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Practical Experiences with a Variety of Instrumentation for Diffuse
Reflectance Measurements
Arnold Eilert
Unity Scientific
Overview
• “Real World” Deviations from the “Ideal”
• Diffuse Reflectance (I/Io) Measurement Approaches – Sample & Reference
• Sample Measurement Considerations, Challenges, Obstacles, and Strategies
• Various Examples to Illustrate
Diffuse Reflectance NIR Measurements
Diffuse Reflectance NIR
Specular Diffuse
Reflectance Modes
Diffuse Reflectance Theory
Ideal versus Reality
Diffuse Reflectance NIR
Impinging Radiation
Detectors
Sample Sample
Incident
Radiation
Return
Radiation
Sample
Integrating
Sphere
Close Proximity
Detectors
Fiber Optic
Bundle
Diffusely Reflected RadiationCollection Schemes
Remote
Non-Contact
Diffuse Reflectance NIR
Diffuse Reflectance NIR
“Absorbance” = -Log(R); R = I/Io
Various Referencing Schemes for Io
Particle Size Effects
Density Effects
Practical Diffuse Refl. NIR
Distance Effects
Residual Sample (Contaminant) Effects
“Practical” Diffuse Refl. NIR
• Flour – Compression/Compaction
• Tissue Paper - Compression
• Tissue Paper – “Infinite Thickness”
Diffuse Reflectance NIR Experiments(“Academic” Tests using Model 2600XT)
“Practical” Diffuse Refl. NIR
Variable Compaction Pressure StudyInfraAlyzer 400 & InfraAlyzer 500 w/ Edapt Probe
“Practical” Diffuse Refl. NIR
• Wheat flour placed in rotating cup on SpectraStar XT unit
• Uniform weights incrementally added to top of plunger
“Practical” Diffuse Refl. NIR
Flour Compaction PressureMeasurement Levels
0.034 PSI
0.689 PSI
Wheat Flour; Variable Compaction PressureAbsorbance Spectra; 680-2600 nm
Wheat Flour; Variable Compaction PressureAbsorbance + SNV + 1st Derivative Spectra; 680-2600 nm
균ж
Variable Compaction – Wheat Flour Protein
Variable Compaction – Wheat Flour Moisture
Variable Compaction – Wheat Flour Ash
A. Tissue Paper Compression
“Academic” Diffuse Refl. NIR
• 15 Layers of Paper Placed on Window
• Increasing Pressure Applied
B. “Infinite Thickness” Demonstration
• Consistent Pressure Applied
• Layers Peeled Off One-by-One
• Influence of Backing Evaluated
1 2
3 4
Tissue Paper (15 Thick) & Styrofoam Plate BackingAbsorbance Spectra
Styrofoam Plate (Backing)
Tissue Paper (15 Thick)
15 Layers Thick (Moderate Compression) = Approx. 0.25 inch Thick
丠
Increasing Compaction
Pressure (PSI)0.05
0.10
0.16
0.21
0.26
0.31
0.37
0.42
0.47
0.52
0.58
Total Paper Thickness ~ 0.25 inch
Tissue Paper (15 Layers Thick)Absorbance Spectra; 680-2600 nm
Increasing
Weight
(Lbs)
丠
Tissue Paper (15 Layers Thick)Absorbance Spectra; 680-1900 nm
680-1100 nm
Tissue Paper (15 Layers Thick)Absorbance + 1st Derivative Spectra; 680-1900 nm
斐С
Tissue Paper (15 Layers Thick)Absorbance + SNV + 1st Derivative Spectra; 680-1900 nm
窠С
Tissue Paper (15 Layers Thick)Predicted “Pulp Viscosity” versus Compression Pressure
“Academic” Diffuse Refl. NIR
“Infinite Thickness” Demonstration
~ 0.6 PSI
15 Layers(0.25”)
1 Layer
Tissue Paper (Varying # of Layers)Absorbance Spectra
Polystyrene “Contaminant”
析С
Tissue Paper (Varying # of Layers)Absorbance Spectra
窠С
Tissue Paper (Varying # of Layers)Absorbance Spectra; 1600-1900 nm
析С
Tissue Paper (Varying # of Layers, 1 - 15)Absorbance Spectra; 680-1750 nm
窠С
Tissue Paper (Varying # of Layers, 1 - 15)Absorbance Spectra; 680-1400 nm
析С
Tissue Paper (Varying # of Layers, 1 - 15)Absorbance + SNV + 1st Derivative Spectra
窠С
Tissue Paper (Varying # of Layers, 1 - 15)Absorbance + SNV + 1st Derivative Spectra
挠Т
Tissue Paper (Varying # of Layers, 1 - 15)Absorbance + SNV + 1st Derivative Spectra; 680-1400 nm
Х
To Grind, or Not to Grind???
