University of Pretoria

INTRODUCTION TO
X-ray FLUORESCENCE SPECTROSCOPY
Jeanette Dykstra
X-Ray Analytical Facility
REASON FOR UNDERSTANDING XRF

Metallurgical engineers and Materials scientists ask:

a. WHAT is in the material?

b. HOW MUCH is in a material?

WHAT = Chemistry quality

HOW MUCH = Quantity

XRF = Elemental quality and quantity analyses

WHAT BENEFIT DOES XRF HAVE?

Chemical
elements

Bulk
sample
chemistry
Concentrations
of each
element
WHAT BENEFIT DOES XRF HAVE?
WHAT WE CAN ANALYSE
WHAT IS XRF?

X-RAYS
W.C. Roentgen 1895 (1st Nobel prize in 1901)
Compared to medical x-ray, detector in place of photographic
plate

Dobbins III, J.T. et al., Chest tomosynthesis: Technical principles and clinical update, European
Journal of Radiology 72 (2009), p. 244 -251.
WHY XRF - COMPARED TO OTHER
TECNIQUES?

Non destructive
Elemental range from F U
Precision
Accuracy
Predictable matrix (sample) effects can be corrected
Lowes Limit of Detection (LLD) to 10ppb
ELEMENTS WE CAN DETECT
WHAT CAN WE NOT ANALYSE WITH XRF?
Fe Fe
Si
O Fe
O Fe
Quartz Hematite Magnetite
O Fe
O O
O O O O

Phases
Oxidation state
Mineral characteristics
 LECTURE 1

X-RAY PHYSICS
LECTURE 1 : X-RAY PHYSICS

Long wavelength Short wavelength

LECTURE 1 : X-RAY PHYSICS

DUANE HUNT LAW

h = Plancks constant

h c (6.626 x 10-34 J s-1)

12.4
E= c = velocity of light
E ( keV ) =
(3 x 108 ms-1)
= wavelength (m)

( A)
LECTURE 1 : X-RAY PHYSICS

Interaction of x-rays with matter

other photons
x-ray photons
X-ray beam (tube) Transmission

coherent
incoherent
LECTURE 1 : X-RAY PHYSICS

Generation of x-rays in a x-ray tube

LECTURE 1 : X-RAY PHYSICS

X-RAY TUBE SPECTRUM

LECTURE 1 : X-RAY PHYSICS

Operating kV influence on tube spectrum

LECTURE 1 : X-RAY PHYSICS

THE CONTINUUM (hump)

LECTURE 1 : X-RAY PHYSICS

Calculating the continuum

12 .4
min = kVapplied Im ax 2 min
min = max =
min = max =
min = max =
min = max =
min = max =
LECTURE 1 : X-RAY PHYSICS

Influence functions of the continuum (kV, mA, Z)

LECTURE 1 : X-RAY PHYSICS

Intensity of the continuum

1
I ( ) = KiZ 1 2
Where
min
I = Wm-2
K = proportionality constant equal to 1.4 x 10-9
i = current in A
Z = atomic number of the target element
= wavelength
LECTURE 1 : X-RAY PHYSICS

Significance of the continuum?

Principal source of excitation x-rays

Principal source of background intensity (noise)
Wavelength characteristic used in certain correction
calculations
LECTURE 1 : X-RAY PHYSICS

CHARACTERISTIC LINE SPECTRUM EXCITATION

ATOM
-Nucleus
protons & neutrons
-Atomic sub-shells (K, L, M, N)
electrons
LECTURE 1 : X-RAY PHYSICS

EXCITATION POTENTIALS IN kV
Element(Z) K LIII MV
Na(11) 1.1 0.03 -
S(16) 2.5 0.16 -
Cr(24) 6.0 0.57 -
Ga(31) 10.4 1.12 -
Rb(37) 15.2 1.81 0.11
Mo(42) 20.0 2.52 0.23
Rh(45) 23.2 3.00 0.32
Ce(58) 40.4 5.73 0.85
W(74) 69.5 10.2 1.80
Au(79) 80.7 11.9 2.22
U(92) 115.6 17.2 3.53
 Primary electron
DECELERATION

Primary electron
SCATTERING
Primary L
electron
K
Rh

Filling
vacancy Rh
Secondary electron characteristic
out of K shell X-ray line
LECTURE 1 : X-RAY PHYSICS

SECONDARY FLUORESCNECE EXCITATION

Ti (22) as a n example
LECTURE 1 : X-RAY PHYSICS

Notation for spectral lines

Dependant on:
empty vacancy
filling electron
NiK 1
Ni chemical symbol of
element
K series symbol
1 line within series
LECTURE 1 : X-RAY PHYSICS

Siegbahn and IUPAC notations for spectral lines

IUPAC = International Union of Pure and Applied Chemistry
Siegbahn = Named after Manne Siegbahn (used in spectroscopy)

Siegbahn IUPAC Siegbahn IUPAC Siegbahn IUPAC

K1,2 K-L2,3 L1 L3-M5 M1,2 M5-N6,7
K1 K-L3 L2 L3-M4 M M4-N6
K2 K-L2 L1 L2-M4
K1 K-M3 L2 L3-N5
K1,3 K-M2,3 L L2-N4
LECTURE 1 : X-RAY PHYSICS

RELATIVE INTENSITIES

Within K, L, M series Between series

K series L series M series K series L series M series
K-L3 100 L3-M5 100 M5-N7 100
K-L2 50 L2-M4 50 M5-N6 100 100 10 1
K-M2,3 20 L3-N5 30 M4-N6 50
K-N2,3 5 L2-N4 10 M3-M5 5
K-L2,3 150 L1-M3 5
L1-M2 3
L3-M1 3
LECTURE 1 : X-RAY PHYSICS

SPECIATION
LECTURE 1 : X-RAY PHYSICS

ABSORPTION
EDGES
LECTURE 1 : X-RAY PHYSICS

SCATTERING OF X-RAYS

Coherent Incoherent
Raleigh scattering Compton scattering

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LECTURE 1 : X-RAY PHYSICS

COMPTON PEAK INTENSITIES

Generated by the X-ray tube target material energy (e.g. Rh)
SiO2
Matrix analyte excitation potential vs. Rh photon energy

Fe2O3

Pb