Production of X-rays

When fast moving electrons strike on a very hard target of high atomic number, e.g. platinum, tungsten,
molybdenum etc, X-rays are produced. Dr. William Collidge, in 1913, designed a tube for the production of X-rays.
This tube is known as collidge tube or modern x-rays tube.
Coolidge X-ray Tube

X-ray collidge
tube
The Coolidge tube consists of a glass tube G exhausted to nearly, perfect vacuum of about 10 -5mm of mercury
provided with a cathode and the target T. The cathode consists of a tungsten filament (F) heated by a low tension
battery. The filament is placed inside a metal cup C to focus the electron on to the target. The target is made like
tungsten or molybdenum having high melting point and high atomic weight held at an angle of 45 o to the horizontal.
The target T held by a copper rod outside the tube. The anode is connected to the positive and cathode to the
negative terminal of the high tension power supply.
Working
The filament F is heated by a passing a suitable current through it. The electrons emitted from the filament are
focused at a point on the target with the help of a metal cup C. On account of the extremely high potential difference
between the cathode and the anode, the electrons arrive at the target with high speed. The speed of the electrons can
be further increased by increasing the accelerating voltage. On striking the anode, the electrons are stopped. Nearly
98% of the energy of the incident electrons is converted into heat. The remaining energy appears in the form of X-
rays. However, intense heat is produced, which may melt the target. Therefore, the target must be cooled to remove
the heat generated in it by continuous electron bombardment. The usual method is to mount the target material on
the hollow copper tube through which cold water is continuously circulated.

Production of X-rays by Coolidge Tube

The Coolidge tube, also called hot cathode tube, is the most widely used device for the production of X-rays.

In the Coolidge tube, the electrons are produced by thermionic effect from a tungsten filament heated by an electric current.
The filament is the cathode of the tube. The high voltage potential is between the cathode and the anode, the electrons are
thus accelerated, then hit the anode and X-ray is produced.
Production of X-rays in Coolidge tube
It consists of an evacuated chamber where electrons are accelerated using high voltage of about 10 4 to 105 volts.
These electrons are allowed to strike a metal target such as Tungsten or Molybdenum (Mo) having high melting
point and atomic weight. Due to this the metal target gets excited to higher energy state and when the excited atoms
return to their ground state X-rays are emitted.

About 98% of the energy is converted into heat and remaining 2% come out as X-rays. This large amount of heat
can melt the metal target. So a copper tube is placed alongside the metal target where cold water is circulated
continuously.

Frequency and wavelength of X-ray produced:

If V be the accelerating voltage applied between two electrodes, then the kinetic energy acquired by the electrons is
given by:

eV = ½mv2max

Where m, e and v be the mass, charge and velocity of the electrons.

Electrons with energy ½mv2max strike the target and exit to their ground state and this energy is released as photon
(hf).

½ mv2max = hfmax

or, eV = hf

or fmax =eV/h………(i)

Equation (i) gives the frequency of x-rays.

Now, we know f = ch/λ

eV = ch/λmin

∴ λmin = ch/eV……(i)

Equation (ii) gives the wavelength of the electron.

 Control of intensity and quality of X-rays:

a. Intensity control: The intensity of x-rays depends on the number of electrons emitted by the filament. This can
be controlled by varying the electric current flowing through the filament.

b. Quality control: The wavelength of X-rays determines the quality of them. We have,

λmin = ch/eV

Here, c, h and e are constant. So, by adjusting the accelerating potential V we can control the quality of X-rays.

Control of Intensity and Quality

Modern X-ray, the tube has the advantage of independent control of intensity and quality.
1. Control of intensity
The intensity of X-rays depends upon the number of electrons emitted from the filament. This depends upon the
electric current flowing through the filament. So by controlling the current with the help of rheostat, we can control
the intensity of X-rays. Hence, the intensity of the can be changed by adjusting the filament current.
2. Control of quality
If V be the potential difference applied across the two electrodes, then the kinetic energy acquired by the electron is
given by
eV=1/2mv2

