X Ray Fluorescence (XRF)

Principle of XRF

XRF spectroscopy is widely used for the qualitative and quantitative elemental analysis of
environmental, geological, biological, industrial and other types of samples. Compared to some
techniques, XRF has the advantage of generally being non-destructive, multi-elemental, fast, and
cost effective. It also provides a fairly uniform detection limit across a large portion of the
periodic table and is applicable to a wide range of concentrations, from a 100% to few parts per
million.

Figure 1 X-ray fluorescence principle

The X-ray fluorescence principle is depicted in Figure 1. An inner shell electron is excited by an
incident photon in the X-ray region. During the de-excitation process, an electron is moving from
a higher energy level to fill the vacancy created by an ejection. The energy difference between
the two shells appears as an X-ray emitted by the atom. The X-ray spectrum acquired during the
above process reveals a number of characteristic peaks. The energy of the peaks leads to the
identification of the elements present in the sample (qualitative analysis), while the peak
intensity provides the relevant or absolute elemental concentration (semi-quantitative or
quantitative analysis).

X-Ray Generation

X-rays are generated when the X-ray tube (Figure 2) accelerates electrons at a high voltage and
bombards them against a metal anode (anti-cathode). In this cathode very high voltages are
applied to cathode. Due to this high amount of heat is also generated. Ejected electrodes are
bombarded on the anode surface by the use of focusing cup which focus the electrons towards
anode and reduce the scattering. Bombarded electrons on the anode surface generates the
primary X-Rays having the wavelength in the range of 0.01 nm to 10 nm.There are two types of
X-ray tubes, the side window type and the end window type. Both are designed to irradiate
intense X-rays on the sample surface as evenly as possible.
A beryllium foil is commonly used as a window for retrieving incident X-rays. Tungsten,
rhodium, molybdenum and chromium are examples of anti-cathodes. Anti-cathode is also
referred to as the target. The anti-cathode is chosen based on what type of samples will be
analyzed. X-ray tubes with anti-cathodes the same as elements being analyzed should not be
used.

Figure 2 X-ray tube

Figure 3 shows a typical XRF spectroscopy arrangement including a source of primary radiation
(usually a radioisotope or an X-ray tube) and equipment for detecting the secondary X-rays.
Specific equipment manufacturers will have slightly different arrangements and options available
(such as filters, collimators, and analyzing crystals). Control and analytical software also varies
between instruments and is frequently not inter-compatible with other vendors.
 Figure 3 Typical XRF spectroscopy arrangement.

Filters
The beam filters are usually seated on a changer (which may include vacant positions) and is
equipped with a selection of absorber foils. It is located between the tube and the sample and
filters out undesirable or interfering components of the tube radiation for certain applications and
improves the signal-to-noise ratio. Al and Cu foils, for example, are used as absorbers in a
variety of thicknesses. Beam filters can be selected to suit individual requirements when
purchasing an instrument.

Collimators
Collimators consist of a row of parallel slats. They are used to select a parallel beam of X-rays
coming from the sample and striking the crystal. The spaces between the slats determine the
degree of parallelism and thus the angle resolution of the collimator. A variety of aperture angles
can be chosen to aid in improving the detection of light (low resolution collimator with 1.5 -
2.0) or heavy elements. Some equipment manufacturers have collimators with very low angle
(<1.5) for high resolution measurements. Using a low-resolution collimator increases the
intensity significantly. This enables intensity to be increased without a loss in angle resolution
when analyzing the light elements.

Discriminator
Depending on the application, higher order peaks or other sources of interference can appear in
the pulse height distribution. A discriminator window is used to set a lower and an upper pulse
height threshold. The pulse heights that lie within these limits are counted. This way only higher
order peaks or interference radiation with pulse heights beyond the window is suppressed.
Discriminator reduces undesirable pulses in the background.

Dead Time Correction

Spectrometer electronics need a certain amount of time to process a pulse during which no other
pulse can be registered. This period is called counter channel dead time for an individual pulse.
As the pulse formation is different for the flow counter and the scintillation counter, the dead
times (typically 300 to 400 ns) are also different for each detector. Total dead time is the result of
an individual pulse multiplied by the pulse rate. As the measured pulses occur statistically
distributed over time, the proportion of pulses occurring during the processing period of a
previously registered pulse depends on the intensity of the radiation. What this means is the total
dead time increases due to the increase of the intensity. This results in a non-linear rise of the
measured intensity with the intensity irradiated in the detector. This means the greater the
incident intensity, the greater the losses during measurement. A correction of the measured
intensities is necessary to produce a linear relationship between incident and measured
intensities. A dead time correction can be made in the analysis set up.

Preparation of Solid Samples

Metals
Preparation of metal samples must be simple, rapid and reproducible. Usually metal samples are
prepared as solid disks by conventional methods of machining, such as cutting, milling and
polishing. Grinding is used in the case of hard alloys and brittle materials such as ceramics.
The best polishing operations require very fine abrasives to produce the scratch-free surface
necessary for most analyses. A mirror-like surface is best if the sample is to be analyzed for light
elements. The surface finish is of prime importance because polishing striations give rise to a
shielding effect, which results in a decrease in fluorescence intensities. The decrease in intensity
is more important for lighter elements when the primary radiation is perpendicular to the
striations and weaker when they are parallel to them. Some XRF spectrometers are equipped
with spinning sample holders to smooth out the influence of sample orientation, resulting in
observed intensities on samples and standards that are reproducible.

