INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

Introduction of X-ray
Fluorescence Analysis
Mr. Ravindra Saini
Institute Instrumentation Centre, IIT Roorkee
Outline

• Fundamentals of XRF Spectrometry

• Sample Preparation
• Applications
• Introduction to Electron Probe Micro Analysis
• Matrix Correction Procedures

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 INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

Fundamentals of
X-ray Fluorescence Spectrometry
Electromagnetic Spectrum

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Characteristics of X-rays

(1) Photographic effect

Fluorescence is emitted when NaI, ZnS, CdS, etc.
(2) Scintillation effect are irradiated.
Applied to the scintillation counter.

(3) Ionizing action Applied to the proportional counter.

(4) Diffraction X-rays are diffracted with the analyzing crystal.

(5) High penetration depth Compared to electron-excitation spectrometry.

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How Do X-Ray Interact with Matter?

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Interaction of X-rays with Matter

X-rays Fluorescent
X-rays
Compton scatter
X-rays
Photo-electron

Sample

Transmitted X-rays Heat

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X-ray Fluorescence: how does it work?

• The different layers of the atom

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X-ray Fluorescence: how does it work?

• Fluorescence involves emission of an X-ray photon after ionization of the atom by a primary beam X-ray

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Source - Sample Interaction

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Source - Sample Interaction

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Transitions between energy levels :

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Principle of X-ray Fluorescence cont.

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Principle of X-ray Fluorescence

Fluorescent X-rays
M shell Kα 4
X-ray tube Primary X-rays 3
1
Photo
Fluorescent X-rays K shell electrons
Primary 2
X-rays Sample Kβ L shell

Lα

① Primary X-rays strike an inner shell electron.

② An inner shell electron is kicked out as a photo electron.
③ An electron shifts from an outer shell.
④ Fluorescent x-rays are produced with equivalent energy difference.

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What We Can See by XRF

Qualitative analysis
Fe-Kα Cr-Kα Check energy/wavelength of peaks.
Ni-Kα
Primary X-rays
Fluorescent To see what elements are contained.
X-rays
Cr Sample contains Ni,Fe and Cr
Fe Ni

Sample To see how much of

Fe-Kα
X-ray intensity
a specific element is

Cr-Kα
contained.

Ni-Kα
Compare to
reference material

Wavelength

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Basis of the method of x-ray fluorescence

• X-rays, known as primary (produced by an x-ray tube) excite all the elements present in a specimen.
• Each of these elements under the impact of primary x-rays, emits its own wavelength.
• These wavelengths are then separated with a crystal monochromator and collected by a detector that converts
photons into electrical pulses.
• The output of the detector is processed electronically and then sent to a pulse counter.
• The number of pulses produced per second (cps) is in first approximation proportional to the concentration of
the element characteristic.
• These intensities (cps) are compared with standard intensities, then a calculation allow to determine the
concentration of the element in question.
• In modern equipment, matrix effects correction (inter element effects) are applied before the results are
delivered by the system.
• Importantly, the method itself is not destructive.

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How do X-Ray interact with Matter?

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X-Ray Emission Energies

• Fluorescence yield

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X-Ray Emission Energies

•B to ~Ba are analyzed using Kα (Kβ)

lines, transitions from L (M) to K.
•Ba to U are analyzed using Lα (Lβ)
lines, transitions from M (N) to L.
•K is the layer that requires the most
energy to excite electrons in an atom.

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WD-XRF and ED-XRF

WD: Wavelength Dispersive ED: Energy Dispersive

Sample Detector Sample

Crystal
X-ray tube (2d sinθ = n λ) X-ray tube Detector
with high energy
resolution
(Si-PIN, SDD, SSD)

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X-Ray Fluorescence: Two ways of doing it - EDX and WDX

• Energy Dispersive X-Ray fluorescence – EDXRF

• uses a detector to process directly the complete spectrum into an energy dispersive scale

• Wavelength Dispersive X-Ray fluorescence - WDXRF

• uses appropriate crystals to separate the emission spectrum into discrete wavelengths before detecting them

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Comparison of Light and Fluorescent X-rays

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EDXRF vs WDXRF

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Comparison between WDX and EDX

Item WDX EDX

Spectral resolution Excellent (26 eV @ Mn-Ka) Medium (~160 eV @ Mn-Ka)
Measurement Sequential Simultaneous
method (or multi-channel) for multi-elements
- 1000 kcps (SC) - 100 kcps (new SDD) in total
Counting
- 2000 kcps (F-PC) - 10 to 20 kcps (SSD) in total
Precision High Low
Monochromatic X-rays
X-rays going into
diffracted with All the x-rays from the sample
the detector
the analyzing crystal
Sensitivity for
Excellent Poor
light elements
Structure Complex Simple
Optical path Long Short

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TUBE-ABOVE SEQUENTIAL WAVELENGTH DISPERSIVE
X-RAY FLUORESCENCE SPECTROMETER
Elemental coverage: Be through U
Optics: Wavelength dispersive, sequential, tube
above
X-ray tube: End window, Rh-anode, 4 kW, 60kV

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XRF capability

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WDXRF Spectrometer

(7) Analyzing crystal

(6) Soller slit

(8) Scintillation
counter (SC)
(1) X-ray tube

(9) Proportional
counter (PC)

(2) Primary beam filter

(5) Attenuator

(3) Sample holder

(4) Diaphragm

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How X-rays are Generated?

