Particle Sizing by Laser Diffraction

Dr Anne Virden
Product technical specialist – diffraction and analytical imaging
anne.virden@malvern.com

© 2017 Malvern Instruments Limited

Overview
› Introduction to particle sizing
› Introduction to laser diffraction
› Smarter particle sizing
 Smarter method development
 Data quality advice
› Method development
 Method development for dispersion in liquid
 Method development for dispersion in air
› Choosing the right specifications
 Understanding the size distribution
› Optical properties and optical modes
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Introduction to particle characterisation
› What is a particle?
› A particle can be defined as:
› ‘a minute portion, piece, fragment, or amount of matter’
› Naturally occurring examples include:
 Sand, soil, clay, pollen, dust, smoke, fog

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Introduction to particle characterisation
› What is a particle?
› A particle can be defined as:
› ‘a minute portion, piece, fragment, or amount of matter’
› The particles that we measure are in:
Dry powders Suspensions Emulsions Sprays

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What can measuring particle size tell us?
› Predicting product performance  Dissolution rate
 Content uniformity
 Mouth feel assessment
 Stability
 Viscosity (of a suspension)
 Colour
 Flowability (of a powder)

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Why is particle size important?
› Controlling production processes
 Blending
 Milling
 Dispersion
 Tableting

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Particles come in many different shapes
(as well as sizes)

 How do we describe the size of these particles?

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Basic concepts of particle sizing

› You are given a regular-shaped object and a ruler and asked

to give a one-number indication of its size
 What would your reply be ?

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Basic concepts of particle sizing

› You may reply: “360x140x120mm”

 Which might be correct but it is not one number.
 It is not possible to describe the size of this 3-dimensional object with a single
number

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Concept of equivalent spherical diameters

226μm

› The rectangular box has the same volume as a sphere of

226µm diameter.
 The volume equivalent spherical diameter is 226μm

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How do we describe the size of a particle?
› Equivalent spheres Min. length
 Maximum length
 Minimum length Max. length

Max. length
Min. length

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How do we describe the size of a particle?
› Equivalent spheres
 Maximum length
 Minimum length Sedimentation rate

 Sedimentation rate

Max. length
Min. length Sedimentation rate

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How do we describe the size of a particle?
› Equivalent spheres
 Maximum length
 Minimum length
 Sedimentation rate
 Sieve aperture

Sieve aperture

Max. length
Sedimentation rate Sieve aperture
Min. length

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How do we describe the size of a particle?
› Equivalent spheres
 Maximum length
 Minimum length Surface area
 Sedimentation rate
 Sieve aperture
 Surface area

Max. length
Sedimentation rate Sieve aperture
Surface area
Min. length

© 2017 Malvern Instruments Limited

How do we describe the size of a particle?
› Equivalent spheres
 Maximum length
 Minimum length Volume
 Sedimentation rate
 Sieve aperture
 Surface area
 Volume

Max. length
Sedimentation rate Sieve aperture
Surface area
Min. length

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Concept of equivalent spherical diameters
› Different particle sizing techniques report different
equivalent spherical diameters
 Dependent on the physical property that is measured

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Introduction to laser diffraction

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The basic principles of laser diffraction
› The diffraction pattern:

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Dependence of diffraction pattern on particle size

Incident light Incident light Large angle

Small angle scattering
scattering

Large particle Small particles

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Measuring the scattering pattern: Spraytec
Data collection lens Detector system
Measurement zone

Collimating Auto-align stage

optics

Data acquisition
system
Light source

IP65 enclosures

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Measuring the scattering data: Mastersizer 3000
Measurement cell Focal plane
detectors
Back scatter
detectors

Side scatter
detectors

633nm red
laser
Precision
folded optics
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Measuring the scattering data: Mastersizer 3000
Measurement cell

Back scatter
detectors

470nm blue Side scatter

light source detectors

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The measured scattering data
Blue light
Red light detectors detectors

Extinction detectors:
51 and 63

Increasing angle / Decreasing particle size

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Example data set: large particles

› Large particles scatter at low angles

› Scattering data is concentrated on low angle detectors
 With high intensity (light energy)

