X-Ray
Fluorescence
Analysis
Chemical and Environmental Engineering
• When an element is placed in a beam of x-rays, the x-rays are
absorbed. The absorbing atoms become ionized (i.e. due to
the x-ray beam ejects the electron in the inner shell).
• An electron from higher energy shell (i.e. the L shell) then fall
into the position vacated by dislodged inner electron and emit
x-rays or characteristic wavelength.
• This process is called x-ray fluorescence.
2
• The wavelength of fluorescence is characteristic of the element
being excited, measurement of this wavelength enable us to
identify the fluorescing element.
• The intensity of the fluorescence depends on how much of that
element is in x-ray beam.
• Hence measurement of the fluorescence intensity makes
possible the quantitative determination of an element.
3
• The process of detecting and analyzing the emitted x-rays is
called “X-ray Fluorescence Analysis.”
• In most cases the innermost K and L shells are involved in XRF
detection.
• A typical x-ray spectrum from an irradiated sample will display
multiple peaks of different intensities.
4
5
• The characteristic x-rays are labeled as K, L, M or N to denote the shells they
originated from.
• Another designation alpha (α), beta (β) or gamma (γ) is made to mark the x-rays that
originated from the transitions of electrons from higher shells.
• Hence, a Kα x-ray is produced from a transition of an electron from the L to the K
shell, and a Kβ x-ray is produced from a transition of an electron from the M to a K
shell, etc.
• Since within the shells there are multiple orbits of higher and lower binding energy
electrons, a further designation is made as α1, α2 or β1, β2, etc. to denote transitions
of electrons from these orbits into the same lower shell.
6
The X-Ray Fluorescence Process
Example: Titanium Atom (Ti = 22)
1) An electron in the K shell
is ejected from the atom by
an external primary
excitation
x-ray, creating a vacancy.
7
2) An electron from the L or M
shell “jumps in” to fill the vacancy.
In the process, it emits a
characteristic x-ray unique to this
element and in turn, produces a
vacancy in the L or M shell.
8
3) When a vacancy is created in
the L shell by either the
primary excitation x-ray or by the
previous event, an electron from
the M or N shell “jumps in” to
occupy the vacancy. In this
process, it emits a characteristic x-
ray unique to this element and in
turn, produces a vacancy in the M
or N shell.
9
“Auger” Electron
The excitation energy from the
inner atom is transferred to one of
the outer electrons causing it to be
ejected from the atom. This
process is a competing process to
the XRF.
10
• X-ray fluorescence's spectroscopy provides a means of
identification of an element, by measurement of its characteristic
X-remission length or energy.
• The method allows the quantification of a given element by first
measuring the emitted characteristic line intensity and then relating
this intensity to elemental concentration.
11
• 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).
12
Advantages of X-ray Fluorescent Analysis
• Rapid analysis
• Nondestructive analysis
• No spectrum is affected by chemical bonding
• Easily analysis of the element among the same family elements
• High accurate analysis (5B to 92U can be analysis)
• Easy qualitative analysis
• Easy sample preparation
13
• Elemental oxygen can be analyzed but oxide content is estimated by
assuming the sample contains certain oxides.
• Consequently oxide content is an estimated result because XRF can
only determine elements.
• Elemental carbon and sulfur can also be analyzed but not CO3=, SO4=,
SO3= .
14
Schematic figure of an x-ray fluorescence spectrophotometer
BASIC PRINCIPLE: n 2d.sin 15
X-ray generator part
To
X-ray Sample
collimator spectrometer
generator chamber
part
Spectrometer Part To
counting
Analyzing and
collimator
crystal recording
part
16
X-RAY GENERATOR
• X-ray tube for XRF spectrometer is a diode (vacuum tube) consist of the
filament generating thermo- electron and the anode (target) generating
x-rays.
• Near the target, there is a window to pass x-rays through to the outside
tube. The window material, Beryllium, is employed because of its nature
for having the excellent transmission (penetration) of x-rays.
17
• There two types of x-ray tubes:
- Side Window Type X-ray Tube
- End Window Type X-ray Tube
18
19
Comparison on the grounding method and window thickness of
x-ray tubes
Type Target Ground Window Max Cooling
Material -ing Thicknes Load Water
s
Side W, Cr, Anode 1000μm, 3 kW City
window Mo, Au, 300μm water
etc (Cr)
End Rh, etc Cathod 127μm 3kW Deionize
window e d water*
* Less than 2 μS/cm (higher than 50x104Ωcm
20
• Rh target end-window type x-ray tube has the features that since it is
effectively sensitive to the element less than the atomic number 16 (S)
and it can also obtain relatively the good sensitivity to the heavy
elements. It can make the measurements from heavy elements to light
elements without exchanging X-tube.
