X-Ray Flourescence (XRF)

Popular for its relatively low-cost of acquisition, ease of use, and limited sample preparation X-ray
Fluorescence (XRF) technology is a popular piece of test equipment for many application needs.

XRF (X-ray fluorescence) is a non-destructive analytical technique used to determine the elemental
composition of materials. XRF analyzers determine the chemistry of a sample by measuring the
fluorescent (or secondary) X-ray emitted from a sample when it is excited by a primary X-ray source. Each
of the elements present in a sample produces a set of characteristic fluorescent X-rays ("a fingerprint")
that is unique for that specific element, which is why XRF spectroscopy is an excellent technology for
qualitative and quantitative analysis of material composition.

The X-ray fluorescence process

1. A solid or a liquid sample is irradiated with high energy X-rays from a controlled X-ray tube.

2. When an atom in the sample is struck with an X-ray of sufficient energy (greater than the atom’s
K or L shell binding energy), an electron from one of the atom’s inner orbital shells is dislodged.

3. The atom regains stability, filling the vacancy left in the inner orbital shell with an electron from
one of the atom’s higher energy orbital shells.

4. The electron drops to the lower energy state by releasing a fluorescent X-ray. The energy of this
X-ray is equal to the specific difference in energy between two quantum states of the electron.
The measurement of this energy is the basis of XRF analysis.

A detailed breakdown of the process is as follows:

1. An x-ray beam with enough energy to affect the electrons in the inner shells of the atoms in a
sample is created by an x-ray tube inside the analyzer. The x-ray beam is then emitted from the
front end of the handheld XRF analyzer.

2. The x-ray beam then interacts with the atoms in the sample by displacing electrons from the inner
orbital shells of the atom. This displacement occurs as a result of the difference in energy between
the primary x-ray beam emitted from the analyzer and the binding energy that holds electrons in
their proper orbits; the displacement happens when the x-ray beam energy is higher than the
binding energy of the electrons with which it interacts. Electrons are fixed at specific energies in
their positions in an atom, and this determines their orbits. Additionally, the spacing between the
orbital shells of an atom is unique to the atoms of each element, so an atom of potassium (K) has
different spacing between its electron shells than an atom of gold (Au), or silver (Ag), etc.

3. When electrons are knocked out of their orbit, they leave behind vacancies, making the atom
unstable. The atom must immediately correct the instability by filling the vacancies that the
displaced electrons left behind. Those vacancies can be filled from higher orbits that move down
to a lower orbit where a vacancy exits. For example, if an electron is displaced from the innermost
shell of the atom (the one closest to the nucleus), an electron from the next shell up can move
down to fill the vacancy. This is fluorescence.

4. Electrons have higher binding energies the further they are from the nucleus of the atom.
Therefore, an electron loses some energy when it drops from a higher electron shell to an electron
 shell closer to the nucleus. The amount of energy lost is equivalent to the difference in energy
between the two electron shells, which is determined by the distance between them. The
distance between the two orbital shells is unique to each element, as mentioned above.

5. The energy lost can be used to identify the element from which it emanates, because the amount
of energy lost in the fluorescence process is unique to each element. The individual fluorescent
energies detected are specific to the elements that are present in the sample. In order to
determine the quantity of each element present, the proportion in which the individual energies
appear can be calculated by the instrument or by other software.

The entire fluorescence process occurs in small factions of a second. A measurement

using this process and a modern handheld XRF gun can be made in a matter of seconds. The
actual time required for a measurement will depend on the nature of the sample and the levels
of interest. High percentage levels will take a few seconds while part-per-million levels will take
a few minutes.

Figure 1. The Concept of Electron – X-ray Interaction

 Figure 1. The XRF process inside a Handheld analyzer

Types of XRF Spectroscopy:

There are two main types of XRF spectroscopy. Energy Dispersive XRF (EDXRF) and Wavelength
Dispersive XRF (WDXRF), which differ primarily in the way the fluorescent X-Rays are detected and
analyzed.

