Amptek Inc.

14 Deangelo Drive
Bedford, MA 01730 USA
www.amptek.com

Overview of X-Ray Fluorescence

Analysis

AMPTEK, INC.
14 Deangelo Drive, Bedford, MA 01730
Ph: +1 781 275 2242 Fax: +1 781 275 3470
sales@amptek.com www.amptek.com

XRF Overview 1
 Amptek Inc.
14 Deangelo Drive
Bedford, MA 01730 USA
www.amptek.com

What is X-Ray Fluorescence (XRF)?

– A physical process:
Emission of characteristic "secondary" (or fluorescent) X-rays from a
material that has been excited by high-energy X-rays or gamma rays.

– A technique in analytical chemistry:

Method to identify elements in a sample and measure their
concentrations

Non-destructive, quick, and simple to carry out.

XRF Overview 2
 Amptek Inc.

Physical Process 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

– Incoming radiation hits an atom

– Ejects an electron from an inner
shell, creating a vacancy

– An electron from an outer shell

“drops down” to fill the vacancy.

– The excited atom emits an X-ray

with energy equal to the difference
between the levels
E Xray =∆E =EK − EL

– Since each element has a unique

set of levels, it produces a unique
set of “characteristic” X-rays

XRF Overview 3
 Amptek Inc.

Physical Process 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

Fe Ni Cu Zn Pb
Atomic Levels
K 1s 7,112 8,333 8,979 9,659 88,005
L1 2s 845 1,009 1,097 1,196 15,861
L2 2p1/2 720 870 952 1,045 15,200
L3 2p3/2 707 853 933 1,022 13,035
M1 3s 91 111 122 140 3,851
M2 3p1/2 53 68 77 91 3,554
M3 3p3/2 53 66 75 89 3,066
Characteristic X-Ray Lines
Kα1 K – L3 6,404 7,478 8,048 8,639 74,969
Kα2 K – L2 6,391 7,461 8,028 8,616 72,804
Kβ1 K – M3 7,058 8,265 8,905 8,572 84,936
Lα1 L3 – M5 705 852 930 1,012 10,552
Lα2 L3 – M4 705 852 930 1,012 10,450
Lβ1 L2 – M4 718 869 950 1,035 12,614

– XRF is similar to optical spectroscopy but at higher energy

– Independent of chemical state → Elemental analysis

XRF Overview 4
 Amptek Inc.

Measurement 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

– Intensity of X-ray line proportional to number of atoms → Quantitative

– X-rays pass through surface into sample
→ Nondestructive and no sample preparation is necessary
Best accuracy requires sample preparation
→ Bulk measurement rather than only surface
Notion of “bulk” vs “surface” depends on the X-ray energy

XRF Overview 5
 Amptek Inc.

Measurement 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

Iron
Nickel
Cu Kα & Kβ Zn Kα & Kβ
Copper
Zinc
Brass (Cu/Zn alloy)

Zn Kα

Cu Kα Zn Kα

Cu Kβ

Ni Kα
Ni Kβ

Fe Kα
Fe Kβ

0 2 4 6 8 10 12 14
Energy (keV)

– Presence of Cu and Zn K lines → Elements are in sample (qualitative)

– Intensity of the lines → How much is in sample (quantitative)

XRF Overview 6
 Amptek Inc.

Measurement 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

7000
Blank
Br Kα RoHS/WEEE Reference
6000 Heavy Metals in PVC Low
High
5000 Cl Kα

4000
Counts

Hg Lα ,Lβ ,Lγ Pb Lα ,Lβ ,Lγ Cd Kα

3000

2000
Backscattered
Cr Kα X-ray tube continuum
1000

0
0 5 10 15 20 25 30
Energy (keV)

Certified XRF

Typical spectrum and results

Cr 1000 + 20 895 + 198
Br 1100 + 22 1089 + 23

High
Cd 300 + 6 264 + 28
Hg 1100 + 22 1050 + 53
– Photopeak intensity varies with concentration Pb
Cr
1200
401
+
+
24
8
1184
388
+
+
39
167

– Final result is quantitative concentration

Br 500 + 10 487 + 13

Low
Cd 100 + 5 68 + 13
Hg 200 + 5 183 + 27
Pb 400 + 8 398 + 23
Cr 0 + 5 7 + 40
Br 0 + 5 1 + 2
Blank Cd 0 + 5 9 + 10
Hg 0 + 5 0 + 0
Pb 0 + 5 10 + 9

XRF Overview 7
 Amptek Inc.

