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Randell Barker
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$Anderson Bonon Key Points to Achieving Successful Laser Diffraction Method Development September$

3 Method Development Goal: Reproducible method that tracks product performance Choose measurement approach (dry vs. suspension) Establish the parameters for the measurement Vary measurement settings that can influence result - Dry: measurement duration, concentration, air pressure - Wet: sampler selection, dispersion, duration, concentration, sample preparation (mixing + ultrasound) Test method reproducibility - Meet ISO, USP or internal guidelines 2018 HORIBA, Ltd. All rights reserved. 3

Method Development Repeatability and Reproducibility Repeatability: prepare sample, add to wet sampler, re-circulate, measure same multiple times (suspensions only) Reproducibility: prepare sample,

5 Method Development Repeatability and Reproducibility Repeatability: prepare sample, add to wet sampler, re-circulate, measure same multiple times (suspensions only) Reproducibility: prepare sample, measure, drain, repeat (suspensions + dry) Coefficient of variance (CoV) When D50 >10 µm When D50 <10 µm ISO USP 429 ISO USP 429 At median (D50) 3% 10% 6% 20% At D10 and D90 5% 15% 10% 30% 2018 HORIBA, Ltd. All rights reserved. 5

6 Measurement Range of the Main Techniques for Particle Characterization 1 Å 1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1 mm Scanning Electron Microscopy (SEM) > 14 nm ~ Transmission Electron Microscopy (TEM) 1 Å 100 nm Sieving 5 µm ~ 125 mm Laser Diffraction 10 nm 5 mm Dynamic Image Analysis ~ 0.8 µm 30 mm Dynamic Light Scattering 0.3 nm 8 µm Particle Tracking 10 nm 15 µm 2018 HORIBA, Ltd. All rights reserved. 6

$Double Beam Laser Diffraction Instrument Schematic Agitation system Main Detector Fourier lens LED (405 nm) Circulation system Mirror$

7 Double Beam Laser Diffraction Instrument Schematic Agitation system Main Detector Fourier lens LED (405 nm) Circulation system Mirror Fourier lens Laser (650 nm) Particle Secondary detectors Flow cell Backscatter detectors Ultrasound 2018 HORIBA, Ltd. All rights reserved. 7

Different Measurement Options Dry Cell Flow cell

9 Instrument Validation/Verification Polystyrene Standards for Particle Size Calibration (Flow, Fraction and Paste Cell) 1 µm 5 µm 10 µm 100 µm 100 nm 300 nm 5 µm 2018 HORIBA, Ltd. All rights reserved. 9

$Refractive Index Chute Riffling Rotary Riffling Measure at 3 different$ pressures (low, medium, high) Determine optimum pressure based on good

wet measurements Adjust other settings to optimize sample concentration &

can occur on vibrating tray, constant mass flow rate important for stable

11 Method Development Dry Dispersion First get sampling right & determine Refractive Index Chute Riffling Rotary Riffling Measure at 3 different pressures (low, medium, high) Determine optimum pressure based on good dispersion while not breaking particles You can also compare dry vs. wet measurements Adjust other settings to optimize sample concentration & duration Ideally measure all of powder placed into the sampler (Segregation can occur on vibrating tray, constant mass flow rate important for stable concentration during measurement) Once settings chosen, test reproducibility 2018 HORIBA, Ltd. All rights reserved. 11

Pressure Effect on Sample Dispersion Magnesium Stearate D50 (µm) D10 (µm) D90 (µm) 7,686 4,286 13,342 7,478

(%) 1,46 0,96 2,21 3 bar 2 bar 1 bar D50 (µm) D10 (µm) D90 (µm) 8,254 4,580 14,898 8,205 4,568 14,678 8,207

D50 (µm) D10 (µm) D90 (µm) 8,626 4,862 15,258 8,587 4,851 15,039 8,686 4,918 15,381 8,566 4,851 15,109 mean

12 Pressure Effect on Sample Dispersion Magnesium Stearate D50 (µm) D10 (µm) D90 (µm) 7,686 4,286 13,342 7,478 4,220 12,791 7,502 4,234 12,822 7,439 4,189 12,720 mean 7,526 4,232 12,919 Std Dev 0,110 0,040 0,285 CoV (%) 1,46 0,96 2,21 3 bar 2 bar 1 bar D50 (µm) D10 (µm) D90 (µm) 8,254 4,580 14,898 8,205 4,568 14,678 8,207 4,579 14,583 8,236 4,595 14,722 mean 8,226 4,581 14,720 Std Dev 0,024 0,011 0,132 CoV (%) 0,29 0,24 0,90 D50 (µm) D10 (µm) D90 (µm) 8,626 4,862 15,258 8,587 4,851 15,039 8,686 4,918 15,381 8,566 4,851 15,109 mean 8,616 4,871 15,197 Std Dev 0,053 0,032 0,153 CoV (%) 0,61 0,66 1, HORIBA, Ltd. All rights reserved. 12

$with Laser diffraction* 2018 HORIBA, Ltd.$

16 Dynamic Image Analysis x c min Width x area Diameter over projection surface x Fe max Length A x c min x Fe max A = A x area Result compatible with Laser diffraction* 2018 HORIBA, Ltd. All rights reserved. 16

$Stainless Steel Powder for 3D Printers Laser Diffraction (LD) Dynamic Image Analysis$ 3 0.4 3.7 CoV 3.0% 1.8% 4.9% S. Steel B S. Steel B D50 D10 D90 LD 49.4 36.0 71.4 DIA 50.

