X-Ray Spectroscopy

History
Wilhelm Conrad Röntgen, a German physicist,was awarded the first Nobel Prize in physics in
1901 for his discovery of X-rays in 1895. His new technology was quickly put to use by other
scientists and physicians, according to the SLACNational Accelerator Laboratory.
The discovery of x-rays by Wilhelm Conrad Röntgen was based on the observation of
fluorescence in materials well away from his tube. Soon it was recognized that photographic
plates and gas-filled ionization chambers (electrometers) are also sensitive to x-rays. With
these principles the basis for x-ray detection was laid almost 70 years ago.
Charles Barkla, a British physicist, conducted research between 1906 and 1908 that led to his
discovery that X-rays could be characteristic of individual substances. His work also earned
him a Nobel Prize in physics, but not until in 1917.
The use of X-ray spectroscopy actually began a bit earlier, in 1912, starting with a father-and-
son team of British physicists, William Henry Bragg and William Lawrence Bragg. They used
spectroscopy to study how X-ray radiation interacted with atoms within crystals. Their
technique, called X-ray crystallography, was made the standard in the field by the following
year and they won the Nobel Prize in physics in 1915.

What is X-Ray Spectroscopy?

X-ray spectroscopy is a general term for several spectroscopic techniques for the
characterization of materials by using x-ray excitation.
X-ray spectroscopy is a technique that detects and measures photons, or particles of light, that
have wavelengths in the X-ray portion of the electromagnetic spectrum. It's used to help
scientists understand the chemical and elemental properties of an object.
There are several different X-ray spectroscopy methods that are used in many disciplines of
science and technology, including archaeology, astronomy and engineering. These methods can
be used independently or together to create a more complete picture of the material or object
being analyzed.

An X-ray spectrograph consists of a high voltage power supply (50 kV or 100 kV), a broad band
X-ray tube, usually with a tungsten anode and a beryllium window, a specimen holder, an
analyzing crystal, a goniometer, and an X-ray detector device. These are arranged as shown in
Fig.

The continuous X-spectrum emitted from the tube irradiates the specimen and excites the
characteristic spectral X-ray lines in the specimen. Each of the 92 elements emits a characteristic
spectrum. Unlike the optical spectrum, the X-ray spectrum is quite simple. The strongest line,
usually the Kalpha line, but sometimes the Lalpha line, suffices to identify the element. The
existence of a particular line betrays the existence of an element, and the intensity is proportional
to the amount of the particular element in the specimen. The characteristic lines are reflected
from a crystal, the analyzer, under an angle that is given by the Bragg condition. The crystal
samples all the diffraction angles theta by rotation, while the detector rotates over the
corresponding angle 2-theta. With a sensitive detector, the X-ray photons are counted
individually. By stepping the detectors along the angle, and leaving it in position for a known
time, the number of counts at each angular position gives the line intensity. These counts may
be plotted on a curve by an appropriate display unit. The characteristic X-rays come out at
specific angles, and since the angular position for every X-ray spectral line is known and
recorded, it is easy to find the sample's composition.

Principle of X-Ray Spectroscopy

XRF works on methods involving interactions between electron beams and x-rays with
samples.
It is made possible by the behavior of atoms when they interact with radiation.
When materials are excited with high-energy, short wavelength radiation (e.g., X-rays), they
can become ionized.
When an electron from the inner shell of an atom is excited by the energy of a photon, it
moves to a higher energy level.
When it returns to the low energy level, the energy which it previously gained by the
excitation is emitted as a photon which has a wavelength that is characteristic for the element
(there could be several characteristic wavelengths per element).
Thus atomic X-rays emitted during electronic transitions to the inner shell states in atoms of
modest atomic number.
These X-rays since have characteristic energies related to the atomic number, and each
element therefore has a characteristic X-ray spectrum which can be used to identify the
element.

How X-ray spectroscopy works

When an atom is unstable or is bombarded with high-energy particles, its electrons transition
from one energy level to another. As the electrons adjust, the element absorbs and releases high-
energy X-ray photons in a way that's characteristic of atoms that make up that
particular chemical element. X-ray spectroscopy measures those changes in energy, which
allows scientists to identify elements and understand how the atoms within various materials
interact.
There are two main X-ray spectroscopy techniques: wavelength-dispersive X-ray spectroscopy
(WDXS) and energy-dispersive X-ray spectroscopy (EDXS). WDXS measures the X-rays of a
single wavelength that are diffracted by a crystal. EDXS measures the X-ray radiation emitted
by electrons stimulated by a high-energy source of charged particles.
In both techniques, how the radiation is dispersed indicates the atomic structure of the material
and therefore, the elements within the object being analyzed.

