Presented By: M.

Ishtiaq Anjum (2018-UET/MS-PHY-15)

Syed Danish Hussain (2018-UET/MS-PHY-10)
OUTLINES
 Introduction
 Basic principle
 Instrumentation
 Working
 Result & Discussion
 Applications & Advantages
 XRF is an analytical method to determine the chemical
composition of all kinds of materials.
 Materials can be solids, liquid, powder, filtered or other form.
 XRF can also sometimes be used to determine the thickness
and composition of layers and coatings.
 This method is fast, accurate and non-destructive and
usually requires only a minimum of sample preparation.
X-RAYS
 Electromagnetic waves with their associated wavelengths or beams of
photons with their associated energies.

INTERACTION OF X-RAYS WITH MATTER

 Three main interactions when x-ray contact

matter:
i. Fluorescence
ii. Compton scattering
iii. Rayleigh scattering

 Fluorescence and scatter depends on the

thickness, density and composition of the
material , and on the energy of the x-rays
X-Ray Fluorescence
 X-ray fluorescence is the emission of characteristic or secondary X-rays from a
material that has been excited by bombarding with high energy electrons, or other
X-ray or γ -ray photons.

Basic Principle
 XRF is based on the principle that
individual atoms, when excited by an
external energy source, emit X-ray
photons of a characteristic energy
or wavelength. By estimating the
energy of photons and counting
the number of photons of each
energy emitted from a sample, the
element
elementspresent
presentmay
maybebeidentified
identified
and
andquantified.
quantitated.
 THEORY
 When an electron beam of high energy strikes a material, one of the results of
the interaction is the emission of photons which have a broad continuum of
energies. This radiation, called “braking radiation”, is the result of the
deceleration of the electrons inside the material.
 Another result of the interaction between the electron beam and the material is
the ejection of photoelectrons from the inner shells of the atoms making up the
material. These photoelectrons leave with a kinetic energy (E-φ) which is the
difference in energy between that of the incident particle (E) and the binding
energy (φ) of the atomic electron. This ejected electron leaves a “hole” in the
electronic structure of the atom, and after a brief period, the atomic electrons
rearrange, with an electron from a higher energy shell filling the vacancy. By way
of this relaxation the atom undergoes fluorescence, or the emission of an X-ray
photon whose energy is equal to the difference in energies of the initial and final
states. Detecting this photon and measuring its energy allows us to determine
the element and specific electronic transition from which it originated
The basic components of all XRF spectrometer includes a source, sample and a
detection system.

Source
The source is generally an X-ray tube which irradiates the sample .

 All X-ray tubes work on the same principle: accelerating electrons in an electrical
field and decelerating them in a suitable anode material.
 The X-rays escape from the housing at a special point that is particularly transparent
with a thin beryllium window.
 The main differences between tube types are in the polarity of the anode and
cathode and the arrangement of the exit window.
 Conventional X-Ray Tubes include:
• End Window X-Ray Tubes
• Side Window X-Ray Tubes
 END WINDOW TUBES :
:

 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
(annular 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.
 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
Detectors:

 detector is composed of a non-conducting or semiconducting material between two charged

electrodes.

 X-ray radiation ionizes the detector material causing it to become conductive, momentarily.

 The newly freed electrons are accelerated toward the detector anode to produce an output
pulse.

 An ionized semiconductor produces electron-hole pairs, the number of pairs produced is

proportional to the X-ray photon energy.

 Different types of detectors are used in XRF, most common are:

• Solid state detector
• Scintillation detector
• Gas filled detectors
 SOLID–STATE DETECTOR

 Constructed with a body of silicon, germanium or

other semiconducting material.
 X- ray photons enter the detector through a
beryllium window.
 Electron-hole pairs are produced as the photons
enter and penetrate into the body of the detector.
 Number of electrons depend on the energy of the
incoming photons.
 The pulse produced can be recorded and is
proportional to the number of electrons and hence
proportional to the energy of the incoming
radiation.
 A multi channel analyzer counts the pulse after
amplification.
GAS-FILLED DETECTORS:

 Constructed from a metal cylinder at

earth potential with a co-axial 50 mm
tungsten anode wire running down its
length and raised to a high voltage.
 X-ray photons enter the detector through
a beryllium window.
 A cloud of electrons is created by the
photon which are then attracted towards
the wire.
 A voltage drop occurs at wire as the
electrons reach the wire, which appears
as a negative pulse in the amplifier.
 No of pulses are the counted.
 SCINTILLATION DETECTOR
 Consists of four main parts including
beryllium window, NaCl scintillator
crystal and a photo multiplier tube with
Sb/Cs .
 X-ray photon pass through the beryllium
window and hit the scintillator crystal,
producing a blue flash light.
 The light photons enter into the
photomultiplier tube and impact on the
photo cathode producing a burst of
electrons, which are accelerated by a
bunch of dynodes .
 electrons reaching the anode cause a
potential drop registered as a negative
voltage pulse in the amplifier.
Spectrometer system are generally divided into main groups:
 Energy Dispersive X-ray fluorescence Spectrometers (EDXRF)
 Wavelength dispersive X-ray fluorescence Spectrometers (WDXRF)

The difference between the two system is found in the detection system.