Practical Diffuse Refl. NIR
Particle Size / Compaction
• To homogenize composition of a larger sample (i.e. representative subsampling)
• To get best results with for some properties with complex/layered products (seeds, coated products, . . .)
• To minimize variable particle size effects
• To minimize “macro” particle size effects
• Simply to make the sample presentable to the instrument
Why Choose the Grinding Option?
Rotating Transport Linear Transport
Diffuse Reflectance NIR
Particle Heterogeneity/Orientation Effects
Unground “Crystal” Ground “Crystal” Unground “High Impact”
Polystyrene Pellets – Ground & Unground
“Crystal” Pellets
“High Impact” Pellets
Gnd “Crystal” Pellets
Clear Layer / Transfl.
Polystyrene Pellets – ComparisonsAbsorbance Spectra
Х
.4
.6
.8
1
1.2
1.4
1.6
1000 1200 1400 1600 1800 2000 2200
High Impact Polystyrene, “Full Range” Spectra
SpectraStar 2200 RTW
512 Element InGaAs Diode Array
Analyzer
湰Ь
Diode Array Unit (512 Element): Ethylene Copolymer Pellets; 920-1700 nm
Absorbance Spectra
All Samples
Varying % Vinyl Acetate
Т
Absorbance Spectra
Select Samples
Varying % Vinyl Acetate
Diode Array Unit (512 Element): Ethylene Copolymer Pellets; 920-1700 nm
Х
1.6%
3.8%
8.8%
9.5%
15.2%
18.3%
27.4%
32.2%
Absorbance + 2nd Derivative Spectra
Select Samples
Varying % Vinyl Acetate
Diode Array Unit (512 Element): Ethylene Copolymer Pellets; 1300-1360 nm
Х
1.6%
3.8%
8.8%
9.5%
15.2%
18.3%
27.4%
32.2%
Absorbance + 2nd Derivative Spectra
Select Samples
Varying % Vinyl Acetate
Diode Array Unit (512 Element): Ethylene Copolymer Pellets; 1580-1650 nm
Х
Absorbance Spectra
2 Wavelength MLR Calibration:
# Samples = 10 + 1 Val Sample
R-Squared = 0.99940
S.E.C. = 0.306
Absorbance + 1st Derivative Spectra
2 Wavelength MLR Calibration:
# Samples = 10 + 1 Val Sample
R-Squared = 0.99993
S.E.C. = 0.103
512 Element Diode Array Unit: Ethylene Copolymer Pellets
Absorbance Spectra
All Samples
Varying % Vinyl Acetate
Т
Smokeless Gunpowder
Graphite Coated Uncoated
Graphite Coated
Uncoated
Smokeless GunpowderAbsorbance Spectra
湰Ь
Soy White Flakes
Ground Unground
White Flake - UngroundAbsorbance Spectra
Measured on SpectraStar 2600 XT
12 Individual Cup Orientations
White Flake - UngroundAbsorbance Spectra
Measured on SpectraStar 2500 XL-R
12 Individual Cup Orientations
White Flake - UngroundAbsorbance + SNV + 1st Derivative Spectra
Measured on SpectraStar 2600 XT
12 Individual Cup Orientations
湰Ь
White Flake - UngroundAbsorbance + SNV + 1st Derivative Spectra
Measured on SpectraStar 2500 XL-R
12 Individual Cup Orientations
湰Ь
White Flake - UngroundAbsorbance Spectra
Measured on SpectraStar 2500 XL-R
12 Repeated Measurements- Step Rotation
湰Ь
Soy White Flake - UngroundAbsorbance + SNV + 1st Derivative Spectra
Measured on SpectraStar 2500 XL-R
12 Repeated Measurements- Step Rotation
析С
White Flake - UngroundAbsorbance Spectra
Measured on SpectraStar 2500 XL-R
12 Repeated Measurements- Continuous Rotation 90 deg/s
析С
White Flake - UngroundAbsorbance + SNV + 1st Derivative Spectra
Measured on SpectraStar 2500 XL-R
12 Repeated Measurements- Continuous Rotation 90 deg/s
湰Ь
Grind & Rotation Comparison
1. Measurements at 12 Different Orientations
2. Step Rotation; 12 Measurements
3. Continuous Rotation 90 deg/s; 12 Measurements
4. Continuous Rotation 30 deg/s; 12 Measurements
A. Unground White Flake
1. Measurements at 12 Different Orientations
2. Step Rotation; 12 Measurements
3. Continuous Rotation 90 deg/s; 12 Measurements
4. Continuous Rotation 30 deg/s; 12 Measurements
B. Ground White Flake
Unground White Flake SampleAbsorbance Standard Deviation
Ground White Flake SampleAbsorbance Standard Deviation
Ground White Flake SampleAbsorbance Standard Deviation
(Expanded Y-Axis)
Unground White Flake Sample
Practical Implications using Spectra to Predict Percent Oil
Grinding – The Only Way to Go???