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Example data set: small particles

› Small particles scatter light at high angles

› Scattering data is concentrated on high number detectors
 With low intensity (light energy)

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Laser diffraction instrumentation

› Wide dynamic range ideal for polydisperse samples

› Wet, dry or spray measurements
› Ensemble method, good sampling
› Lab (Mastersizer, Spraytec) and process (Insitec) solutions
› Widely accepted and standardized
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Particle size measurement ranges

Particle size
0.1nm 1nm 10nm 100nm 1μm 10μm 100μm 1mm 10mm

Laser diffraction
Spatial filter velocimetry
Sieving
Automated imaging
Electrozone sensing
Sedimentation
Dynamic light scattering
Nanoparticle tracking
Resonant mass measurement
Taylor dispersion analysis

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Smarter particle sizing

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Introducing the Mastersizer 3000
› Extensive measurement capabilities
 10nm to 3.5mm range
 10kHz data acquisition
› Rapid and effective wet dispersion
 Efficient in-line sonication
› Cutting-edge dry dispersion
 Suitable for fragile and cohesive samples
› Software that eases your workload
 Direct measurement feedback
 Method development guidance
 Data quality assessment
 Easy result reporting

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Laser diffraction measurement process
Sampling

Dispersion and stabilisation

Optical alignment

Background signal collection

Sample signal collection

Data analysis

Reporting and interpreting results

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 Sampling
When do sampling and dispersion matter?

Dispersion

% Error

Sampling

Instrumentation

Particle size

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 Sampling
How much sample do I need to measure
› A certain number of particles must be measured in order to
obtain a representative result
 For larger particles a greater mass of sample must be measured to ensure sufficient
particles are measured

2.50

2.00
Minimum mass / g

1.50

1.00

0.50

0.00
0 200 400 600 800 1000
Dv90 / μm

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 Sampling
Data Quality: Ensure representative sampling

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 Dispersion and stabilisation
The Mastersizer 3000: Wet dispersion units

Hydro EV Hydro LV Hydro MV Hydro SM Hydro SV

Volume/mL 1000/600ml 600ml 120ml 50-120 6-7ml

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 Dispersion and stabilisation
How do we disperse particles in liquid?
› Stirring and ultrasound are used to disperse agglomerates
1: Before ultrasound 2: During ultrasound 3: After ultrasound

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 Dispersion and stabilisation
Direct feedback on measurement stability is provided

after ultrasound

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 Dispersion and stabilisation
Smarter method development: SOP player

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 Dispersion and stabilisation
Diagnosing stability problems

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Hydro Sight
› In-line imaging accessory allowing
users to view the dispersion
› Helps users to optimise and
troubleshoot their methods

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Hydro Sight
› Size range
 Measurement: 9 - 1000 µm
 Observation: 1.4 - 1400 µm
› Measures size and elongation
 Also calculates the degree of sample dispersion
› Works with recirculating liquid
sample dispersion units:
 Hydro SM / EV / LV / MV
› Simple installation
 Connected between the dispersion unit and the
optical bench

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Hydro Sight aids method development by providing sample
images which show the state of dispersion

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Following dispersion trends using Hydro Sight

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The software can also be configured to automatically
detect sample anomalies

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Dry powder dispersion - Aero
› 0.1 mm to 3500 mm
› Precise pressure control
 0.1 to 4.0 bar range
› Modular venturi disperser
 Standard suitable for most powders
 Options for cohesive or abrasive samples
› Modular sample tray design
 Hopper unit for large sample quantities
 Micro and Macro trays for smaller quantities
› Full software control

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 Dispersion and stabilisation
Exchangeable dispersers enable the development
of a range of applications

Standard Venturi High-Energy Venturi

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 Optical alignment
Data Quality: Optical alignment

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 Background signal collection
Data Quality: Background
› Background level and stability can be assessed before sample
addition
 Ensures confidence in measurement quality

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 Sample signal collection
Data Quality: How much sample should I add

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 Sample signal collection
Data Quality: How much sample should I add

