X-Ray Fluorescence

Spectrometer

Dr. Umesh Chandra

School of Materials Science and Engineering
 X-Rays
 X-ray are invisible, highly penetrating electromagnetic
radiation of much shorter wavelength (higher frequency)
than visible light. They are produced by the deceleration
of electron in the inner orbital of atoms.
 Xrays have a wavelength range of 10-5 Angstron to 100
Angstron. But conventional Xrays spectroscopy is largely
confined to 0.1 Angstron to 25 Angstron.
 The Origin of X-rays

Electrons lose energy

• Change in their state of motion
• Deceleration
• Changing direction
• Moving to a lower energy level

The deceleration of electrons and the transition

from higher energy level in the atomic shell to a
lower one play an important part in the creation of
X-rays in the field of X-ray analysis.
 X-Ray Production Sources
• All modern X-ray tubes owe their existence to Coolidge’s
hot-cathode X-ray tube (Coolidge 1913).
• It consists essentially of a vacuum sealed glass tube
containing a tungsten filament for the production for
electrons, an anode and a beryllium window.
• From variety of modifications, two geometries have
emerged as the most suitable for all practical purposes:
The end-window tube
The side-window tube

Both having their own merits and limitations.

The general requirements are as follows:
 Side-window Tubes

• In side-window tubes, a negative high voltage is applied to

the cathode. The electrons emanate from the heated cathode
and are accelerated in the direction of the anode. The anode
is set on zero voltage and thus has no difference in potential
to the surrounding housing material and the laterally
mounted beryllium exit window
• The scattering electrons contributes to the heating up of the
surrounding material, especially the exit window, the exit
window must withstand high levels of thermal stress any
cannot be selected with just any thickness.

• The minimum usable thickness of a beryllium window for

side-window tubes is 300 μm. this causes an excessively high
absorption of the low-energy characteristic L radiation of the
anode material in the exit window.
End-window Tubes
• The distinguishing feature of the end-window tubes is that
the anode has a positive high voltage and the beryllium exit
window is located on the front end of the housing

• The cathode is set around the anode in a ring (anular

cathode) and is set at zero voltage. The electrons emanate
from the heated cathode and are accelerated towards the
electrical field lines on the anode. Due to the fact that there is
a difference in potential between the positively charged anode
the surrounding material, including the beryllium window,
the back-scattering electrons are guided back to the anode
and thus do not contribute to the rise in the exit window’s
temperature.

• The beryllium window remains cold and can therefore be

thinner than the side-window tube. Windows are used with a
thickness of 125 mm and 75 mm. this provide a prerequisite
for exciting light elements with the characteristic L radiation
of the anode material
 Properties of X-Rays
• Invisible;
• Propagate with velocity of light (3*108 m/s)
• Unaffected by electrical and magnetic fields;
• Differentially absorbed in passing through matter of
varying composition, density and thickness;
• Reflected, diffracted, refracted and polarized;
• Capable of ionising gases;
• Capable of affecting electrical properties of solids and
liquids;
• Capable of blackening a photographic plate;
• Able to liberate photoelectron. And recoils electrons
• Emitted in a continuous spectrum;
• Emitted also with a line spectrum characteristic of the
chemical element;
• Found to have absorption spectra characteristic of the
chemical element.
Dr. Rabiul Hussein
X-Ray Fluorescence - The Basic Process
• X-Ray Fluorescence (XRF) can be considered in a simple three step
process occurring at the atomic level:
– An incoming X-Ray knocks out an electron from one of the orbitals
surrounding the nucleus within an atom of the material.
– A hole is produced in the orbital, resulting in a high energy, unstable
configuration for the atom.
– To restore equilibrium, an electron from a higher energy, outer orbital
falls into the hole. Since this is a lower energy position, the excess
energy is emitted in the form of a fluorescent X-Ray.

• The energy difference between the expelled and replacement

electrons is characteristic of the element atom in which the
fluorescence process is occurring – thus, the energy of the emitted
fluorescent X-Ray is directly linked to a specific element being
analyzed. It is this key feature which makes XRF such a fast
analytical tool for elemental composition.
• In general, the energy of the emitted x-ray for a particular element
is independent of the chemistry of the material. For example, a
calcium peak obtained from CaCO3, CaO and CaCl2 will be in
exactly the same spectral position for all three materials.
 XRF Instrumentation
• – Sources.
• - Samples
• – Detectors
 X-Ray sources
X-Ray tubes:
• – Hi spec/power, usually bulky & water
cooled.
• – Light weight low power for EDXRF
Radio-nuclides emitting X-rays or low energy
g rays:
 Detectors: three types

Gas filled detectors:

• – Proportional counters, good for low e x-rays.
Scintillation Counters:
• – Better for higher energy x-rays
Semiconductor detectors:
• – Becoming the detector of choice for
portable/small systems.
 Detectors: gas proportional counter