White, Yellow, Pink (w/ TiO2)
Red, Green, Blue, Violet (w/o TiO2)
Black (w/ Carbon Black)
Polypropylene Plastic Container Parts; Various ColorsGround Product Spectra; I/A 500 w/ Rotating Cup Drawer
뫀л
Polypropylene Plastic Container Parts; Various ColorsGround Product Spectra; I/A 500 w/ Rotating Cup Drawer
3 Wavelength MLR Calibration for % Slip
Red, Green, & Blue Parts
Corr. Coef. = 0.993
S.E.C. = 0.080
@ې
3 Wavelength MLR Calibration for % Slip
Skew & Bias Adjusted for White Parts
S.E.P. = 0.144
Polypropylene Plastic Container Parts; Various ColorsGround Product Spectra; I/A 500 w/ Rotating Cup Drawer
뫀л
3 Wavelength MLR Calibration for % Slip
Skew & Bias Adjusted for White Parts
S.E.P. = 0.144
Polypropylene Plastic Container Parts; Various ColorsGround Product Spectra; I/A 500 w/ Rotating Cup Drawer
Excluded
@ܠ
Particle Size / Compaction
• Calibrations estimating particle size
• Wheat hardness estimation (using MLR equation)
• Avoid heating / moisture loss caused by grinding
• Avoid grinding step – practical trade-off
Q: When might you NOT want to minimize variance due to particle size variation(using preprocessing, grinding, . . .)???
Diffuse Reflectance NIR
Diffuse Transflectance Mode
Q: Which sampling mode is most appropriate for the application?
A: Determined by the optical and physical characteristics of the product being analyzed:
• Powders / Granulates - Reflectance
• Formed Solids - Reflectance / Transmission
• Liquids / Films / Gels
Clear - Transmission / Transflectance
Semi-Opaque - Transflectance
Opaque - Reflectance / Transflectance
Diffuse Reflectance NIR
1 2
3 4
Liquid Cup + Transflectance Insert
Egg Yoke – SpectraStar 2400 RTW
0.1 mm Insert
0.2 mm Insert
0.3 mm Insert
0.4 mm Insert
Transflectance Mode; Absorbance Spectra
뫀л0.1 mm Insert
0.2 mm Insert
0.3 mm Insert
Egg Yoke – SpectraStar 2400 RTWTransflectance Mode; Absorbance Spectra
뫀л
0.1 mm Insert
0.2 mm Insert
0.3 mm Insert
0.4 mm Insert
Egg Yoke – SpectraStar 2400 RTWAbsorbance + 1st Derivative Spectra
뫀л
Egg Yoke – SpectraStar 2400 RTWAbsorbance + SNV + 1st Derivative Spectra
뫀л
1 2
3
“Special Purpose” Compression Transflectance Cup
Caramel Sample Placed in SpectraStar Drawer
Final Tightening Step – Change with Position
1
2
3
4
5
1
2
3
4
5
Absorbance Spectra
Final Tightening Step – Change with Position
Final Tightening – Change with Position
Absorbance + SNV + 1st Derivative Spectra
Different Caramel Products
Absorbance Spectra
Absorbance + SNV + 1st Derivative Spectra
Different Caramel Products
Intact Measurement – The Only Way to Go???