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 Data analysis
Data Quality: Optical models and optical properties
› The data quality system provides advice on the choice of
optical model and optical properties

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 Reporting and interpreting results
Customise reports for your application
› Customise reports with
 Graphs
 Tables
 Parameters
 Calculations (text, tables and graphs)
 Signature tables
 Pictures

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 Reporting and interpreting results
Easily review results from multiple record files

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 Reporting and interpreting results
Direct support is provided via the Malvern Portal

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Choosing the right specifications
The particle size distribution explained

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Understanding particle size results: Distribution type
› Type of distribution result depends on measurement
technique
 Number
 Mass
 Volume
 Intensity

› Always set specifications using the type of result measured

by the system
 Transforming the result type greatly increases the potential error

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Particle size distribution statistics: Median and Mode
› Median = midpoint of the distribution
› Mode = most commonly occurring size class
Gaussian Distribution

Median Mode
% Volume
%

Diameter

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PSD Statistics: Median and Mode
› If the distribution shape is more complex then these
parameters will diverge
Bimodal Distribution

Mode

Median
% Volume
%

49% 51%

Diameter

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PSD Statistics: Percentiles
› Percentiles are the size below which there is a certain
volume of the sample
 Taken from the cumulative distribution

100

90

Cummulative distribution / %
80

70
% Volume

60

50

40

30

20

10

0
Diameter
Dx10 Dx50 Dx90

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PSD Statistics: Mean particle sizes
› The most familiar mean is the arithmetic mean
11 + 21 + 31 1 + 2 + 3
𝑋𝑛𝑙 = 𝐷 1,0 = 0 0 0
= =2
1 +2 +3 3
› Different particle sizing techniques report different mean
sizes, depending on the sensitivity of the technique
 Image analysis reports a number weighted mean
• D[1,0]
 Laser diffraction reports the volume weighted mean
• D[4,3]
• And surface area weighted mean, D[3,2]

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PSD Statistics: Volume weighted mean
› D[4,3] is sensitive to changes in the coarse particle fraction
 Useful for monitoring milling or dispersion

D[4,3] =7.95

D[4,3] = 11.2

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PSD Statistics: Surface area weighted mean
› D[3,2] is sensitive to changes in the fine particle fraction
 Useful when surface area is important

D[3,2] = 34.4μm
D[3,2] = 59.1

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Particle size distribution statistics: Summary

Volume
%%

Dx100

D[1,0] Dx10 D[3,2] Dx50 D[4,3] Dx90 Diameter

› Percentiles
› Averages, weighted by number, surface area or volume
› Avoid parameters with high variability, such as Dx100
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Choosing the right parameter to follow the process
› Blend of coarse and fine particles
100
90
Cumulative volume %

80
70
coarse
60 1% fines
50 5% fines
10% fines
40
20% fines
30 30% fines
20 fines

10
0
0.1 1 10 100 1000 10000
Size / um

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Choosing the right parameter to follow the process
› Choose the parameter that shows the greatest sensitivity in
the region of interest
300

250

200
Size / um

Dv10
150 D[3,2]
Dv50
100 D[4,3]
Dv90
50

0
0 20 40 60 80 100
Fines /%

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Example: Factors affecting the tableting process
› Particle size
 Smaller particle size increases particle adhesion
 Greater adhesion can lead to voiding, cracking and breakage
 Affects flowability of powder into the die
› Particle size distribution
 Close overlap between actives, excipients and binders is ideal
 Narrow distributions improve content uniformity
 Wider distributions increase packing density

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Example: Tablet formulation

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Example: Tablet formulation

Parameter Target value Size specification

(μm) (μm)
Dv10 >30 40 ± 20%
Manufacturing spec 32 to 48
D[4,3] >80 110 ± 20%
Manufacturing spec 88 to 132
Dv90 <1000 200 ± 20%
Manufacturing spec 160 to 240

Evolutions in Direct Compression, Douglas McCormick, Pharmaceutical Technology, April 2005. Pg 52-62

