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 mTorr) or No Vacuum (Air) Navigation by Optical Microscope Detection limits improve: 10x 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 – 200X 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 100x Eagle Video (color) Small Fracture in Diamond Table ? Glass-Filled ? Conclusion: Yes! 10x Eagle Video (B/W) * Rh Tube * Aperture/Rh filter

“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 (40kV, 40W) 300µm monocapillary Video: 10× colour; 100× colour (plus 2× digital zoom) Sapphire™ 80 mm2 Si(Li) detector Genesis 2000 (Windows XP) Vision32 version 4 software (patented FP and Comb32)

Configuration — Eagle III - OPTIONS 100µm monocapillary in lieu of the 300µm collimators (1 & 2mm) manually interchangeable filters (for collimator only) 40kV, 20W Cr-anode X-ray tube 50 kV, 50W X-ray tube (Mo, Rh or W anodes) 30 mm2 Si(Li) detector rotation table OR sample backlighting LineScan, Mapping & Image processing software

Sample Illumination: White LEDs Directionally adjustable LED arrays Individual arrays for both Low- & High-mag image views Individual light output adjustment to both arrays at both magnification views Low-mag 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 Normal (100×) Digital Zoom (2× “normal”) Blue security-fibre in banknote

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

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

Si(Li) Detector properties Active area (mm2) Be (coated) window Processing TC (µsec) Countrate (cps) Resolution @MnKa (eV) 30 nominal 8µm 35 5000 ≤145 10 15000 ≤165 80 12µm ≤155 ≤185 100,000cps processing capability Absolute intensities: I30 ≈ I80× 55%

Detector’s relative low energy performances 30mm2 80mm2 NaKa MgKa AlKa SiKa 500 700 900 1100 1300 1500 1700 1900 (eV) Glass sample (srm620) Spectra normalised to CaK (3690eV)

Si(Li) Cooling Standard: Liquid Nitrogen 30 mm2 or 80 mm2 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 This is accomplished by … Improve Limits of Detection Make analysis possible Remove Tube Characteristic Lines Reduce Bremsstrahlung in limited region Eliminate Bragg Diffraction Peaks in limited region This is accomplished by … The Back Arrow will take you to the Outline Slide.

Example: Ni Filter High Sensitivity Region Useful Region Ni Absorption Edge Filter Band Pass Starting from low energy end, filter absorbs all X-rays. (You see detector shelf at low end.) As X-ray energy approaches XRF energy of filter material, the filter transmits more X-rays. Here, we have a Ni filter. You see Ni energy X-rays passing through filter. When we pass the Ni absorption edge, X-rays are heavily absorbed because we have just exceeded the Ni absorption edge. This is the high sensitivity region where background is lowest. Further increase in X-ray energy shows more X-rays passing through filter. It is possible to use the low background region on the low energy side of the filter band pass for elemental information also.

Example: Ni Filter – Improve Limits of Detection

Hardware status monitor for System Maintenance Status of instrument settings & parameters may be monitored in Vision software, for example: Vacuum circuit Safety interlocks Tube/cabinet temperatures Tube power

“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 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   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 Ni(K) 19.7 19.6 0.5 Mo(K) 0.32 0.23 39.1 Total 100 99.41 This is a Stainless Steel with all major alloying elements having X-ray lines of similar energy. This is a best case situation for standardless FP analysis. The 2 big advantages of FP Quantification are that: (1.) Standardless analysis is possible depending on desired accuracy; (2.) If improved accuracy is desired, then accuracy is improved by using a limited set of type standards. Even 1 type standard is enough to improve accuracy in many situations. 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 These are multi-point analyses of 2 areas on a silicon wafer where depositions of test phosphor materials were made. Notice that one of the depositions is extremely inhomogeneous.

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 Fe Map The “Chameleon” ink on a US $100 bill is mapped. The ink contains a mineralogical component. Generation of BMP Elemental Maps

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 The manufacturer of the facial tissue intended for there to be hot spots in the Silicone distribution. The total silicone loading on the tissue was about 1.4 wt%. The low-level silicone distribution was unintended. 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 5x5 Hi-Mag montage Map Image: Total XRF counts in each map pixel

Quantitative Mapping: Geological Sample FeK Intensity Fe2O3 Wt%

Quantitative Mapping: Geological Sample SiK Intensity SiO2 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: Counterfeit Coin * Pixels: 64 x 50 Map * Dwell time: 0.3 s/pixel * Total time ~ 20 minutes

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