Contents

Definition: x-ray fluorescence analysis.............................2

Chemical theory or working:............................................2
Characteristic of element:...............................................3
Analysis:........................................................................3
The X-Ray Fluorescence Process:.....................................5
Qualitative analysis:.......................................................6
Quantitative analysis:.....................................................6
Schematic diagram:........................................................6
Instrumentation:.............................................................7
x ray generator:.......................................................7
Analyzing crystal:.....................................................7
Example of Quantitative Analysis:...................................8
Advantages of X-ray Fluorescent Analysis:.......................8
XRF Application:.............................................................8

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 X-Ray Fluorescence Analysis

Definition: x-ray fluorescence analysis

X-ray fluorescence (XRF) is the emission of characteristic
"secondary" (or fluorescent) X-rays from a material that has been
excited by bombarding with high-energy X-rays or gamma rays.
The phenomenon is widely used for elemental analysis and
chemical analysis, particularly in the investigation of metals,
glass, ceramics and building materials, and for research in
geochemistry, forensic science, archaeology and art objects such
as paintings and murals.

Chemical theory or working:

When an element is placed in a beam of x-rays, the x-rays
are absorbed. The absorbing atoms become ionized (e.g.
due to the x-ray beam ejects the electron in the inner shell).

An electron from higher energy shell (e.g., the L shell) then

fall into the position vacated by dislodged inner electron and
emit x-rays or characteristic wavelength.

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 This process is called x-ray fluorescence.

Characteristic of element:
The wavelength of fluorescence is characteristic of the
element being excited, measurement of this wavelength
enable us to identify the fluorescing element.

The intensity of the fluorescence depends on how much of

that element is in x-ray beam.

Hence measurement of the fluorescence intensity makes

possible the quantitative determination of an element.

Analysis:
The process of detecting and analyzing the emitted x-rays is
called X-ray Fluorescence Analysis.

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 In most cases the innermost K and L shells are involved in
XRF detection.

A typical x-ray spectrum from an irradiated sample will

display multiple peaks of different intensities.

The characteristic x-rays are labeled as K, L, M or N to

denote the shells they originated from.

Another designation alpha (), beta () or gamma () is

made to mark the x-rays that originated from the transitions
of electrons from higher shells.

Hence, a K x-ray is produced from a transition of an

electron from the L to the K shell, and a K x-ray is produced
from a transition of an electron from the M to a K shell, etc.

Since within the shells there are multiple orbits of higher and
lower binding energy electrons, a further designation is
made as 1, 2 or 1, 2, etc. to denote transitions of
electrons from these orbits into the same lower shell.

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The X-Ray Fluorescence Process:

1) An electron in the K shell

is ejected from the atom by
an external primary
excitation

x-ray, creating a vacancy.

2) An electron from the L or M shell jumps in to fill the vacancy.

In the process, it emits a characteristic x- ray unique to this
element and in turn, produces a vacancy in the L or M

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 shell.

X-ray fluorescence's
spectroscopy
provides a means of
identification of an
element, by measurement of its characteristic X-remission
length or energy
The method allows the quantification of a given element by
first measuring the emitted characteristic line intensity and
then relating this intensity to elemental concentration

Qualitative analysis:
The energy of the peaks leads to the identification of the
elements present in the sample (qualitative analysis).

Quantitative analysis:
while the peak intensity provides the relevant or absolute
elemental concentration (semi-quantitative or quantitative
analysis).

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Schematic diagram:

Instrumentation:
x ray generator:
X-ray tube for XRF spectrometer is a diode (vacuum tube) consist
of the filament generating thermo- electron and the anode
(target) generating x-rays.

Near the target, there is a window to pass x-rays through to the

outside tube. The window material, Beryllium, is employed
because of its nature for having the excellent transmission
(penetration) of x-rays.
Analyzing crystal:
The diffraction phenomenon of x-ray through the single crystal is
utilized for the dispersion of x-rays. This crystal is called the
analyzing crystal. In accordance with the wavelength region of

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the fluorescence x-rays, the optimum analyzing crystal is
employed respectively.

Example of a qualitative measurement result.

Example of Quantitative Analysis:

XRF is a reference method; standards are required for
quantitative results.

Standards are analysed, intensities obtained, and a

calibration plot is generated (intensities vs.
concentration).

XRF instruments compare the spectral intensities of unknown

samples to those of known standards

Advantages of X-ray Fluorescent Analysis:

Rapid analysis
Non-destructive analysis

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 No spectrum is affected by chemical bonding
Easily analysis of the element among the same family
elements
High accurate analysis
Easy qualitative analysis
Easy sample preparation

XRF Application:
During the last two decades, the development in X-ray
detectors has established the XRF method as a powerful
technique in a number application fields, including:
Ecology and environmental management: measurement of
heavy metals in soils, sediments, water and aerosols
Geology and mineralogy: qualitative and quantitative
analysis of soils, minerals, rocks etc.
Metallurgy and chemical industry: quality control of raw
materials, production processes and final products
Paint industry: analysis of lead-based paints