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What precision values are reasonable?
› ISO13320-1: Section 6.4
 Dv50 - 5 different readings: COV < 3%
 Dv10 and Dv90: COV < 5%
 “Below 10μm, these maximum values should be doubled.”
› In ideal conditions
 0.5% COV on parameters >1μm
 1% COV on parameters <1μm

› USP <429> and EP 2.9.31

 Provides reproducibility ranges
 Dv50 or any central value: <10%
 Dv10, Dv90 or any non-central value: <15%
 “Below 10μm, these maximum values should be doubled.”
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Example: Tablet formulation
› Specifications should be tightened to account for analytical
variation
 Ensures that the manufactured material is in specification
› Using the USP guidance for reproducibility
 10% on central values
 15% at distribution edges
Parameter Target value (μm) Size specification (μm)
Dv10 >30 40 ± 20%
Manufacturing spec 32 to 48
(narrow specification by 15%) Measurement limits 36.8 to 40.8
D[4,3] >80 110 ± 20%
Manufacturing spec 88 to 132
(narrow specification by 10%) Measurement limits 96.8 to 118.8
Dv90 <1000 200 ± 20%
Manufacturing spec 160 to 240
(narrow specification by 15%) Measurement limits 184 to 204
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Linking measurement data and manufacturing
specifications
Lower Measurement Limit Upper Measurement
Limit

Measurement
s Specification s

Product Specification

Particle Size

Lower Product Upper Product

Acceptance Limit Acceptance Limit

How to Establish Manufacturing Specifications, Donald J. Wheeler, Statistical Process Controls Inc.
Posted on spcpress.com May 2003

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Method development for dispersion in liquids

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The purpose of method development
› A laser diffraction measurement requires
‘a representative sample, dispersed at an adequate concentration in a suitable liquid
or gas’
<USP429>

› Method development must define appropriate

 Sampling
 Dispersion
 Measurement conditions

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Is sampling or dispersion more important?
› The greatest source of error in particle size measurements
depends on particle size
 Dispersion is most important for fine particles
 Sampling is most important for coarse particles

Coarse
Fine particles
particles
Choice of
Sampling
dispersant
Sonication
Measurement
(dispersion
time
energy)

Dispersant
Sampling

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What happens to particles during transportation
› Particle can segregate during transit
 This can lead to sampling bias

Courtesy of A.J. Morris, M. Glover and M. Probert

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What happens to particles during transportation
› Particle can segregate during transit
 This can lead to sampling bias

Courtesy of A.J. Morris, M. Glover and M. Probert

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Measuring in the appropriate state of dispersion

Agglomerated Dispersed

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The liquid dispersion process

Wetting the sample

Adding energy to improve dispersion
Choose an appropriate
dispersant Stabilising the dispersion
Stirring/pumping by the
dispersion unit
Carry out a beaker test Check repeatability after
ultrasound
Application of ultrasound
Use surfactant to improve
the dispersion Additives can be used to
prevent re-agglomeration

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Wetting the sample Dispersant requirements
Sample wetting
Choose an Not dissolve the sample
appropriate Bubble free
dispersant Suitable viscosity
Transparent to the laser beam
Different refractive index to the sample
Chemically compatible with the instrument
Carry out a
beaker test Dispersant
Water/DI water

Polarity
Organic acids
Use surfactants Alcohols
(methanol / ethanol / isopropyl alcohol)
to improve Simple alkanes
wetting (hexane / heptane/ iso-octane / cyclohexane)

Long-chain alkanes and alkenes

(dodecane / mineral oils / sunflower oils / palm oil)
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Wetting the sample
DI water DI water + surfactant
Choose an
appropriate
dispersant

Carry out a
beaker test
Stabilization Examples

Steric Igepal CA-360, Tween 20/80, Span

20/80
Use surfactants
Electrosteric Anionic: SDS (sodium dodecylfulfate),
to improve AOT (sodium-bis-2-
wetting etheylhexylsulfosuccinate)
Cationic: CTAB (cetyltimethlammonium
bromide)
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Adding energy to improve dispersion
100

90

80

70

60
Size / um

50
Stirring
40

30

20

10

0
0 2 4 6 8 10 12 14 16 18 20
Measurement no.