Cylindrical metallic tube in the middle of which a thin wire

(counting wire) is mounted.
Tube is filled with a suitable gas (e.g. Ar +10% CH4).
A positive high voltage (+ve) is applied to the wire.
The tube has a lateral aperture or window that is sealed
with a material permeable to X-ray quanta
 Detectors: gas proportional counter

 An X-ray floroscence (Photons) penetrates the window into

the counter's gas chamber where it is absorbed by ionizing
the gas atoms and molecules.
 Resulting +ve ions move to the cathode (the metallic tube),
the free electrons to the anode (the wire).
 The number of electron-ion pairs created is proportional to
the energy of the X-ray photons.
 Detectors: Scintillation Counter (SC)

Scintillation crystal:
• sodium iodide crystal in which thallium atoms are
homogeneously distributed "NaI(Tl)." The density of the
crystal is sufficiently high to absorb all the XRF high
energy quanta.
• Energy of the X-ray photon is transferred step by
step to the crystal atoms that then radiate light and
cumulatively produce a flash of light
• The amount of light in this scintillation flash is
proportional to the energy that the X-ray photon
has passed to the crystal.
• Resulting light strikes a photocathode, easily
ejecting electrons. These electrons are accelerated
in a photomultiplier and, within an arrangement of
dynodes, produce secondary electrons giving a
measurable signal.
• Height of the voltage pulse produced is proportional
to the energy of the detected X-ray photons.
 Detectors: Semiconductor based

• Usually based on a p-n-type diode. The diode can only pass an

electric current in one direction (rectification mechanism).
• When a voltage is applied against the current (reverse bias) and
light is allowed to enter, electrons are excited into a conductive
band and only the current for the excited electrons will travel.
• X-ray detection is performed by measuring, one by one, each
current pulse that corresponds to an incident X-ray photon.
• The instantaneous current value of a single pulse is
proportional to the incident X-ray energy:
– X-ray energy can be found by measuring the pulse height of the
current pulse.
 XRF Samples

1) Solids: generally solids must be polished as surface

roughness may give erratic results.
2) Powders and pellets: powdered samples are often
pressed into pellets, suspensions may also be
analysed
3) Liquids /solutions: a x-ray transparent cover and
sample cup must be provided to be able to measure
liquid samples.
 Powders Samples

• Grinding is an effective way of eliminating large and/or

inconsistent grain sizes to produce homogeneous samples
from loose powders.
• Pressing (hydraulically or manually) compacts more of the
sample into the analysis area, and ensures uniform
density and better reproducibility.
 Loose Powders
• The simplest approach to analyzing a loose powder
sample is to simply fill a sample cup approximately ¾
full and analyze it without any additional preparation,
or simply tapping the cup on a clean surface to pack it
to a more consistent density.

Beads
Fusing powdered samples into beads is now widely seen
as an excellent way of overcoming problems of particle
size variation as well as surface and mineralogy effects.
The powdered sample is mixed with a flux, heated in a
crucible to between 900-1300 °C, then cast in a dish to
produce a homogeneous glass-like bead.
 Solid Samples
• Among the samples that can be analyzed as solids are
metals and plastics, as well as ores, slags and geological
materials. Here, the samples are usually in the form of
solid discs, drillings, filings, small pieces and shavings.
Some advices concerning solid samples:

• 1) Orient surface patterns in same manner so as minimise

scatter affects.
• 2) Polishing surfaces will also minimise scatter affects.
• 3) Flat samples are optimal for quantitative results.
 Liquid Samples
• General Liquid Sample Preparation
• Solutions should be well mixed prior to pipetting them into
a sample cup. The sample should be taken from the center
of the container since some components may concentrate
on the walls. Issues associated with use of liquid samples:

• Evaporation
• Precipitation
• Wicking
 Sample Cups
Diameter
• Cups come in a variety of diameters from 20 mm to 40 mm.
• The penetration depth of the x-rays for the elements of interest is
also important. For characteristic x-rays above 10 keV,
penetration depths of more than 1 cm are possible. With a 20
mm cup the x-rays may hit the cup wall.
• Larger diameter cups, 40 mm, are recommended for higher
atomic number elements in transparent matrices to achieve the
best performance.

Height
• Height selection is also a function of penetration depth. It is
important to know the angle of the x-ray source when making
this determination. If it is at a 45 degree angle there is generally
no benefit to having a cup that is taller than it is wide. If the
source points straight upward then a deeper cup is beneficial
when analyzing high energy x-rays from a x-ray transparent
sample.
Quantitative Analysis

• XRF is a quantitative technique – the peak height

for any element is directly related to the
concentration of that element within the sampling
volume.
Applications:
1. Most of the elements in the periodic table, both metals and
nonmetals, respond to this technique.
2. Detection limit is between 10 to 100 ppm. One of the significant
uses of this method is in the medical field in identifying and
determining the sulfur in protein.
Disadvantages:
1. The sensitivity gets affected for elements with lower atomic
numbers, particularly elements with atomic number lower than
15 are difficult to analyze.
2. The sensitivity is also limited by matrix absorption, secondary
fluorescence and scattering of the particles. Instruments are
often large, complicated and costly.