Measurement 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

What are the main factors limiting XRF?

– Counting variance
• The measurement is based on count discrete X-rays
• Arise from random processes → Inherent statistical variation in number of X-rays
• Percent uncertainty = 1/√N
– 100 X-rays detected → 10% precision
– 1,000 X-rays detected → 3% precision
– 1,000,000 X-rays → 1000 ppm precision
• Good precision means many X-rays which means high count rates or long times

– Detector response
• Photopeak has some width
• There is always spectral background and overlapping peaks
• Ability to remove these depends on counting variance, energy resolution, and
accuracy of software algorithms
• Better energy resolution helps but there are physical and practical limits

XRF Overview 8
 Amptek Inc.

Measurement 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

What are the main factors limiting XRF?

– Attenuation lengths
• Penetration depth depends on energy & therefore element
– In silica, Al X-rays go 3 µm while Sn go 3 mm
• Response depends on energy/element
• Sample condition & homogeneity are critical
1.0E+01
Atten length silica (cm)

1.0E+00 1 cm

1.0E-01 1 mm

1.0E-02 0.1 mm

1.0E-03 10 micron

Mg Al Si P S Cl Ca Cr Fe Ni Zn As Br Zr Ag Sn Ba Sm W Pb U
1.0E-04
1 10 100
Energy (keV)

XRF Overview 9
 Amptek Inc.

Measurement FAQ 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

• How accurate is EDXRF?

– In the best case, relative accuracy ~ 0.2% (1.00% + 20 ppm).
Requires sample prep, a known matrix, good statistics, etc
– Nondestructive screening, relative accuracy ~ 2% (1.00 + 0.02%)
Requires careful optimize and setup, known sample type
– Quick check on unknown, relative accuracy ~20% (1.0 + 0.2 %)

• What is the detection limit for EDXRF?

– <1 ppm for prepared samples in a known matrix under good conditions
– 10 ppm in nondestructive screening with no interfering elements
– When elements interference or overlap, 1% of other element

• What elements can be analyzed with EDXRF?

– Na to U (down to Be with EDS)
– Low Z elements (below S) are a challenge
– Need multiple measurements to cover a wide range of elements

XRF Overview 10

Measurement
XRF is one of many methods
used in material analysis
Advantages of XRF
– Non-destructive
– No sample preparation
– Fast (seconds to minutes)
– Good precision and accuracy
– Measure Na to U
– Suitable for portable
equipment and field use
XRF Overview
Amptek Inc.
14 Deangelo Drive
Bedford, MA 01730 USA
www.amptek.com
Disadvantages of XRF
– Limits of detection modest (10
ppm typical)
– Accuracy usually modest (few %
relative)
– Difficult to use for lower Z
elements
Best results require
– Sample preparation (damaging)
– System optimization
– Matched calibration standards
11
 Amptek Inc.
14 Deangelo Drive
Bedford, MA 01730 USA
www.amptek.com

XRF Applications

How is XRF used?

XRF Overview 12
 Amptek Inc.

Hazardous Material Screening 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

• Is there cadmium on this toy?

• Is there lead in this paint?

• Does this circuit board contain

Pb, Cd, or Cr?