Dx (10) (μm) Dx (50) (μm) Dx (90) (μm)

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Adding energy to improve dispersion
100

90

80

70

60
Size / um

50

40
Ultrasound
30

20

10

0
0 2 4 6 8 10 12 14 16 18 20
Measurement no.

Dx (10) (μm) Dx (50) (μm) Dx (90) (μm)

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Adding energy to improve dispersion
100

90

80

70

60
Size / um

50

40

30
After
20
Ultrasound
10

0
0 2 4 6 8 10 12 14 16 18 20
Measurement no.

Dx (10) (μm) Dx (50) (μm) Dx (90) (μm)

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Identifying dispersion: obscuration
› Obscuration increases as agglomerates disperse
12

10

8
Obscuration / %

Ultrasound off
6

Ultrasound on
2

0
0 5 10 15 20 25 30
Measurement no.
Obscuration

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Dispersion trend: scattering data
› During dispersion, as the particles get smaller
 Scattering on inner detectors decreases
 Peak shifts to higher angle detectors

Loss of scattering
on inner detectors
Trend across repeat
measurements

Reminder: detector number increases with angle

Scattering from larger particles falls on low angle detectors
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Dispersion trend: Particle size distribution
› Overlay the results of an ultrasound titration
 Should show gradual dispersion

Agglomerates dispersing

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The dispersion process: Verification

Without
ultrasound

With
ultrasound

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Stabilising the dispersion
100

90

80

70

60
Size / um

50

40

30

20

10

0
0 2 4 6 8 10 12 14 16 18 20
Measurement no.

Dx (10) (μm) Dx (50) (μm) Dx (90) (μm)

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Stabilising the dispersion
100

90

80

70 Admixtures – increase particle charge

60
• e.g. Sodium hexametaphosphate,
sodium pyrophosphate, Ammonium
Size / um

50 citrate
40
• pH can also be important
• ‘The use of zeta potential measurements for
improving dispersion during particle size
30
determination’ (MRK373)

20

10

0
0 2 4 6 8 10 12 14 16 18 20
Measurement no.

Dx (10) (μm) Dx (50) (μm) Dx (90) (μm)

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How stable should the results be?
› ISO13320-1: Section 6.4
 Dv50 - 5 different readings: COV < 3%
 Dv10 and Dv90: COV < 5%
 “Below 10μm, these maximum values should be doubled.”
› In ideal conditions
 0.5% COV on parameters >1μm
 1% COV on parameters <1μm

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Checking the stability of the results
› The live trend shows the variability of the results
 RSDs should be within ISO limits

Av RSD
13.3μm 13.3 0.465%

Av RSD
7.32μm 7.32 0.11%

Av RSD
3.77μm 3.77 0.0357%

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How do measurement conditions affect results?
› Appropriate amount of sample
 Good signal to noise ratio
 Avoid multiple scattering
› Correct stir speed
 Fast enough to prevent sedimentation for large/dense particles
 Slow enough not to break emulsions
› Correct measurement duration
 Long enough to sample all of the particles in the dispersion unit

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What defines the low obscuration limit?
› Signal to noise ratio
 Large particles scatter a lot of light
 Even at low obscuration's there will be a lot of sample data (relative to the
background and noise)
Scattering from ~40 micron glass
beads, at 7% obscuration,
produces ~250 units of light energy
- significantly higher than the
background

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What defines the low obscuration limit?
› Signal to noise ratio
 Small particle scatter light more weakly
 It is important to make sure that the background is stable before measuring fine
particles
Scattering from 2 micron latex, at 5%
obscuration produces ~8 units of light
energy – still sufficiently higher than
the background

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What defines the low obscuration limit?
› The reproducibility of the measurement may also define the
low obscuration limit
 Particularly if the particle size is large and the distribution is broad
› You can test this by measuring several sub samples of your
material
 If the results are within acceptable variation then the obscuration is sufficient
 Measurements with high variability may be improved by measuring at higher
obscuration (more sample)

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What defines the upper obscuration limit?
› If we add too much sample the results may be affected by
multiple scattering
 This generally affects samples smaller than 10μm
High
angle
detectors
Measurement cell

