What is XRF ?

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What is XRF ?
• X-Ray Fluorescence (XRF) is an analytical method to
determine the chemical composition of all kinds of
materials.
• The types of material that can be analyzed are
– Solids
– Liquids
– Powders
– Filters
– Fusion beads

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What is XRF?
• Analysis as push button method
• Precise: 0.1 – 0.3 % relative
• Accurate: LLDs 0.1 ppm to 100%
• Easy sample preparation without chemicals
• Fast throughput time of analysis (sample
preparation and measuring)
• Fit for integration and automation
• Quantitative and qualitative analysis of all elements
from Be to U

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What is XRF?
H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba L Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra A

L La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

A Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

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Where is XRF used?
• Materials characterization and (process) monitoring in
research, development, engineering and product and quality
control a.o. for:
– Chemical and petrochemical
– Cement and industrial minerals
– Mining
– Steel and non-ferrous
– Environmental and pollution
– Pharmaceutical and cosmetic
– Food

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What are X-rays ?
Electromagnetic radiation: Wavelength 0.01 nm - 10.0 nm

hc 1.2396
E (keV ) = =
λ (nm) λ (nm)

Energy 124 keV - 0.124 keV

γ -rays X-rays UV Visual light

0.001 0.01 0.1 1.0 10.0 100 200 nm

1nm = 10Å = 10-9m = 10-6mm

X-rays are highly energetic, therefore dangerous for humans etc.
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X-ray sources in XRF spectrometry

• In an X-ray spectrometer there are two places where X-rays

are generated
– The X-ray tube
• In the x-ray tube the excitation is provided by electrons from
the tube filament
– The sample
• In the sample the analyte elements are excited by the photons
originating from the X-ray tube

(Note: Power off => X-ray’s off, no radiation possible)

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The X-ray tube
The x-ray tube
• filament
• acceleration voltage
• current
• vacuum
• anode material
• exit window

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The side window x-ray tube

20..100kV
anode
Current
electrons
filament

Be window X-ray photons

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Production of x-rays in a sample

Fluorescence

Incoming x-rays
Passed x-rays

Rayleigh
Scatter
Compton
ρ
Scatter

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Production of x-rays in a sample

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Characteristic lines: electron shells

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The X-ray Fluorescence Spectrometer
• Schematic System Design

• Spectrometers can be divided into

two main groups:
– Wavelength dispersive (WD-XRF)
– Energy dispersive (ED-XRF)

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ED-XRF vs WD-XRF
Sample Sample

Primary
collimator

Source Source

Detector

Detector

Analysing crystal
2θ

Epsilon 3 Axios
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ED-XRF
• The voltage of the pulse produced within a detector is
proportional to the x-ray photon energy that produces it.
• Detector may be solid state e.g. Si(Li), a gas-filled
proportional counter or scintillation counter.
• Pulses are sorted by energy in a multi-channel analyser,
where the channel number is proportional to pulse voltage
and the number of pulses in each channel are counted.
• Elemental range is Na – U, from ppm to 100%

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ED XRF system

channel
counts

sample
energy (KeV)

X-ray tube
amplifier and
multi-channel
detector analyser

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ED-XRF
• Advantages
– All elements can be measured simultaneously.
– Relatively inexpensive.
– Simple operation and maintenance

• Disadvantages
– Poor performance for light elements
– Poor resolution for light elements.
– Some detectors require liquid N2.

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EDXRF optics: basic differences

Direct excitation (2D) Polarized excitation (3D)

Sample
X-ray tube Sample

X-ray tube

Secondary target
Detector
Detector

Epsilon 3 Epsilon 5
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Simple 2D EDXRF Optics

X-ray tube Detector

Typically a Rh
anode

Primary tube filters

(5 + blank)
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Polarized EDXRF

Sample
Polarised optical design
Polarized
x-rays Fluorescent • Very low backgrounds
radiation
• High peak:background ratio
Tube • Best LLD’s

Non-polarized
primary radiation

Targets Detector

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2D vs. 3D optics

Direct excitation (2D) Polarized excitation (3D)

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EDXRF System

Epsilon 3 XLE Epsilon 5

Epsilon 3X
Epsilon 1

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WD-XRF
• Uses single crystals or multilayer to diffract selected
wavelength into the detection system.
• High resolution for all elements.
• Quantitative and qualitative analyses.
• Elemental range is Be – U, from ppm to 100%

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WD XRF system

CPS

sample
degrees 2q

primary
collimator

X-ray tube
amplifier,
PHS and
detect counting
or circuitry
analysing crystal
2q

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WD-XRF

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The WDXRF Spectrometer

Bragg's law:

2d sinӨ = nλ
WDXRF System

Axios Family Axios Fast Zetium

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 Direct excitation Secondary excitation
Sample Sample
X-ray tube Sample

Promary
collimator

X-ray tube
Detector
X-ray tube

Secondary target
Analysing crystal Detector
2θ Detector

I I
P1 P3 P3
P1 P3 P1
P2 P2 P2
P4
B3
B1 B4 B B
B2
P4
E E E
WDXRF EDXRF Polarized EDXRF
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XRD Family

X’Pert Cubix3 X’Pert pro MRD EMPYREAN

Powder
Global and near
Resourceful
Experienced

Thank you

The Analytical X-ray Company

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