• Nondestructive critical for

screening products!
3,500 3,000 2,000

Amptek SDD Lead paint on wood Amptek SDD

Cu Kα Br Kα Ti Kα
3,000 "Pb free" circuit board 2,500 Pb Lα & Lβ & Lγ
Cd painted PVC
1,500 Cr Kα Cd Kα & Kβ
2,500
2,000 Fe Kα
Ti Kα Zn Kα
Sn Kα Cl Kα
2,000
Ag Kα
Pb Lα & Lβ
Counts

Counts
Counts

1,500 Ca Kα 1,000

1,500

1,000
1,000
500

500
500

0 0 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 0 5 10 15 20 25 30 35 40
Energy (keV) Energy (keV) Energy (keV)

XRF Overview 13
 Amptek Inc.

Metal Alloy Analysis 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

• Are these bolts stainless steel 316? 4,500

Au
Gold plated
4,000
High-rel connector
• Is there Ni in this scrap metal?
Lα & Lβ & Lγ
3,500

• Is there Cd plating on this MILSPEC

3,000
Cu Kα

2,500
Zn Kα

connector?

Counts
2,000

• How much Au is in a white gold ring?

1,500

1,000

• Speed critical, accuracy moderate 500

0
0 5 10 15 20 25 30
Energy (keV)

2,500
40,000

Stainless steel 316 White gold ring

35,000
Fe Kα Au Lα & Lβ & Lγ
2,000
Cu Kα
30,000

Zn Kα
25,000 1,500
Ni Kα

Counts
Counts

20,000

1,000
15,000
Cr Kα

10,000
Mo Kα 500

5,000 Ni Kα

0
0 0 5 10 15 20 25 30 35 40
0 5 10 15 20 25 30
Energy (keV)
Energy (keV)

XRF Overview 14
 Amptek Inc.

Art and Archeology 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

• How did the artist make their paints?

• Is this an ancient or a modern
pigment?
• What is the effect of cleaning on the
surface of a statue?

• Nondestructive testing is vital for art!

XRF Overview 15
 Amptek Inc.

Process Control 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

• Is there any change in spectrum? Multilayer metal

• Absolute composition not needed but

quick, real-time, non-destructive vital.

XRF Overview 16
 Amptek Inc.

Field Measurements 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

Measuring ores in mines. Identifying minerals

on Mars.
3.0E+04
Ca Kα
Amptek FastSDD
Fe Kα
Rare Earth Ore
Sr Kα
2.0E+04
Counts

1.0E+04

Pb L lines Backscatter from

X-ray tube
La Kα Ce K
α

0.0E+00
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
Energy (keV)

Measuring soil
contamination

XRF Overview 17
 Amptek Inc.
14 Deangelo Drive
Bedford, MA 01730 USA
www.amptek.com

Related Analytical Methods

XRF Overview 18
 Amptek Inc.

Related 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

Energy Dispersive X-ray Spectroscopy

– a.k.a. EDS, EDX, XEDS, EDXA
• Uses electron beam in vacuum chamber to excite the atoms
• Electrons have short range in matter → Only way to measure lightest
elements, down to Be (Z of 4)
• High spatial resolution (75 um spatial, 1 um in depth)

1.0E+05

8.0E+04
Amptek FastSDD
Be Kα

6.0E+04
Counts

C Kα O Kα

4.0E+04

2.0E+04 Al Kα

0.0E+00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Energy (keV)

XRF Overview 19
 Amptek Inc.

Related 14 Deangelo Drive

Bedford, MA 01730 USA
www.amptek.com

Wavelength Dispersive X-ray Spectroscopy (WDXRF)

– Crystal diffractometer disperses the X-ray wavelengths much like a
prism disperses visible light.
– X-rays at a particular wavelength (energy) are recorded by a detector.
– It measures only one energy at a time; It obtains a spectrum by
sweeping the wavelength over time

– Advantages of WDXRF
• Much better energy resolution
• Leads to much better accuracy and detection limits
– Disadvantage of WDXRF
• Very long time to acquire whole spectrum
• Requires destructive sample preparation

– Uses similar detectors and signal processors

XRF Overview 20