where m, e and v be the mass change and velocity of the electron. Therefore, the quality of X-rays depends upon
their energy which, in turn, depends upon the kinetic energy of the incident electrons. The kinetic energy of the
incident electrons depends upon the potential difference between the anode and the cathode. Hence, quality of X-
rays can be adjusted by changing the potential difference across the tube. X-rays having low penetrating power are
called soft X-rays whereas X-rays having high penetrating power are called hard X-rays.
Frequency and Wavelength of X-rays Produced
When the whole of the kinetic energy of the electron is converted into the energy of the X-rays produced, then X-ray
of maximum frequency is obtained. Therefore, if fmax is the maximum frequency of the emitted X-rays, then we have
hfmaxwhere, h is a Planck's constant.∴fmax=12mv2=eV=eVhhfmax=12mv2=eVwhere, h is a Planck's
constant.∴fmax=eVh

If c is the velocity of light in vacuum and λmin be the minimum possible wavelength of the –rays produced, then
λmin=Cfmax=hceVλmin=Cfmax=hceV

Nature of X-rays
X-rays as waves similar to light waves, but of much shorter wavelength about 10 -10 m or 0.1 nm. However, the
wavelength of visible light is nearly 10 3 times more than the wavelength of X-rays. While the wavelength of the
visible light ranges from 4000 A to 8000 A, the wavelength of X-rays generally lies between 1 to 3 A. Since
wavelength is inversely proportional to frequency, therefore the frequency of X-rays is nearly 10 3 of visible light.
Again, since the energy of the photon is directly proportional to frequency, therefore, x-ray photons are much
stronger than the photons of visible light.
Properties of X-rays
1. X-rays are electromagnetic waves having a wavelength in the range from 1 A to 100 A.
2. X-rays can ionize atoms and molecules of matter.
3. They travel by a velocity of light i.e. 3×1010 ms-1 in vacuum or air.
4. They are not deflected by magnetic or electric fields and, therefore, do not possess any charge.
5. X-ray can produce the photoelectric effect.
6. X-rays can affect photographic plates.
7. X-rays can ionize a gas through which they pass.
8. X-rays can be made to reflect, refract and diffract. X-rays show the phenomenon of interference and polarization.
9. X-rays can produce fluorescence in certain metal
10. When certain x-rays fall on certain metals, secondary X-rays are produced.
11. They show particle-like properties in interacting with matter as in photoelectric effect and Compton effect.
Reference
Manu Kumar Khatry, Manoj Kumar Thapa, Bhesha Raj Adhikari, Arjun Kumar Gautam, Parashu Ram
Poudel. Principle of Physics. Kathmandu: Ayam publication PVT LTD, 2010.
http://serc.carleton.edu/research_education/geochemsheets/techniques/XRF.html

X-Ray Fluorescence (XRF)

Karl Wirth, Macalester College and Andy Barth, Indiana University~Purdue University, Indianapolis

What is X-Ray Fluorescence (XRF)

An X-ray fluorescence (XRF) spectrometer is an x-ray instrument used for routine, relatively non-destructive
chemical analyses of rocks, minerals, sediments and fluids. It works on wavelength-dispersive spectroscopic
principles that are similar to an electron microprobe (EPMA). However, an XRF cannot generally make analyses at
the small spot sizes typical of EPMA work (2-5 microns), so it is typically used for bulk analyses of larger fractions
of geological materials. The relative ease and low cost of sample preparation, and the stability and ease of use of x-
ray spectrometers make this one of the most widely used methods for analysis of major and trace elements in rocks,
minerals, and sediment.

Fundamental Principles of X-Ray Fluorescence (XRF)

The XRF method depends on fundamental principles that are common to several other instrumental methods
involving interactions between electron beams and x-rays with samples, including: X-ray spectroscopy
(e.g., SEM - EDS) Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), X-ray
diffraction (XRD), and wavelength dispersive spectroscopy (microprobe WDS).

The analysis of major and trace elements in geological materials by x-ray fluorescence 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. If the energy of the radiation is sufficient to dislodge a tightly-held
inner electron, the atom becomes unstable and an outer electron replaces the missing inner electron. When this
happens, energy is released due to the decreased binding energy of the inner electron orbital compared with an outer
one. The emitted radiation is of lower energy than the primary incident X-rays and is termed fluorescent radiation.
Because the energy of the emitted photon is characteristic of a transition between specific electron orbital in a
particular element, the resulting fluorescent X-rays can be used to detect the abundances of elements that are present

in the sample.