Working of X-Ray Spectroscopy

An XRF spectrometer works because if a sample is illuminated by an intense X-ray beam,

known as the incident beam, some of the energy is scattered, but some is also absorbed within
the sample in a manner that depends on its chemistry.
The incident X-ray beam is typically produced from a Rh target, although W, Mo, Cr and
others can also be used, depending on the application.
When x-ray hits sample, the sample emits x-rays along a spectrum of wavelengths
characteristic of the type of atoms present.
If a sample has many elements present, the use of a Wavelength Dispersive Spectrometer
allows the separation of a complex emitted X-ray spectrum into characteristic wavelengths
for each element present.
Various types of detectors used to measure intensity of emitted
radiation.
The intensity of the energy measured by these detectors is proportional to the abundance of
the element in the sample.
The exact value for each element is derived from standards from prior analyses from other
techniques. Instrumentation of X-Ray Spectroscopy.

Components for X-ray spectroscopy are:

X-ray generating equipment, (X-ray tube) Collimator, Monochromators and Detectors.

A. X-ray generating equipment (X-ray tube)

X-rays can be generated by an X-ray tube. X-rays tube is a vacuum tube that uses a high voltage to
accelerate the electrons released by a hot cathodeto a high velocity.
The high velocity electrons collide with a metal target,the anode, creating the X-rays.

B. Collimators
A collimator is a device that narrows a beam ofparticles or waves.
Narrow mean to cause the directions of motion tobecome more aligned in a specific direction
(i.e., collimated or parallel).
Collimation is achieved by using a series of closely spaced ,parallel metal plates or by a bundle
of tubes , 0.5 or less in diameter.

C. Monochromator
Monochromator crystals partially polarize an unpolarized X-ray beam. The main goal of a
monochromator is to separate andtransmit a narrow portion of the optical signal chosenfrom a
wider range of wavelengths available at the input.
Types of Monochromator Metallic Filter
Type Diffraction grating type.

D. X-ray Detectors
The most commonly employed detectors include:Solid State Detectors Scintillation Detectors.
The charge carriers in semiconductor are electronsand holes.
Radiation incident upon the semiconducting junctionproduces electron-hole pairs as it passes
through it.
Electrons and holes are swept away under theinfluence of the electric field, and the proper
electronics can collect the charge in a pulse.

Scintillation detectors

Scintillation detectors consist of a scintillator and adevice, such as a PMT (Photomultiplier tubes),
thatconverts the light into an electrical signal.
It consists of an evacuated glass tube containing aphotocathode, typically 10 to 12 electrodes
called dynodes, and an anode.

Electrons emitted by the photocathode are attracted to the first dynode and are accelerated to
kinetic energies equal to the potential difference between thephotocathode and the first dynode.
When these electrons strike the first dynode, about5 electrons are ejected from the dynode for
each electron hitting it.
These electrons are attracted to the second dynode, and so on, finally reaching the anode.
Total amplification of the PMT is the product of theindividual amplifications at each dynode.
Amplification can be adjusted by changing the voltageapplied to the PMT.
Advantages of X-Ray

Following are the advantages of X-Ray:

➨It is cheaper and simple technique.
➨It has lower radiation compare to CT scan.
➨X-rays are not absorbed very much by air, hence specimen need not be in an evacuated
chamber.
➨It helps to diagnose tumours easily without the needof surgery.
➨X-rays are widely used by radiologists to identify cracks, for infections, to identify level of
injury, and toidentify abnormal bones.
➨It helps to locate alien objects inside or aroundbones.

Disadvantages of X-Ray

Following are the disadvantages of X-Ray:

➨It does not provide 3D information.
➨Bones can block significant diagnostic data as it absorbs the radiation.
➨They do not interact very strongly with lighter elements.
➨Due to its radiation, it mutates cells which causes ionization. This often leads to cancer.
➨It does not produce the best image but medium quality image

Applications of X-Ray Spectroscopy

X-ray spectrometry is used in a wide range ofapplications, including
➨Research in igneous, sedimentary, and metamorphicpetrology
➨Soil surveys
➨Mining (e.g., measuring the grade of ore)Cement production

➨Ceramic and glass manufacturingMetallurgy (e.g., quality control)

➨Environmental studies (e.g., analyses of particulate matter on air filters)

➨Petroleum industry (e.g., sulfur content of crude oilsand petroleum products)
➨Field analysis in geological and environmental studies (using portable, hand-held XRF
spectrometers)
Limitations of X-Ray Spectroscopy
The technique requires the availability of a compoundas a single crystal.
Most chemists find this process very tedious, timeconsuming and it requires a skillful
hand.

References

https://slideplayer.com/slide/5770713/
http://instructor.physics.lsa.umich.edu/adv-labs/X-Ray_Spectroscopy/x_ray_spectroscopy_v2.pdf
https://www.iucr.org/__data/assets/pdf_file/0013/733/chap16.pdf
http://www.issp.ac.ru/ebooks/books/open/X-Ray_Spectroscopy.pdf
https://en.wikipedia.org/wiki/X-ray_spectroscopy
https://www.britannica.com/science/X-ray-spectroscopy
http://umich.edu/~jphgroup/XAS_Course/Harbin/Lecture1.pdf
https://www.ixasportal.net/ixas/images/ixas_mat/Giuliana_Aquilante.pdf
http://www.spectroscopyonline.com/x-ray-spectroscopy
https://www.slideshare.net/nanatwum20/xrf-xray-fluorescence
.