Detector
Low angle
detectors

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What defines the upper obscuration limit?
› If we add too much sample the results may be affected by
multiple scattering
 This generally affects samples smaller than 10μm
High
angle
detectors
Measurement cell

Detector
Increase in
scattering angle

Low angle
detectors

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How does multiple scattering affect the results
› This can be tested by measuring at increasing obscuration
› For this 1μm sample results at obscurations of 9% and
above show a reduction in size due to multiple scattering

Obscuration (%) Dv (10) (μm)

5.3 0.38
7.04 0.37
9.17 0.34
14.78 0.27
18.81 0.20

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Target obscuration ranges: Wet measurements
Particle size range Example Obscuration
Very fine <5%
Very low obscurations are used to avoid
multiple scattering

Fine 5% to 10%
Low obscurations are used to avoid multiple
scattering

Coarse 10% to 20%

Higher obscurations are used to improve
sampling

Very polydisperse 10% to 20%

Higher obscurations are used to improve
sampling- test with multiple sub samples

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Determine the correct stir speed
› For coarse or dense materials particle size will increase with
stir speed until all particles are suspended
 A stable particle size is obtained above 2500rpm
d10 dv50 d90
180
160
140
Particle size / μm

120
100
80
60
40
20
0
500 1000 1500 2000 2500 3000 3500
Stir speed / rpm

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Determine the correct measurement duration
› For broad distributions measurement duration must be
sufficient to sample all particles in the system.

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Affect of measurement duration on variability
› Result variability is reduced as measurement duration is
increased
 Variability is within ISO limits when duration ≥10s
8

5
% RSD (Dv50)

0
0 5 10 15 20 25
Measurement duration / s

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Summary of wet method development
› Dispersion
 Choice of dispersant
 Adding energy to disperse agglomerates
 Stabilising the dispersion
 Verifying the state of dispersion
› Measurement conditions
 Sample concentration – obscuration
 Stirrer speed – particle suspension/shearing
 Measurement duration

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Method development for dry dispersion

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When is dispersion important
› The greatest source of error in particle size measurements
depends on particle size
 Dispersion is most important for fine particles
 Sampling is most important for coarse particles

Air pressure
Sampling
Coarse
Fine particles
particles
Feed
Air rate
pressure

Sampling
Feed rate

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Dry powder dispersion: Mechanisms

Energy/aggression

› Importance of each mechanism depends on:

 Disperser geometry
 Flow rate or air pressure
 Material type
› Higher impact energies may improve the dispersion
effectiveness
 Needs to be balanced against the risk of particle break-up
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Dry powder dispersion: Disperser design
› Standard disperser
 Straight through design
 No direct wall impaction
 Suitable for most types of sample

› High energy disperser

 Elbow design
 Direct impaction surface
 Suitable for robust aggregated samples

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Step 1: Setting the feed rate
› Keep the obscuration in range during the measurement
Target range
Obscuration

Time

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Dry powder dispersion: ISO guidance
› Degree of dispersion is controlled by primary air pressure
 Monitor change in size distribution with pressure
• Carry out pressure titration – Step 2

› Check that particle breakup has not occurred

 Compare dry results to a well dispersed wet measurement – Step 3
 Choose the pressure which agrees with the wet results
• Shows dispersion and not particle breakage

Dry dispersion steps:

Step 1: Set up feed rate
Step 2: Measure pressure titration
Step 3: Compare to reference result

© 2017 Malvern Instruments Limited

Step 2: Measure a pressure titration
› Make measurements at 4, 3, 2, 1, 0.5 and 0.1 bar.
› Make repeat measurement at each pressure to check for
sample segregation

© 2017 Malvern Instruments Limited

Step 3: Compare dry results to wet
› Low pressure dry result shows larger result
 Indicates sample is not fully dispersed

© 2017 Malvern Instruments Limited

Step 3: Compare dry results to wet
› High pressure shows good agreement
 Suggests the material is dispersed

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Optional Step 4: High energy venturi
› For robust, highly agglomerated materials the high energy
venturi may be required.
Low pressure