X-Ray Fluorescence (XRF) Instrumentation - How Does It Work?

The analysis of major and trace elements in geological materials by XRF is made possible by the behavior of atoms
when they interact with X-radiation. 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.
 Show Caption

When this primary X-ray beam illuminates the sample, it is said to be excited. The excited sample in turn emits X-
rays along a spectrum of wavelengths characteristic of the types of atoms present in the sample. How does this
happen? The atoms in the sample absorb X-ray energy by ionizing, ejecting electrons from the lower (usually K and
L) energy levels. The ejected electrons are replaced by electrons from an outer, higher energy orbital. When this
happens, energy is released due to the decreased binding energy of the inner electron orbital compared with an outer
one. This energy release is in the form of emission of characteristic X-rays indicating the type of atom present. If a
sample has many elements present, as is typical for most minerals and rocks, the use of a Wavelength Dispersive
Spectrometer much like that in an EPMA allows the separation of a complex emitted X-ray spectrum into
characteristic wavelengths for each element present. Various types of detectors (gas flow proportional and
scintillation) are used to measure the intensity of the emitted beam. The flow counter is commonly utilized for
measuring long wavelength (>0.15 nm) X-rays that are typical of K spectra from elements lighter than Zn. The
scintillation detector is commonly used to analyze shorter wavelengths in the X-ray spectrum (K spectra of element
from Nb to I; L spectra of Th and U). X-rays of intermediate wavelength (K spectra produced from Zn to Zr and L
spectra from Ba and the rare earth elements) are generally measured by using both detectors in tandem. The intensity
of the energy measured by these detectors is proportional to the abundance of the element in the sample. The exact
value of this proportionality for each element is derived by comparison to mineral or rock standards whose
composition is known from prior analyses by other techniques.
 Applications
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)
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 (in abundances >1 ppm; Ba, Ce, Co, Cr, Cu, Ga, La, Nb, Ni, Rb, Sc,
Sr, Rh, U, V, Y, Zr, Zn) in rock and sediment - detection limits for trace elements are typically on the order of a
few parts per million
X-ray fluorescence is limited to analysis of
 relatively large samples, typically > 1 gram
 materials that can be prepared in powder form and effectively homogenized
 materials for which compositionally similar, well-characterized standards are available
 materials containing high abundances of elements for which absorption and fluorescence effects are reasonably
well understood
In most cases for rocks, ores, sediments and minerals, the sample is ground to a fine powder. At this point it may be
analyzed directly, especially in the case of trace element analyses. However, the very wide range in abundances of
different elements, especially iron, and the wide range of sizes of grains in a powdered sample, makes the
proportionality comparison to the standards particularly troublesome. For this reason, it is common practice to mix
the powdered sample with a chemical flux and use a furnace or gas burner to melt the powdered sample. Melting
creates a homogenous glass that can be analyzed and the abundances of the (now somewhat diluted) elements
calculated.

Strengths and Limitations of X-Ray Fluorescence (XRF)?

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 (see TIMS and SIMS).
 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.

User's Guide - Sample Collection and Preparation

Virtually any solid or liquid material can be analyzed, if adequate standards are available. For rocks and minerals,
typical commercial instruments require a sample constituting at least several grams of material, although the sample
collected may be much larger. For XRF chemical analyses of rocks, samples are collected that are several times
larger than the largest size grain or particle in the rock. This initial sample then suffers a series of crushing steps to
reduce it to an average grain size of a few millimeters to a centimeter, when it can be reduced by splitting to a small
representative sample of a few tens to hundreds of grams. This small sample split is then ground into a fine powder
by any of a variety of techniques to create the XRF sample. Care must be taken particularly at this step to be aware
of the composition of the crushing implements, which will inevitably contaminate the sample to some extent.

Data Collection, Results and Presentation.

Block Diagram of XRF

X-ray absorption spectroscopy (XAS) is a technique that uses synchrotron radiation to

provide information about the electronic, structural, and magnetic properties of certain
elements in materials. This information is obtained when X-rays are absorbed by an
atom at energies near and above the core level binding energies of that atom.
Therefore, a brief description about X-rays, synchrotron radiation and X-ray absorption
is provided prior to a description of sample preparation for powdered materials.