Eagle III MicroEDXRF System Eagle System Schematic XRF

Eagle III — Micro-EDXRF System

Eagle System Schematic

XRF Advantages Non-destructive: No beam damage or coating of sample Minimal Sample Preparation: • conductivity not required • sample shape can be irregular Low Vacuum (~ 100 m. Torr) or No Vacuum (Air) Navigation by Optical Microscope Detection limits improve: 10 x or better (vs. SEM-EDS) X-rays are penetrating (microns to millimeters)

Advantages to EDS (Matt’s addition) Cheaper to add EDS to a microscope than to buy an XRF system Orders of magnitude better image quality • CCD camera in XRF has magnification of 150 – 200 X • Resolution comparable to XRF: about 10 nm • SEM image quality can be orders of magnitude better Smaller analytical volume • One order of magnitude always • Another order of magnitude if you can live with lower voltage

Non-Destructive Testing 100 x Eagle Video (color) Small Fracture in Diamond Table ? Glass-Filled ? Conclusion: Yes! * Rh Tube * Aperture/Rh filter 10 x Eagle Video (B/W)

“As Delivered” Sample Analysis Chemical Residues from suspected drug lab X-ray Excitation minimizes sample preparation Qualitative answer in < 2 minutes

High Sensitivity Reduced background

Eagle System Schematic

Configuration — Standard Eagle III Standard features • • • Rh or Mo tube (40 k. V, 40 W) 300µm monocapillary Video: 10× colour; 100× colour (plus 2× digital zoom) Sapphire™ 80 mm 2 Si(Li) detector Genesis 2000 (Windows XP) Vision 32 version 4 software (patented FP and Comb 32)

Configuration — Eagle III - OPTIONS Options • • 100µm monocapillary in lieu of the 300µm collimators (1 & 2 mm) manually interchangeable filters (for collimator only) 40 k. V, 20 W Cr-anode X-ray tube 50 k. V, 50 W X-ray tube (Mo, Rh or W anodes) 30 mm 2 Si(Li) detector rotation table OR sample backlighting Line. Scan, Mapping & Image processing software

Sample Illumination: White LEDs Directionally adjustable LED arrays Individual arrays for both Low- & High-mag image views Low-mag Individual light output adjustment to both arrays at both magnification views High-mag

Color Low-Magnification Image (single) $20 banknote (US)

Color Low-Magnification Image (montage) $20 banknote (US)

Hi-Magnification Image - Montage 5× 5

Hi-Magnification Image - Montage 3× 3

Hi-Magnification Image (Single) + Digital Zoom Blue security-fibre in banknote Normal (100×) Digital Zoom (2× “normal”)

Transmission Sample Backlighting Fine “Hi-Purity” Silica particles Reflective lighting Transmission lighting

Transmission Sample Backlighting Transmission lighting (Low Mag View) (High Mag View)

Si(Li) Detector properties Active area (mm 2) 30 80 Be (coated) window Processing TC (µsec) Countrate (cps) Resolution @Mn. Ka (e. V) 35 5000 ≤ 145 10 15000 ≤ 165 35 5000 ≤ 155 10 15000 ≤ 185 nominal 8µm nominal 12µm 100, 000 cps processing capability Absolute intensities: I 30 ≈ I 80× 55%

Detector’s relative low energy performances 30 mm 2 80 mm 2 Glass sample (srm 620) Spectra normalised to Ca. K (3690 e. V) Na. Ka Mg. Ka Al. Ka Si. Ka 500 700 900 1100 1300 1500 1700 1900 (e. V)

Si(Li) Cooling Standard: Liquid Nitrogen • • 30 mm 2 or 80 mm 2 5 L dewar ≥ 3 day hold time Detector can be allowed to warm when not in use. Detector High Voltage bias is switched off when detector warms.