High pressure

© 2017 Malvern Instruments Limited

Comparing standard and high energy venturis

Aero Standard Aero High Energy Wet Dispersion

140
130
120
110
Dv50 / um

100
90
80
70
60
50
40
0 0.5 1 1.5 2 2.5 3 3.5 4
Air Pressure / bar

© 2017 Malvern Instruments Limited

Segregation in dry measurements
› Segregation can occur with free-flowing powders with wide
particle size distributions
 Characterized by a decrease in size over repeat measurements
 Make several quick repeat measurements at each pressure
 This can be done as part of the pressure titration

© 2017 Malvern Instruments Limited

Segregation in dry measurements
› Segregation can occur with free-flowing powders with wide
particle size distributions
 Characterized by a decrease in size over repeat measurements
 Make several quick repeat measurements at each pressure
 This can be done as part of the pressure titration
› Always measure the whole sample, either by:
 Making enough short measurements to use the whole sample and then create an
average
 Make one long measurement long enough to use up all of the sample.

© 2017 Malvern Instruments Limited

Summary of dry method development
› Dispersion mechanisms
› Measurements conditions
 Feed rate
› Pressure titration
 Comparison to well dispersed wet measurement
› Segregation

© 2017 Malvern Instruments Limited

Optical properties and optical models

© 2017 Malvern Instruments Limited

What does laser diffraction measure?
› Laser diffraction systems measure the scattering pattern
produced by an ensemble of particles suspended in a laser
beam

© 2017 Malvern Instruments Limited

What does an optical model do?
› An optical model predicts the scattering pattern produced by
a particle

© 2017 Malvern Instruments Limited

What does an optical model do?
› And can predict the scattering pattern produced by many
particles
10

Volume density / %
6

0
0.01 0.1 1 10 100 1000 10000

Size classes / m

© 2017 Malvern Instruments Limited

How do we use the optical model?
› The Mastersizer measures scattered light energy vs angle
for samples of unknown size distribution
› An optical model can predict the scattering pattern
(scattered light energy vs angle) given a known particle size
distribution
› To obtain a particle size distribution from an unknown
sample we must use the optical model as part of a iterative
process…

© 2017 Malvern Instruments Limited

How do we use the optical model?
Use optical
model

© 2017 Malvern Instruments Limited

Scattering models: Mie Theory
› Models the interaction of light with matter
 Assuming that the particles are spherical
 Assuming that it is a two phase system
› Valid for all wavelengths of light and all particle sizes
› Predicts the dependence of scattering intensity on particle
size
› Predicts that secondary scattering is observed for small
particles

‘For particles smaller than about 50μm Mie theory offers the best general solution’
ISO13320

© 2017 Malvern Instruments Limited

Mie Theory: Predicted scattering

Refracted light

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Mie Theory: Optical properties

Absorption

“….. the Mie theory offers the best

general solution.”
ISO 13320: 2009
© 2017 Malvern Instruments Limited
Scattering models: Fraunhofer approximation
› Basic assumption are similar to Mie Theory
 Assumes the particles are disc shaped
 Assumes it is a two phase system
› Plus the additional assumptions that
 The refractive index difference is high (RRI > 1.3)
 The particles are opaque
 The wavelength of light is much smaller than the particle size
 The angle of the scattered light is small
› In the Mastersizer 3000 software the Fraunhofer approximation is
available as a particle type

‘The advantage of this equation is that it is relatively simple and quick to calculate
‘This Fraunhofer approximation does not make use of any knowledge of the optical
properties of the material’
ISO13320
© 2017 Malvern Instruments Limited
Scattering models: Fraunhofer approximation

© 2017 Malvern Instruments Limited

Comparing the results of the scattering models
Fraunhofer Approximation
Mie Theory

‘If the Fraunhofer approximation is applied for samples containing an

appreciable amount of small, transparent particles, a significantly
larger amount of small particles may be calculated.’