Energy Dispersive XRF

Energy Dispersive X-ray Fluorescence (EDXRF) is one of two general types of X-ray Fluorescence
techniques used for elemental analysis applications. In EDXRF spectrometers, all of the elements in the
sample are excited simultaneously, and an energy dispersive detector in combination with a multi-channel
analyzer is used to simultaneously collect the fluorescence radiation emitted from the sample and then
separate the different energies of the characteristic radiation from each of the different sample elements.
Resolution of EDXRF systems is dependent upon the detector, and typically ranges from 150 eV – 600 eV.
 The principal advantages of EDXRF systems
are their simplicity, fast operation, lack of moving parts, and
high source efficiency.

X-ray optics can be used to enhance EDXRF

instrumentation. For conventional XRF instrumentation,
typical focal spot sizes at the sample surface range in
diameter from several hundred micrometers up to several
millimeters. Polycapillary focusing optics collect X-rays from
the divergent X-ray source and direct them to a small
focused beam at the sample surface with diameters as small
as tens of micrometers. The resulting increased intensity
delivered to the sample in a small focal spot allows for
enhanced spatial resolution for small feature analysis and
enhanced performance for measurement of trace
elements for Micro EDXRF applications.

Doubly curved crystal optics direct an intense micron-

sized monochromatic X-ray beam to the sample
surface for enhanced elemental analysis.

Wavelength Dispersive X-ray Fluorescence (WDXRF)

Wavelength Dispersive X-ray Fluorescence (WDXRF) is one of two general types of X-ray
Fluorescence instrumentation used for elemental analysis applications. In WDXRF spectrometers, all of
the elements in the sample are excited simultaneously. The different energies of the characteristic
radiation emitted from the sample are diffracted into different directions by an analyzing crystal or
monochrometer (similar to the action of a prism dispersing different colors of visible light into different
directions). By placing the detector at a certain angle, the intensity of X-rays with a certain wavelength
can be measured. Sequential spectrometers use a moving detector on a goniometer to move it through
an angular range to measure the intensities of many different wavelengths. Simultaneous spectrometers
are equipped with a set of fixed detection systems, where each system measures the radiation of a specific
element. The principle advantages of WDXRF systems are high resolution (typically 5 – 20 eV) and minimal
spectral overlaps.

X-ray optics can be used to enhance WDXRF instrumentation. For conventional XRF
instrumentation, typical focal spot sizes at the sample surface range in diameter from several hundred
micrometers up to several millimeters. Polycapillary focusing optics collect X-rays from the divergent X-
ray source and direct them to a small focused beam at the sample surface with diameters as small as tens
of micrometers. The resulting increased intensity delivered to the sample in a small focal spot, allows for
enhanced spatial resolution for small feature analysis and enhanced performance for measurement of
trace elements for Micro WDXRF applications. Polycapillary collimating optics allow for efficient collection
of the characteristic fluorescence X-rays from a small spot on the sample surface and redirection as a
parallel beam to the analyzing flat crystal for energy dispersion.

Conversely, instead of using a polycapillary collimating optic and a flat crystal for fluorescence collection
and dispersion, a doubly curved crystal monochrometer can be used to collect select emitted fluorescence
from the sample and direct it to a detector.

Additionally, two doubly curved crystal optics can be used for monochromatic WDXRF with the advantage
of very high sensitivity for a specific sample element of interest. The technology has been successfully
used for measurement of low levels of sulfur in petroleum available in the XOS SINDIE analyzer.
XRF Instrumentation and Components:

X-Ray Source

The “front end” of both types of XRF’s is the X-ray source. The source consists of an evacuated
chamber with a heated cathode, which is usually a tungsten wire, and an anode, which is held at a
potential difference of several tens of kilovolts relative to the cathode. Thermal electrons are released
from the cathode and accelerated toward the anode. When the electron beam impinges upon the anode,
bremsstrahlung radiation as well as X-ray lines characteristic of the anode material are emitted. These
photons escape through a beryllium window built into the side of the tube.