Capillary X-ray Optics Jc = f(1/E) “Total” Reflection of X-rays inside glass capillary

Incident X-Ray Spectral Distribution (Modified Excitation Spectrum)

Multilevel Sample Analysis

Filter Benefits Improve Limits of Detection Make analysis possible This is accomplished by … Remove Tube Characteristic Lines Reduce Bremsstrahlung in limited region Eliminate Bragg Diffraction Peaks in limited region

Example: Ni Filter Band Pass High Sensitivity Region Useful Region Ni Absorption Edge

Example: Ni Filter – Improve Limits of Detection

“Vision” Software: Modes of Operation Manual point to point Automated multiple point, lines or matrices Analyze within an area and add spectra together Line Scan (generates a plot) Elemental Imaging and Spectral Mapping

“Vision” Software: Applications Qualitative Analysis (what elements and where) Quantification: • Fundamental Parameter Modeling Quantification without standards and with type standard(s) {Patented} • Semi-empirical quantification with type standards

“Vision” Software: Applications (cont’d) Coating thickness • FP modeling with standards correction Spectral Match (Known alloys - ID unknown) Line Scan Elemental Imaging and Spectral Mapping Image Manipulation and Overlay

Manual Control and Analysis

Automated Multiple Point Analyses Navigate to Feature Save Coordinates in Stage Table

Automated Multi-Point Analysis: Example: Foreign Particulates

Foreign Particulates in Silica Transmission lighting (Low Mag View) Transmission lighting (High Mag View)

FP “Standardless” Analysis: Particle 1 Element: Wt% Cr (K) 18. 88 Mn (K) 0. 44 Fe (K) 69. 47 Ni (K) 11. 21 Particle 1 = Stainless Steel

FP “Standardless” Analysis: Accuracy Bulk Compositional Standard: Stainless 310 Element: Measured Wt% Given Wt% % Error Si(K) 0. 53 0. 51 3. 9 Cr(K) 24. 97 24. 88 0. 4 Mn(K) 1. 44 1. 39 3. 6 Fe(K) 53. 03 52. 8 0. 4 Ni(K) 19. 7 19. 6 0. 5 Mo(K) 0. 32 0. 23 39. 1 Total 100 99. 41 Note: Measured with Poly-capillary lens

Foreign Particulates in Silica Particle “ 2” Particles “ 3” and “ 4”

Foreign Particulates in Silica Particle 2 Particle 1 “Stainless” Steels Same Alloy

Foreign Particulates in Silica Particle 3 Particle 4 Silica particles with impurities

Multi-Point Analysis: Chemical Distribution • Automated Matrix Point Collection • Data ported into Excel

Spectral Mapping Definition Collect and save XRF spectrum at each map pixel Database correlating each spectrum to position (X, Y)

Spectral Mapping: Search and Use of Data Spectral Display: • Point by point • Summation of selected region or total map • Display of Linear Distributions Return to Sample using Map for collection of spectrum with improved statistical significance Quantitative mapping

Spectral Mapping: Mapping Examples

Elemental Spatial Distribution Maps: Paper Fe X-rays penetrate paper Mg Map Al Map • Generation of BMP Elemental Maps Fe Map

Spatial Distribution Maps: Facial Tissue • Tissue masked with carbon tape for Si-free zone • Mapping region 15. 6 mm x 11. 3 mm

Spatial Distribution Maps: Facial Tissue • Recall spectra from mapped pixels • Hot Si spots hide low-level Silicone coverage

Spatial Distribution Maps: Facial Tissue • 3 individual color logarithmic scales (NIST) • Low level Silicone distribution exposed in Green

Quantitative Mapping: Geological Sample • Sedimentary rock • Epoxy-embedded “puck” used to make thin sections • Map area defined by 5 x 5 Hi-Mag montage Map Image: Total XRF counts in each map pixel

Quantitative Mapping: Geological Sample Fe. K Intensity Fe 2 O 3 Wt%

Quantitative Mapping: Geological Sample Si. K Intensity Si. O 2 Wt%

Multi-Field Mapping: Geological Sample • 7 adjacent High Mag Camera FOV • Map more layers in shorter time • Maps are stitched together in SW utility while adjusting map intensities

Spectral Mapping - Bone Fossilization Fe K P Si Na

Map Image Overlays: Bone Fossilization Fe – Red K – Blue Si – Yellow P – Gray Na - Green

Metal Analysis: Coins (Non. Destructive) * Rare Coin (2 Reichsmark - 1927? ) Conclusion: * Pixels: 64 x 50 Map * Dwell time: 0. 3 s/pixel * Total time ~ 20 minutes Counterfeit Coin

Eagle Applications Glass, Ceramics (inhomogeneity, inclusions, particles) Metal alloys (inhomogeneity, particles, wire filament) Inorganic contaminants, residues, deposits (ex. Corrosion) Inorganic additives polymers, paints, inks Inclusions in plastics, “light element” materials Coating thickness and distribution of coating thickness