• The frequency of using this Rh target X-ray tube is high.
21
• In case of side window type x-ray tube, the W and Mo target x-ray tubes
will be applied for the analysis of heavy elements and the Cr target x-
ray tube will be applied for the analysis of light elements.
• Especially , the Mo target x-ray tube will be frequently applied for the
analysis of environmental pollution such as Hg, Pb, As and so on.
22
Analyzing crystal
• The diffraction phenomenon of x-ray through the single crystal is
utilized for the dispersion of x-rays. This crystal is called the analyzing
crystal. In accordance with the wavelength region of the fluorescence
x-rays, the optimum analyzing crystal is employed respectively.
23
• Analyzing crystals such as TAP, RAP, ADP, EDDT, PET, NaCl etc. are
sensitive to humidity. If they are left in the air, their surface will
deliquesce, leading to lower x-ray reflection intensities and deteriorated
resolution. It is therefore necessary to keep the interior of the
spectroscopic chamber in a vacuum even during the time that the x-ray
spectrometer is not used.
• Samples which are highly acid or alkaline, or which will sublime at low
temperatures will deteriorate analyzing crystal leading to lower reflection
intensities.
24
• The fluorescence x-ray excited from the specimen are diffracted through
the analyzing crystal by scanning goniometer.
• The diffracted x-rays are detected by the counter and through the
electronic circuit, the intensities are recorded automatically on the
charge recorder.
• The characteristic wavelength (λ) emitted by each element in the sample
is analyzed by applying a diffracting (an analyzing) crystal which has a
certain d value.
25
• Diffracting angles (θ) are measured and λ of each element is
determined using Bragg’s law.
• By determining the elemental spectra recorded on a chart, we can
learn the name of elements containing in the specimen.
26
Example of a qualitative measurement result.
Fluorescent spectrum
recording of a
stainless steel
27
• The primary radiation was supplied by tungsten-target tube operated at
50 kV, and the sample was stainless steel containing 18%Cr and 8% Ni.
• The K lines of all the major constituents (Fe, Cr and Ni) and of some of
the minor constituents (Mn and Co) are apparent.
• In addition tungsten L lines can be seen; these always be present when
a tungsten tube is used. The copper K lines are due to copper existing
as an impurity in the tungsten target.
28
• Consider the quantitative analysis result of a dry limestone sample which is
obtained from XRF analysis ;
ELEMENT SPECTRUM WT%
Mg Mg Kα 1.2
Ca Ca Kα 90.0
Fe Fe Kα 2.3
Si Si Kα 6.5
• Mg and Ca are found as carbonates, while Fe and Si as oxides. Convert the data
to mol % of the actual substances (CaCO3, MgCO3, Fe2O3 and SiO2) present in
the limestone. Mol weight : Ca = 40.1; Mg = 24.3; C = 12.0; O = 16.0 and Fe =
55.8, Si=28.1.
• Spectra of oxygen and carbon are not considered.
29
Quantitative Analysis
•XRF is a reference method, standards are
required for quantitative results.
•Standards are analysed, intensities obtained,
Concentration
and a calibration plot is generated
(intensities vs. concentration).
• XRF instruments compare the spectral
intensities of unknown samples to those of
known standards.
30
Sample Preparation
Powders:
•Grinding (<400 mesh if possible) can minimise scatter affects due to
particle size. Additionally, grinding insures that the measurement is
more representative of the entire sample, vs. the surface of the sample.
•Pressing (hydraulically or manually) compacts more of the sample into
the analysis area, and ensures uniform density and better
reproducibility..
31
• Solids:
• Orient surface patterns in same manner so as minimise scatter affects.
• Polishing surfaces will also minimise scatter affects.
• Flat samples are optimal for quantitative results.
32
• Liquids:
• Samples should be fresh when analysed and analysed with short analysis time - if
sample is evaporative.
• Sample should not stratify during analysis.
• Sample should not contain precipitants/solids, analysis could show settling trends
with time.
33
XRF Application
• During the last two decades, the development in X-ray detectors has established the
XRF method as a powerful technique in a number application fields, including.
• Ecology and environmental management: measurement of heavy metals in soils,
sediments, water and aerosols.
• Geology and mineralogy: qualitative and quantitative analysis of soils, minerals,
rocks etc.
• Metallurgy and chemical industry: quality control of raw materials, production
processes and final products.
• Paint industry: analysis of lead-based paints.
34
XRF Application
• Jewelry: measurement of precious metals concentrations.
• Fuel industry: monitoring the amount of contaminants in fuels.
• Food chemistry: determination of toxic metals in foodstuffs.
• Agriculture: trace metals analysis in soils and agricultural products.
• Archaeology and archaeometry.
• Art Sciences: study of paintings, sculptures etc.
35