ISO13320
© 2017 Malvern Instruments Limited
Mie vs Fraunhofer: Data quality advice

© 2017 Malvern Instruments Limited

Mie vs Fraunhofer: Data Quality advice

© 2017 Malvern Instruments Limited

Which optical properties do we need?
› To use Mie theory correctly we need to know three optical
properties
 The refractive index of the dispersant
 The refractive index of the sample material
 The absorption of the sample material
• Also called the imaginary part of the refractive index

‘Good understanding of the influence of the complex refractive index in the light scattering
from particles is strongly advised in order to apply the Mie theory or the Fraunhofer
approximation appropriately.’
ISO13320

© 2017 Malvern Instruments Limited

The absorption (or imaginary refractive index)
› The absorption can be determined by looking at the
dispersed sample under a microscope and observing its
 Shape
 Transparency
 Internal structure
› Absorption is generally required to a factor of 10
 E.g. 0.1 or 0.01 (not 0.023)

Images of some calcium carbonate

particles, an absorption of 0.01 would be
used for these particles, due to the
observed transparency of the particles.

© 2017 Malvern Instruments Limited

Estimating absorption from particle appearance
Appearance Absorption Example

0 Latices

0.001 Emulsions

0.01 Crystalline milled powders

0.1 Slightly colored powders

1.0+ Highly colored

(complementary) and metal
powders
© 2017 Malvern Instruments Limited
Methods for determining the refractive index
› Four main routes to refractive index information
References Microscope observations
 ISO 13320 appendix
 Malvern material database
 CRC handbook
 Manufacturers label (dispersant)
 Online (luxpop, webelements,
google scholar)

Refractometer measurements
Empirical/semi-empirical

© 2017 Malvern Instruments Limited

Choosing the refractive index
› A Refractive Index is generally only required to 2 decimal
places
 e.g. 1.42 not 1.4234
 And to an accuracy of ±0.02
› Can be estimated based on similar materials
Refractive index
1 1.5 2 2.5 3

Plastics and elastomers (1.38 – 1.57)

Organic compounds (1.4 – 1.7)

Inorganic salts (1.52 – 1.8)

Metal Oxides (1.6 – 2.5)

© 2017 Malvern Instruments Limited

Assessing the data fit
› The fit report shows the measured and calculated scattering
data
› How well these overlay is known as the data fit
› The residual quantifies how good the fit is
 Residual = area between the two curves

Residual = 0.83%

© 2017 Malvern Instruments Limited

Inspecting the data fit: refractive index
› A poor fit to the focal plane or side-scatter detectors
suggests an incorrect choice of refractive index

Poor fit indicates

incorrect choice of
refractive index

© 2017 Malvern Instruments Limited

Inspecting the data fit: absorption index
› Misfits to the extinction detectors indicate an incorrect
absorption value
 51 in the red light
 63 in the blue light
Poor data fit here indicates
poor choice of absorption

© 2017 Malvern Instruments Limited

Weighted and un-weighted data fits
Example - weighted

Example - unweighted

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Assessing the data fit: Example
› The user is seeing an “unexpected” mode of small material.
› The optical properties used were:
 RI:1.4, Absorption: 0.01

© 2017 Malvern Instruments Limited

Assessing the fit using 1.4/0.01
Weighted fit Weighted Residual = 3.26

Un-Weighted fit Residual = 0.82 Poor fit

= incorrect RI

© 2017 Malvern Instruments Limited

Assessing the fit using 1.54/0.01
Weighted fit Weighted residual = 0.48

Un-Weighted fit Residual = 0.57

Improved fit

© 2017 Malvern Instruments Limited

Looking at the results
› Sample is calcium carbonate
 Reference RI is between 1.53 and 1.63

© 2017 Malvern Instruments Limited

The optical property optimiser (OPO)
› Offers a quick way to adjust optical properties and assess
the fit and result

© 2017 Malvern Instruments Limited

Overview
› Introduction to particle sizing
› Introduction to laser diffraction
› Smarter particle sizing
 Smarter method development
 Data quality advice
› Method development
 Method development for dispersion in liquid
 Method development for dispersion in air
› Choosing the right specifications
 Understanding the size distribution
› Optical properties and optical modes
© 2017 Malvern Instruments Limited