designated the - + POTENTIAL
NERNST Potential, and the +
potential at the shear plane is - +
designated the ZETA Potential. +
ZETA Potential is a useful
measurement quantity because
it is a measure of surface electric
activity in colloidal particles. potential
Nernst
(millivolts) Potential

Zeta
Potential
Distance (Angstroms)

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 Pop Quiz

As particle size distribution becomes

wider….

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 What we’ll talk about

Sampling techniques

Particle wetting, surfactant use

Dispersing agglomerates

Tips for HORIBA size analyzers

© 2012 HORIBA, Ltd. All rights reserved.

 Dispersion: Mechanical Energy
 The purpose of applying energy is to separate particles for a
sufficient period to allow surfactants to develop a coating.
 TYPES OF ENERGY DEVICES
 Blenders
 Stirrers
 Ultrasonic Devices
• Ultrasonic Bath
• Ultrasonic Probe ENERGY
Surfactant

 Dilute surfactant is mixed with suspending liquid before particulate sample

is added. As energy is applied, the surfactant is able to attach to the
particles, providing sufficient charge to keep individual particles apart.

© 2012 HORIBA, Ltd. All rights reserved.

 Dispersion: Ultrasonic Energy
 Ultrasonic waves generate Ultrasonic Bath
microscopic bubbles or cavities
(cavitation) which produce shearing
action causing the liquid and
suspended particles to become
intensely agitated.

 Agglomerates are broken apart.

 In some cases fragile particles are shattered.
 The selection of appropriate type and level of
ultrasonic energy must be made carefully.

Ultrasonic Probe

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 Effect of Applied Energy
 The effect of applied energy is to
break up agglomerates into
individual particles for size
measurement. However, if too
much energy is applied, particles Optimum Range
may by broken into fragments.

AVERAGE SIZE
The desired result is to apply
just enough energy to disperse
material into basic particles for
measurement without damaging
friable materials.

INCREASING ENERGY

 The graph illustrates how this can be accomplished. Effects of applied energy on
particulate samples can be tested by using results from measurements made on the
instrument. By treating the sample with varying levels of ultrasonic power,
performing analyses, and noting the average particle size (mean, median) as a
function of power level, one can choose a range of applied energy that is optimum
for that material.

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 Dispersion vs. Breakage

 Dispersion and breakage can both occur

Ideal World

Real World

© 2012 HORIBA, Ltd. All rights reserved.

 What we’ll talk about

Sampling techniques

Particle wetting, surfactant use

Dispersing agglomerates

Tips for HORIBA size analyzers

© 2012 HORIBA, Ltd. All rights reserved.

 Laser Diffraction

Starting from a powder…

Solubility issues? Can measure dry!
– Sampling critical
– Air pressure only dispersion choice
– Take a look at webinar TE016: Optimizing Dry
Powder Measurements
Solubility OK? Many options
– Make paste w/ surfactant to wet
– Sample from paste

© 2012 HORIBA, Ltd. All rights reserved.

 Laser Diffraction

Starting from an emulsion…

Sampling typically less critical
Dispersion stable upon dilution?
– pH, shear forces, temperature, surfactant conc.
Avoid high pumping speeds, avoid high
ultrasonic

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 Dynamic Light Scattering

Starting from a powder…

Very few nanopowders 
Dispersion very critical
Use filters to remove agglomerates/dust
Dispersion conditions directly affect zeta
potential
Starting from a suspension/emulsion…
Visually inspect for “crud”
Use filters to remove agglomerates/dust

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 Dynamic Image Analysis

Vast majority are powder applications

Sampling critical
– Recommend Retsch PT100 rotary splitter for
CAMSIZER
– Recommend Retsch chute rifflers for
CAMSIZER XT
– Measure every particle on the chute
– If comparing with sieving, then same good
sampling practices need to be applied to sieves
Suspensions (XT only) follow diffraction

© 2012 HORIBA, Ltd. All rights reserved.

 Summary
Surfactants wet powders
Use admixture to alter surface chemistry
Sodium hexametaphosphate
Sodium pyrophosphate
Ultrasound reduces size
De-agglomeration %
SAMPLE PREPARATION SAMPLE EXTRACTION

and/or breakage E
R
R

REMEMBER! O
R INSTRUMENT ERROR

PARTICLE SIZE

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Contact us directly at [email protected]

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