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Production of X-RAY

• The cathode is heated by a current of several amperes.

• Between the cathode and the anode, which is built with a metal characteristic, we apply a rectified high voltage.
• By thermo-ionic effect, the cathode emits electrons that are accelerated by the high voltage (e.g. 40-60kV).
• When these high energy electrons hit the anode, it emits X-rays.
• As a vacuum exists within the tube, the produce current is a few milliamps.
• <1% of the energy of the electron beam is converted into X-ray, the rest > 99% is dissipated as heat.
• The spectrum obtained is a continuous spectrum which is superposed to a spectrum characteristic of the
discontinuous nature of the anode.
• It should be noted that the continuous spectrum (Bremsstrahlung or Continuum) is independent of the nature of
the anode.

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The continuous spectrum

• The continuous spectrum comes from the sudden deceleration of electrons on the anode.
• The position of maximum intensity of the spectrum depends on the voltage (kV) applied between the filament
(electron gun) and the anode.
• The higher the voltage increases, the minimum wavelength for excitation (λ0) decreases.
• It is observed that the position of characteristic lines, which are superposed on the spectrum, do not change
when you change the voltage.

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Output of the X-ray tube

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End window X-ray tube

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X-ray tube

Excitation energy
Tube voltage (kV)
X-ray intensity

Tube current (mA) X-ray intensity

(proportional to mA)

Be window thickness X-ray intensity for light elements

Increase/decrease of sensitivity
Target material Interference by scattering of tube
target lines

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Primary beam filter

Function
◆ Eliminates the scattering peaks derived from the x-ray tube (Thomson
and Compton scattering)
◆ Reduces background to improve peak/background ratios
Note) Peak intensities are also reduced.

Material (thickness [μm]) Function and target element

Eliminates the scattering peaks from the Rh target;
Ni400
Rh, Ru, Cd, Ag ...
Ni40 Reduces background; Pb, As, Mo, Zr ...
Al125 Reduces background; Co, Fe, Ce, Pr, Nd ...
Reduces background and eliminate the scattering from the
Al25
Rh target (L lines); Cl, Cd (L), Ag (L) ...
Be Protects the x-ray tube from falling sample

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Diaphragm

Function
◆ Confines detected area from the sample, such as 30 mm in diameter so
that sample area only within the sample mask opening is measured.
Note) The primary x-rays are not confined.

X-ray tube To the optical chamber

Diaphragm

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Attenuator

Function
◆ Reduces x-ray intensity to avoid counting loss without change of tube
voltage (kV) or current (mA).

When measured x-ray intensity is higher than the linear counting limit for the
detector (e.g. 1000kcps for SC, 2000kcps for F-PC), the intensity can be reduced
with the attenuator and without changing kV or mA and it ensures stable analysis.
Without attenuator,
•Decrease mA
•Insert a primary x-ray beam filter
•Change to a finer slit
Changing kV and mA can cause instable analysis owing to the power change.
There are many cases that It is not possible to adjust intensity by the other
conditions.

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Soller Slit

Function
◆ Turns the x-rays from the sample into parallel beams.

The spacing of foils determines resolution and sensitivity.

With a higher resolution Soller slit, resolution improves and, however, the
intensity drops.

Example) On the ZSX PrimusII

S1 slit* S2 slit S4 slit S8 slit
Resolution Very high > High > Middle > Low
Intensity Very low < Low < Middle < High
Default slit : S2 for SC, S4 for PC ( S8: for B-N analysis using PC )

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Analyzing Crystal

Function
◆ Guides the x-rays of interest into the detector by diffraction.

Monochromatic X-rays

Bragg’s law 2d sinθ = n λ n: natural number (1, 2, ...)

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Analyzing Crystal
Atomic N. 4 5 6 7 8 9 11 12 13 14 15 16 17 19 20 22 23 24 25 26 27 28 29 30 33 - 60
K Line Be B C N O F Na Mg Al Si P S Cl K Ca Ti V Cr Mn Fe Co Ni Cu Zn As - Nd
L Line 48Cd 56Ba 74W 82Pb
LiF(200)
LiF(220)
LiF(420)
PET
Ge
RX25
RX35
RX40
RX45
RX61
RX61F
RX75
RX85
RX4
RX9

Excellent Good

Bragg’s law 2d sinθ = n λ n: natural number (1, 2, ...)

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Detector

Function
◆ Detects the x-rays entering the detector.