There is no one-size-fits-all approach for source selection in XRF. X-ray tube powers may be set
up at very different levels, from a fraction of a watt for EDXRF instruments with high detection efficiencies
to several kilowatts for WDXRF instruments. In this latter case, the tube must be liquid-cooled since the
majority of the power is dissipated as heat. The anode materials must be carefully chosen as well, since
the wavelength of their characteristic lines is important for proper excitation of the sample. Some example
single-element anode materials are aluminum, chromium, tungsten, palladium, or gold. For detection of
light elements, a high intensity of low energy, i.e. 1-10 keV, radiation must be available, while heavy
elements require excitation at higher energies up to 50 keV (Jenkins 1995: 43-47, Skoog 1998: 274). It is
also important to keep in mind that the primary source of detector background will be the intense primary
radiation from the tube, above which the secondary sample radiation must be detected. The use of
secondary targets, or filters, can greatly reduce the background and improve sensitivity for specific
portions of the spectrum.

For instruments that are designed to acquire the entire spectrum with good sensitivity on light as
well as heavy elements, a different approach is taken. A tube anode material is chosen to give a high
bremsstrahlung or continuum output, which is used to excite a secondary fluorescer, or target, which
gives off its own characteristic lines without the continuum. The sample is then excited by the emission
from the target, which is chosen to efficiently excite elements in a certain Z range. A system may be set
up to change targets automatically during the analysis so that the low, middle, and high end of the sample
spectrum may be sequentially boosted. When an EDXRF instrument uses such a system, tube powers must
be increased dramatically since most of the original X-ray intensity is lost.

Certainly XRF excitation is not limited only to X-ray tubes. Less common excitation sources include
gamma-emitting radioisotopes (241Am, 109Cd, 153Gd, and others), electron sources where the sample
is the tube anode, and synchrotrons, which produce highly intense, coherent, monochromatic X-ray
beams (Jenkins 1988: 56, Jenkins 2000).

Sample Chamber

Up to this point, little has been said regarding what kinds of samples may be analyzed by XRF. The
development of portable XRF (PXRF) instruments has greatly expanded the range of samples suitable for
analysis. There is no longer a need to fit a sample into a small chamber. In the case of PXRF, it is possible
to analyze the samples with the instrument in a stand or the instrument can be moved to the sample, as
in the case of analyzing a exposed rock outcrop or a large painting. The majority of the samples analyzed
by XRF at MURR are small obsidian artifacts that are placed on the nose of the instrument. We have
recently acquired an automated sample changer that allows us to load up to 20 samples at a time and
operated much like the sample changers on large lab-based instruments.

Detector Systems

The two main types of XRF spectrometers (WD and ED) differ completely in their detection systems. EDXRF
systems depend on semiconductor-type detectors which receive the entire emitted spectrum from the
sample and decode it into a histogram of number of counts versus photon energy. WDXRF spectrometers,
however, use an analyzing crystal to disperse the emitted photons based on their wavelength and place
the detector in the correct physical location to receive X-rays of a given energy.

Application of XRF Technologies

Majority of XRF application is involved in geological sciences. The determination of the elemental
composition of geological samples is widely achieved through the use of this technology. Industrial
applications of XRF is also mostly on mining and mineral processing industries. The specific application of
XRF analyzers in these industries is in the determination of concentrate grade and quality control. Due to
nature of the process involved, XRF can be quite accurate. However, the technology is not perfect. Several
factors can easily interfere with the device. A comparison of the device’s advantages and disadvantages
is shown below:

Advantages Disadvantages
• Cost-efficient • Relative humidity and/or temperature affect
• In-situ analysis both the analyzer and the substrate
• Easy in use • Density and geometry of the substrate can
• Lightning Fast analysis influence results
• Available in Handheld portable • Interferences caused by elements other than
• Detects Unique Energy Signature of Elements the metal of interest (by absorption, scattering, or
enhancing the fluorescence)
• Detection limits of the metal of interest. Some
metals have really low detection limits (up to ppm
only)