3 0.4 3.7 CoV 3.0% 1.8% 4.9% S. Steel B S. Steel B D50 D10 D90 LD 49.4 36.0 71.4 DIA 50.

17 Stainless Steel Powder for 3D Printers Laser Diffraction (LD) Dynamic Image Analysis (DIA) S. Steel A S. Steel A D50 D10 D90 LD DIA Std Dev CoV 3.0% 1.8% 4.9% S. Steel B S. Steel B D50 D10 D90 LD DIA Std Dev CoV 1.1% 4.7% 4.6% 2018 HORIBA, Ltd. All rights reserved. 17

) Sampler selection: sample volume Pump & stirrer settings Concentration Measurement

18 Method Development Wet Dispersion First determine RI Choose solvent (water, surfactants, hexane, etc.) Sampler selection: sample volume Pump & stirrer settings Concentration Measurement duration Does the sample need ultrasound? Document size-time plot Disperse sample, but don t break particles Check for reproducibility 2018 HORIBA, Ltd. All rights reserved. 18

2 (3.0%) D50: 102.4 (0.7%) D10: 72.4 (0.2%) D90: 153.

19 Alumina in Different Dispersants D50: 97.2 (2.6%) D10: 71.2 (3.5%) D90: (3.0%) D50: (0.7%) D10: 72.4 (0.2%) D90: (2.2%) Dry Disp. Water D50: 94.8 (1.5%) D10: 68.9 (0.2%) D90: (4.0%) D50: 93.9 (0.7%) D10: 68.0 (0.4%) D90: (1.8%) Ethanol Isopropanol 2018 HORIBA, Ltd. All rights reserved. 19

Alumina in Different Dispersants Dispersion D50 D10 D90 Span Dry 97.2 71.2 135.2 0.659 Water 102.4 72.4 153.2 0.789 Ethanol 94.8 68.

$Alumina Via Orthogonal Techniques Laser Diffraction$ Zoom Camera Basic Camera D50 D10 D90 LD (Dry) 97.

21 Alumina Via Orthogonal Techniques Laser Diffraction (LD) Dynamic Image Analysis (DIA) Dry Dispersion Zoom Camera Basic Camera D50 D10 D90 LD (Dry) LD (H 2 O) DIA CoV 4.2% 1.6% 8.4% Scanning Electron Microscopy (SEM) 2018 HORIBA, Ltd. All rights reserved. 21

$CuO Refractive Index: 2.$

$Refracted Absorbed Polystyrene$ $600i Diffracted Cu(OH) 2 1.72 0.$ 100i Emulsion 1.75 0.

$(Complex Refractive Index) 1.$ valor) Imaginary Index

25 Optical Events Reflected Refracted Absorbed Polystyrene i Copper i Diffracted Cu(OH) i Emulsion i The use of the Mie Theory requires the knowledge of sample optical properties (Complex Refractive Index) i Refractive Index (Real valor) Imaginary Index (absorption) For transparent particles use 0 for the imaginary component For slightly opaque materials use 0.01 or 0.1 For opaque materials use 1.0 or higher 2018 HORIBA, Ltd. All rights reserved. 25

$Refractive Index Effect Most pronounced when: - Particles are spherical - Particles are$ Least pronounced when: - Particles are not spherical - Particles are opaque - RI of particle is

Least pronounced when: - Particles are not spherical - Particles are opaque - RI of particle is

26 Refractive Index Effect Most pronounced when: - Particles are spherical - Particles are transparent - RI of particle is close to RI of fluid - When particles are smaller than ~35-40 µm Least pronounced when: - Particles are not spherical - Particles are opaque - RI of particle is larger than RI of the fluid - When particles are larger than ~35-40 µm 2018 HORIBA, Ltd. All rights reserved. 26

Does result No change Yes keep working significantly? RI: 1.53-0.1i D50: 7.36 µm RI: 1.97-0.0i D50: 7.

27 Practical Approach Measure the sample once Change the RI Determine real component, vary imaginary component to minimize residual R value. Stop worrying! Does result No change Yes keep working significantly? RI: i D50: 7.36 µm RI: i D50: 7.67 µm CoV: 2.9% RI: i D50: 0.43 µm RI: i D50: 0.58 µm CoV: 21.0% Starch emulsion Pectin emulsion 2018 HORIBA, Ltd. All rights reserved. 27

$Refracting$ Valor 2018

$Refracting Index$ 2018 HORIBA, Ltd.

Data Treatment Bimodal Distribution Position the cursor

Case of Study - Wafer Filler First trial: Water dispersion

Case of Study - Wafer Fillers Partial sample solubilization 0.31 µm 10.

72.95 µm Dispersion in iso-propanol After

$Refraction Index$ Improvement

$Data Treatment Refraction Index$ iso-propanol Generic 1.6-0.

Conclusions Must have representative sample Powders: select air pressure Suspensions: wet, disperse Check accuracy w/microscope Investigate system

44 Conclusions Must have representative sample Powders: select air pressure Suspensions: wet, disperse Check accuracy w/microscope Investigate system settings: concentration, agitation, ultrasound Design for maximum precision Follow guidelines in standards 2018 HORIBA, Ltd. All rights reserved. 44

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2018 HORIBA, Ltd. All rights reserved. 1

2018 HORIBA, Ltd. All rights reserved. 1 HORIBA Ltd, Automotive Measurement R&D Dept. Shun Fukami Development Tools for Advanced On-Board Emissions Measurements of NMHC and Particulates, Plus a Coaching