EDXRF Spectrometers:

They have a detector that is able to measure the different energies of the
characteristic radiation coming directly from the sample. The detector can separate
the radiation from the sample into the radiation from the elements in the sample. This
separation is called dispersion.
WDXRF SPECTROMETERS:

They use an analyzing crystal to disperse the different energies. All

radiation coming from the sample falls on the crystal. The crystal diffracts
the different energies in different directions , similar to a prism that
disperses different colors in different directions.
Diffraction:

The two most common diffraction instruments are the crystal and multilayer. Both work
according to Bragg’s formula: nλ = 2d · sinθ

 In XRF, the d-value of the analyzer crystal is known and we can solve Bragg's equation
for the element characteristic wavelength (λ).
n = integer
d = crystal lattice or multilayer spacing
θ = The incident angle
λ= wavelength
 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.
 Sample Preparation:

There are numerous methods of sample preparation for analysis by an XRF spectrometer,
including:
 Solid sample preparation;
 Liquids;
 Powders;
 Pellets;
 Fused beads.

Solid samples can be analyzed by an XRF spectrometer with little to no sample

preparation, but surface area variations and irregularities can introduce a high degree of
error analysis due to the sensitive calibration of the XRF equipment. Ideally, solid samples
will be cut and finished using grinding methods and an application of a fusion flux
mixture. Granular mixtures of 64.7% lithium metaborate and 35.3% lithium tetraborate
fusion flux are ideal for solid sample preparation, with optimal analytical results for
various aluminosilicates.
 Liquid samples are prepared for XRF analysis through the application of a support
film which exhibits little interference with the XRF spectrometer’s incident beam.
Powders are prepared using a similar methodology.

 Pellets provide better insights into the homogenous composition of a sample. They
are produced specifically for analysis in an XRF spectrometer by grinding a sample
to a fine powder using a laboratory crusher or pulverizer and mixing it with a binding
agent, prior to compressing the mixture into a denser sample. This provides
exceptional analysis quality; however, pellets retain mineralogical structures which
interfere with or alter the fluorescent process, impacting results accuracy.

 The preparation of samples as fused beads or discs reduces this issue, providing a
near-perfect representation of the homogenous XRF reaction. This process involves
crushing the sample, then mixing it with a fusion flux of varying ratios into a
platinum crucible. The mixture is then heated to temperatures up to 1000°C
(1832°F) and cast as a disc or a bead. An XRF spectrometer can accurately
examine a fusion bead or disc sample due to the reduction of its mineralogical
matrixes.
Spectrum of a soil sample
X-Ray fluorescence is used in a wide range of applications, including

 research in igneous, sedimentary, and metamorphic petrology

 soil surveys
 mining (e.g., measuring the grade of ore)
 cement production
 ceramic and glass manufacturing
 metallurgy (e.g., quality control)
 environmental studies (e.g., analyses of particulate matter on air filters)
 petroleum industry (e.g., sulfur content of crude oils and petroleum products)
 field analysis in geological and environmental studies (using portable, hand-
held XRF spectrometers)
Strengths and Limitations

Strengths:

X-Ray fluorescence is particularly well-suited for investigations that involve:

 bulk chemical analyses of major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P) in
rock and sediment

 bulk chemical analyses of trace elements (>1 ppm; Ba, Ce, Co, Cr,Cu, Ga, La,
Nb, Ni, Rb, Sc, Sr, Rh, U, V, Y, Zr, Zn) in rock and sediment
Limitations:

In theory the XRF has the ability to detect X-ray emission from virtually all elements,
depending on the wavelength and intensity of incident x-rays. However...

 In practice, most commercially available instruments are very limited in their ability
to precisely and accurately measure the abundances of elements with Z<11 in
most natural earth materials.

 XRF analyses cannot distinguish variations among isotopes of an element, so

these analyses are routinely done with other instruments.

 XRF analyses cannot distinguish ions of the same element in different valence
states, so these analyses of rocks and minerals are done with techniques such as
wet chemical analysis or Mossbauer spectroscopy.
Benefits of XRF Analysis :

 Minimal or no sample preparation

 Non-destructive analysis
 Na11 to U92 analysis, ppm to high % concentration range
 No wet chemistry – no acids, no reagents
 Analysis of solids, liquids, powders, films, granules etc.
 Rapid analysis – results in minutes
 Qualitative, semi-quantitative, to full quantitative analysis
 For routine quality control analysis instrument can be ‘used by anyone’