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!

* Rh Tube * Aperture/Rh filter 10x 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 (40kV, 40W) 300µm monocapillary Video: 10 × colour; 100× colour (plus 2× digital zoom) Sapphire™ 80 mm 2 Si(Li) detector Genesis 2000 (Windows XP) Vision32 version 4 software (patented FP and Comb32)

Configuration — Eagle III - OPTIONS

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 mm 2 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 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) Transmission lighting (High Mag View)

Si(Li) Detector properties

Active area (mm 2 ) Be

(coated)

window Processing TC (µsec) Countrate (cps) Resolution @MnKa (eV) 30 80

nominal

8µm 35 5000 10 15000 35 5000

nominal

12µm 10 15000

100,000cps processing capability Absolute intensities: I 30 ≈ I 80

×

55%

≤145 ≤165 ≤155 ≤185

Detector’s relative low energy performances 30mm 2 80mm 2

Glass sample (srm620) Spectra normalised to CaK (3690eV) NaK a MgK a AlK a SiK a 500 700 900 1100 1300 1500 1700 1900 (eV)

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

J

c = 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

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 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: Cr (K) Mn (K) Fe (K) Ni (K) Particle 1 Wt% 18.88

0.44

69.47

11.21

 Particle 1 = Stainless Steel

FP “Standardless” Analysis: Accuracy Bulk Compositional Standard: Stainless 310

Element:

Si(K) Cr(K) Mn(K) Fe(K) Ni(K) Mo(K) Total

Measured Wt%

0.53

24.97

1.44

53.03

19.7

0.32

100

Given Wt%

0.51

24.88

1.39

52.8

19.6

0.23

99.41

Note: Measured with Poly-capillary lens % Error

3.9

0.4

3.6

0.4

0.5

39.1

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

 Silica particles with impurities

Multi-Point Analysis: Chemical Distribution

• Automated Matrix Point Collection • Data ported into Excel

Y Position (mm)

45.82

42.6

43.14

43.67

44.21

45.28

44.75

X Position (mm)

86.1

85.69

85.28

84.86

84.45

Y Position (mm)

84.04

83.63

83.22

82.81

X Position (mm)

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 5x5 Hi-Mag montage Map Image: Total XRF counts in each map pixel

Quantitative Mapping: Geological Sample

FeK Intensity Fe 2 O 3 Wt%

Quantitative Mapping: Geological Sample

SiK Intensity SiO 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?) *

Pixels: 64 x 50 Map * Dwell time: 0.3 s/pixel * Total time ~ 20 minutes

Conclusion: 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