X-Ray Spectroscopy

Absorption, Diffraction and

Fluorescence
 Introduction
• X-Rays are short wavelength electromagnetic radiation produced by
the deceleration of high-energy electrons or by electronic transitions
of electrons in the inner orbital of atoms.

• X-ray spectroscopy is based on measurement of emission,

absorption, scattering, fluorescence, and diffraction of
electromagnetic radiation.

• X-ray fluorescence and X-ray absorption methods are widely used

for the qualitative and quantitative determination of all elements in
the periodic table having atomic numbers greater than that of
sodium
 Origin of X-rays

§ X-rays are generated when high velocity electrons are bombarded on metal
target.
§ Inner orbital electrons in K or L shells of metal atoms are knocked out
§ Outer shell electrons undergo transitions to the lower shells and give off
high energy X-Rays
Continuous and line spectrum

From electron transitions

involving inner shells

•Atomic number >23

- 2 line series K and L
- E K> EL

•Atomic number < 23

- K only
-
 Interaction of X-rays with matter
(a) Absorption:
• When a beam of X-rays is passed through a thin layer of matter, its intensity or power
is generally diminished as a consequence of absorption.

• The absorption spectrum of an element, is simple and consists of a few well-defined

absorption peaks.

Absorption of X rays follows Beer’s law:

• Ln P0/P = µMηX

η is density of the sample

µM is mass absorption coefficient

X is thickness of sample

• µM = CN/A* Z^4* l
 (b) Diffraction:

AP + PC = n l
AP = PC = d sin q
n l = 2 d sin q
nl
sin q =
2d

§Diffraction is based on scattering of X rays by crystals.

§ Every crystalline substance scatter X rays in its own unique diffraction pattern producing
fingerprint of its atomic and molecular structure.
§ If l is known and q can be measured then you can calculate d.
Applications:
•State of anneal in metals
•Particle size distribution
• Polymer Characterization
• To determine crystallinity of polymer
• Crystal material will include crystal structure
and will produce definite diffraction lines and
spots
• Comparing crystallinity with standards
(c)Fluorescence:
• Emission of x-ray from excited
elements

– Absorption removes electron

– Fluorescence involves inter

electron transfers

• The process of emissions of

characteristic x-rays is X-ray
Fluorescence (XRF)

– innermost K and L shells are

involved in XRF detection
X-ray Fluorescence
 X-Ray Instrumentation
(a) Source:
The X-ray Tube

Radioisotopes

Secondary Fluorescent Sources

(b) Collimator:
X-rays produced are randomly
directed which are narrowed
down by collimator .
(c)Monochromator:
Filters and Crystal Monochromator

(d) Detectors:
Proportional Counters, Ionization Chambers, Scintillation Counters, Geiger-muller tube.
 Applications
• Absorption:
– To locate trace elements in barium and iodine in body

– To detect blow hole and segregation of impurities such as oxides at the welds.

– To detect fractured bones in human body

– to identify shapes and sizes of veins and capillaries

• Diffraction:
– Identify crystal structure.

– Polymer Characterization – Degree of crystallization

– State of anneals in metals

– To identify corrosion products

• Fluorescence:
– Silica in slurries of ores, Cr in SS, Mn in plain steels, W in HSS, elemental analysis
of slags etc

– In rubber industries, determination of vulcanizing element

– Trace elements in plants and food, P in fertilizers etc.

Thank you