However, the shielding effect may still be present; sample rotation will compensate for it only if
the magnitude of the effect is the same for standards and samples. Striations must be of the same
size and the compositions of the standards and samples must be similar (same effective
wavelength). In practice, striation depths of 100 mm are acceptable for elements with
characteristic lines of short wavelengths, but striations deeper than few mm may significantly
impair the accuracy of Si, Al and Mg measurements.

Very fine grits of Al2O3, SiC, B6C (80 to 120 grits or finer) are commonly used to obtain the
desired surface finish for most metals (Fe, Ni and Co bases). Mechanical polishing may be
undesirable for soft, malleable, multiphase alloys because of smearing of the softer components.
The intensities of the elements in softer phases increase while those of the harder phases
decrease. In such cases, special precautions must be taken during milling and final polishing of
metals with Ag, Au, Pb, Cu, Al, Zn or Sn bases. Polishing may be a source of contamination
since currently used abrasives, SiC and Al2O3, contain two elements that are often determined in
commercial alloys. Sample surface cleaning may be necessary to remove contamination as well
as grease and handling residue.

Pressed Pellets

Since powders are not affected by particle size limitations, the quickest and simplest method of
sample preparation is to press the powders directly into pellets of equal density, with or without
the use of a binder. Provided that the powder particles are less than about 50 mm in diameter, the
sample will pelletize at 10 to 30 ton. If the self-binding properties of the powder are poor, higher
pressure may have to be employed or in extreme cases a binder may have to be used. It is
sometimes necessary to add a binder before palletizing. The choice of the binding agent must be
made with care. The binder must be free from significant contaminant elements and must have
low absorption. It must be stable under vacuum and irradiation conditions and it must not
introduce significant inter-element interferences. There are a large number of binding agents
proven to be successful; some of the most useful are wax and ethyl cellulose.
The analysis of powders is invariably more complex than metal samples since in addition to inter
element interferences and macro-scale heterogeneity, particle size effects also play a critical role.
Inhomogeneity and particle size can often be minimized by grinding and pelletizing at high
pressure, however, the effects cannot be completely removed because the harder compounds
present in a particular matrix are usually not broken down. These effects produce systematic
errors in the analysis of specific type of material, such as siliceous compounds in slag, sinters,
and certain minerals.

Preparation of Liquid Samples

Provided that the liquid sample being analyzed is single phase and relatively involatile, it is an
ideal form for XRF analysis. A special sample cup (liquid sample holder) and helium path
instrument are used for measurement. The liquid phase is particularly convenient since it offers a
very simple means for the preparation of standards and most matrix interferences can be
successfully overcome by introducing the sample into a liquid solution. The majority of matrix
interferences can be removed by the solution technique, but sometimes the process of dealing
with a liquid rather than a solid can present special problems which can limit the usefulness of
the technique.
For example, the introduction of a substance into a solution inevitably means dilution and
combined with the need for a support window in the sample cell, plus the extra background
arising from scatter by the low atomic number matrix, leads to a loss of sensitivity, particularly
for longer wavelengths (greater than 2.5 ). Problems can arise from variations in the thickness
and composition of the sample support film. The most commonly used types of film is 2.5 to 6.5
mm Mylar.

Instrumentation and details

 16 turret 8 turret

Figure 4 XRF instrument and its sample holding container

Features :
Concentration range of analysis: ppm(0.0001%) to 100 %, except for carbon, only > 10%
Sample can be analyzed either in air/vacuum/helium
Sample size : 0.5 mm to 300mm (max size : 360mm dia. X 150mm ht.)
Sample exposure area = 10mm dia
Vacuum required : 30 pa (Pascal)

calibration methods :

1. fundamental parameter method(FP method)

2. calibration curve method
Energy calibration : using std. Al sample
Intensity calibration : using std S.S. sample
Actual analysis takes place in two following stages, one after another.
1. For C to Sc ( i.e. Carbon to Scandium )
2. For Ti to U ( i.e. Titanium to Uranium )

Temperature 10 to 30 degree Celsius

Applied voltage 5 to 50 kV with Rh target
Current- 1-1000 microampere

Working

1. Calibration of the instrument

2. Sample chamber is opened ,sample is kept and it is closed
3. Selection of the medium
4. Registration of the sample name (content data or intensity data)
5. Optimum calibration curve for sample is selected
6. Measurement time
After that all indications are shown in this way :

Figure 5 Indication of all working parts

Results

Figure 6 Intensity v/s Energy

Figure 7 Intensity v/s Energy (Use of filter)

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)

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
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.

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 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 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.

Conclusion
Since X-ray fluorescence analysis can analyze a sample non-destructively and quickly, it can be
applied to a wide range of uses such as manufacturing and quality control. Recently, the
quantitative analysis of trace elements became possible because of high-sensitivity technologies
such as filtering, which eliminates background interference, and thin film methods. In the future,
X-ray fluorescence analysis will become more widespread particularly in measuring hazardous
metals in materials and soils.