Filled Sample Cup Placed for Measurement
Smear of an Individual Capsule Liquid onTransflectance-Mode Reflector Surface
Transflectance Reflector placed in Liquid CupAgainst Glass for Measurement (0.3 mm Path Length)
Bulk Capsules in Rotating Open CupReflectance Mode
Exctracted Liquid from Single CapsuleTransflectance Mode
Nutraceutical Capsules – SpectraStar 2500X RTWReflectance versus Transflectance Mode; Absorbance Spectra
뫀л
Nutraceutical Capsules – SpectraStar 2500X RTWReflectance versus Transflectance Mode; Absorbance Spectra
Bulk Capsules in Rotating Open CupReflectance Mode
Exctracted Liquid from Single CapsuleTransflectance Mode
뫀л
Individual Pack (Black) vs Average of 4 Packs (Red)
Nutraceutical Capsules – SpectraStar 2500X RTWBulk Capsules in Rotating Open Cup; Absorbance Spectra
뫀л
Nutraceutical Capsules – SpectraStar 2500X RTWBulk Capsules in Rotating Open Cup; Absorbance + SNV + 1st Deriv Spectra
Individual Pack (Black) vs Average of 4 Packs (Red)800-2200 nm Range
뫀л
Regions of Highest Degree of Undesirable Variance “Blotted Out”
Nutraceutical Capsules – SpectraStar 2500X RTWBulk Capsules in Rotating Open Cup; Absorbance + SNV + 1st Deriv Spectra
Individual Pack (Black) vs Average of 4 Packs (Red)800-2200 nm Range
뫀л
Confirmed misidentified (bad) sample in test set
A-Type CapsulesQuantitative Feasibility Evaluation
뫀л
A
E
A
E
A
E
A
E
Bad
Bad
Regions of Highest Degree of Undesirable Variance “Blotted Out”
Nutraceutical Capsules – SpectraStar 2500X RTWBulk Capsules in Rotating Open Cup; Absorbance + SNV + 1st Deriv Spectra
Discriminant Analysis Potential Evaluation
Nutraceutical Capsules – SpectraStar 2500X RTWBulk Capsules in Rotating Open Cup; Absorbance + SNV + 1st Derivative
Cluster Model Discriminant Analysis
嵐У
Corn Syrup Types:
DE28DE63DE9942FCS55FCSHMCS
Corn Syrup Grades – SpectraStar 2400DTransflectance Mode; 0.3 mm PL; Absorbance Spectra
я
Corn Syrup Grades – SpectraStar 2400DTransflectance Mode; 0.3 mm PL; Absorbance + SNV + 1st Deriv Spectra
All Calibration Spectra
Corn Syrup Types:
DE28DE63DE9942FCS55FCSHMCS
Average Spectra for Each Type
Corn Syrup Grades – SpectraStar 2400DTransflectance Mode; 0.3 mm PL; Absorbance + SNV + 1st Deriv Spectra
Corn Syrup Types:
DE28DE63DE9942FCS55FCSHMCS
뫀л
Average Spectra for Each Type1450-1820 nm
Corn Syrup Grades – SpectraStar 2400DTransflectance Mode; 0.3 mm PL; Absorbance + SNV + 1st Deriv Spectra
뫀л
Corn Syrup Grades – SpectraStar 2400DTransflectance Mode; 0.3 mm PL; Absorbance + SNV + 1st Deriv Spectra
Average Spectra for Each Type2050-2350 nm
뫀лDE9942FCS
DE28
HMCS55FCS (HFCS)
DE63
Cluster Model for Corn Syrup Qualification; Scores Plot of Factor 3 vs Factor 2(Circles represent Factor Space Occupied by Corresponding Type)
Cluster Model Discriminant Analysis
뫀л
10oC - 86oC RangeT
Temperature can influence band shape and peak position
뫀л
T
뫀л
Diffuse Reflectance NIR
• Sample presentation consistency (minimize controllable variables)
• Optimize optics, general performance of instrument, sampling mode
• Utilize the optimal spectral region
• Optimize the calibration (# factors / wavelengths, mathematical pretreatment, proper exclusion of outliers . . .)
Getting Optimal Results
• Keep an open mind . . .- but keep in mind the fundamentals
• Diffuse reflectance NIR doesn’t do it all- but it does a lot!
Summary
Diffuse Reflectance NIR
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