1. Eagle III — Micro-EDXRF System

2. Eagle System Schematic

3. 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)

4. 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

5. 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

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

7. High Sensitivity
Reduced background

8. Eagle System Schematic

9. 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)

10. 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

11. 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

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

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

14. Hi-Magnification Image - Montage 5×5

15. Hi-Magnification Image - Montage 3×3

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

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

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

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

20. Detector’s relative low energy performances
30mm2
80mm2
NaKa
MgKa
AlKa
SiKa
(eV)
Glass sample (srm620)
Spectra normalised to CaK (3690eV)

21. 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.

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

23. Incident X-Ray Spectral Distribution (Modified Excitation Spectrum)

24. Multilevel Sample Analysis

25. 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.

26. 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.

27. Example: Ni Filter – Improve Limits of Detection

28. 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

29. “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

30. “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

31. “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

32. Manual Control and Analysis

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

34. Automated Multi-Point Analysis:
Example: Foreign Particulates

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

36. 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

37. 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

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

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

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

41. 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.

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

43. 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

44. Spectral Mapping:
Mapping Examples

45. 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

46. Spatial Distribution Maps: Facial Tissue
Tissue masked with carbon tape for Si-free zone
Mapping region mm x 11.3 mm

47. 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

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

49. 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

50. Quantitative Mapping: Geological Sample
FeK Intensity
Fe2O3 Wt%

51. Quantitative Mapping: Geological Sample
SiK Intensity
SiO2 Wt%

52. 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

53. Spectral Mapping - Bone FossilizationFe K P Si Na

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

55. Metal Analysis: Coins (Non-Destructive)
* Rare Coin (2 Reichsmark ?)
Conclusion:
Counterfeit Coin
* Pixels: 64 x 50 Map
* Dwell time: 0.3 s/pixel
* Total time ~ 20 minutes

56. 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