“X-ray intensity” : kcps (kilo counts per second)

Number per unit time of X-ray photons going into the detector

SC: Scintillation counter

Short wavelength ( – 0.28 nm)
Heavy elements (22Ti – )
PC: Proportional counter
Long wavelength (0.14 nm – )
Light elements ( – 21Sc)
(Longer wavelength lines of heavy elements [e.g. Cd-Lα, Pb-Mα] )

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Scintillation Counter (SC)

Be window Scintillator (NaI) Anode

Photocathode

X-rays
To the counting circuit

Electrons

Ultraviolet rays Dynode Electrical pulse

Light shielding Photomultiplier tube

material

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Proportional Counter (PC)

Window: Al-coated thin P-10 gas (Ar 90% + CH4 10%)

polymer film

Ar → Ar+ + e-

X-rays Center wire (anode)

To the counting circuit

Gas-flow proportional counter (F-PC)

GDS: gas density stabilizer

Electrical pulse
P-10 gas

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PHA (Pulse Height Analyzer)

The Pulse Height Analyzer discriminates the x-ray pulses by the pulse heights to
remove noise of low level and the pulses of higher order lines in order to pick
up the pulses of first order line x-rays.

2nd
- Fe-Kβ1-4th
order

Upper Level

- Si-Kα

Pulse height
1st Window
X-ray intensity

order

Lower Level
- Si-Kα

Without PHA (Base line)

Time
With PHA

105 107 109 111

Pulse height
2θ

Time
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PHA (Pulse Height Analyzer)

Element line n (order) 2θ (deg) λ (nm) E (keV)

Pb-Lβ1 1 28.22 0.09828 12.62
Sn-Kα 2 28.22 0.04906 25.27
[Energy of the 2nd order line] = 2 x [Energy of the 1st order line]
E (keV) = 1.24 / λ (nm) 2d sinθ =nλ
= hc n/E
Pb-Lβ1 0.09828 nm
Hence, n/E = const.
Sn-Kα 0.04906 nm
n=2 n=2

n=1 n=1
Detector PHA
Pb-Lβ1
window
Sn-Kα

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INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

Sample Preparation
Points in Sample Preparation

◆ Prepare homogeneous samples

◆ Consistent preparation procedure
◆ Avoid contamination

Select the type of sample preparation depending on

required precision, affordable labor hour and
performance of instruments.

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Metal: Grinding/Polishing

Sample Polishing Analysis

Grinder

• Iron/Steel Hard metal

• Ni base alloy Belt Surfacer

• Cu-Alloy, Al-Alloy, Lathe Soft metal

• Zn-Alloy, Lead-Alloy

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Powder: Grinding and Pressing

Sample

Drying 110 ⁰C,

for an hour or longer

Grinding ( → Drying → ) Pressing

Ground into less than 50 μm Pressure : 100 – 300 kN
（10 – 30 t)
Pulverize until you do not difficult to form
sense the powder roughness Mix Binder
with your fingers.
Typically 5 – 20% of the sample weight
(need to precisely weigh out)
Recommended to pulverize the
sample with the binder.

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Grain-size effect

Relative X-ray intensity

Less than 44 μm

± 0.45 mass%

10 20 30
Al2O3 mass%

Relative X-ray intensity Less than 75 μm

± 1.50 mass%

10 20 30
Al2O3 mass%
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Powder: Fusion

Bead Sampler Pt crucible Fusion bead

(fusion machine)

Sample Weighing Fusion Fusion bead

• Ground less • Sample • Flux Li2B4O7, etc. • Keep in
than 100 mesh 0.3 – 2.5 g • Temperature desiccators
• Sample : Flux 1000-1250 ⁰C
= 1:1 – 1:20 • Fusion time
• Weigh to 0.1 mg 3 – 10 minutes

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Powder: Loose Powder

• Powder samples are packed into liquid cells with sample film.
• Samples can be measured even without being pressed.
• The repeatability is not as good as that of other sample
preparation methods for powder samples.

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Applications
Industries where XRF is used

• Production control
• Cement plants
• Foundries (steels, brass, aluminum,…)
• Industries of glass and refractory
• Chemistry
• Petrochemicals
• Polymers and plastics
• Pharmacy and food
• Mines and Mineralogy

• Research Universities and research centers

• Industry
• Automotive
• Construction
• Pharmacy and food
• Geology

• Environment
• Police and customs

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Strong Points of XRF

• Simple sample preparation

• Safe and lower analysis cost
• Short total analysis time
• High repeatability/reproducibility
• Small personal error
• Wide dynamic range (ppm to 100mass%)

• Quality control
• Process control
• Research and development
• Screening

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Electron Probe Micro Analysis

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WDS vs EDS

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EPMA typical results

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Advantages of X-ray Over Electron Excitation in Microanalysis

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Advantages of X-ray Over Electron Excitation in Microanalysis

• •Unlike those used in electron excited EDS, XRF samples need not be electrically
conductive. There is no electrical charge being transported in XRF samples.
• Measurement of liquid and organic samples is possible because the electron beam
does not require vacuum. Samples may remain in an air environment during
analysis.
• X-ray excitation does not heat a sample as there is no absorbed kinetic energy of
electrons. This means that temperature sensitive samples, such as thin films, can
be analyzed.

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Matrix Effect
Matrix Correction

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Matrix Corrections- Peak Above Background

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Matrix Correction-Z

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Matrix Correction-A

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Matrix Correction- X-ray Absorption effect (A) Cont.

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Matrix Corrections-F

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INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

Thank You