XRF

~Hn~d H~~n R~nu
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Ahmad Mansour
a_mansour01@yahoo.com / XRF 1
< Introduction.
< General concept.
< INTERACTION OF X-RAYS WITH MATTER
< X-RAY ABSORPTION PHENOMENA
< ABSORPTION EDGES
< X-ray wavelength and energy scales
< Selection rules
< Fluorescence Yield
< Photon Transmission
< Wavelength dispersive XRF
< Energy dispersive XRF
< Microscopic XRF
< Basic XRF Setup
< Calibration Theory
< ABSORPTION FACTOR
< ENHANCEMENT FACTOR
< Qualitative analysis
< Quantitative analysis
Ahmad Mansour
< %he benefits of using XRF rather than a traditional analysis
method are that it is quick, non-destructive, and all-inclusive
(multiple tests are not required). %he power of XRF analysis was
first realized by Henry Moseley in 1912, seventeen years after
Wilhelm Rntgen had discovered the x-ray.
< %he purpose of X-ray fluorescence spectrometry is the
qualitative and quantitative determination of the elements in a
sample by measuring their characteristic radiation .
< %he use of x-rays had a great advantage over the use of
electrons;because of the inefficient energy conversion by
electrons.
< %he x-ray intensity is proportional to both the elemental
concentration and the strength of the ionizing source.
Ahmad Mansour
< %he emitted x-rays produced from this process are called
"X-ray Fluorescence, or XRF. %he process of detecting
and analyzing the emitted x-rays is called "X-ray
Fluorescence Analysis.
< When a primary x-ray excitation source strikes a sample,
the x-ray can either be absorbed by the atom "photoelectric
effect. or scattered through the material.
< electrons are ejected from the inner shells, creating
vacancies. %hese vacancies present an unstable condition
for the atom.
< As the atom returns to its stable condition, electrons from
the outer shells are transferred to the inner shells and in
the process giving off a characteristic x-ray
Ahmad Mansour
< AnaIyticaI chemistry
Analytical chemistry is the study of the separation, identification, and
quantification of the chemical components of natural and artificial
materials. Qualitative analysis gives an indication of the identity of the
chemical species in the sample and quantitative analysis determines
the amount of one or more of these components.
< EIementaI anaIysis
lemental analysis is a process where a sample of some material
(e.g., soil, waste or drinking water, minerals, chemical compounds) is
analyzed for its elemental and sometimes isotopic composition.
lemental analysis can be qualitative (determining what elements are
present), and it can be quantitative (determining how much of each
are present).
Ahmad Mansour
< Concentration
t is the measure of how much of a given substance there
is mixed with another substance.
Concentration may be expressed both qualitatively
('informally') and quantitatively ('numerically').
QuaIitative notation Qualitatively, solutions of relatively
low concentration are described
using adjectives such as "dilute," or "weak," while solutions
of relatively high concentration are described as
"concentrated," or "strong."
Ahmad Mansour
Quantitative notation:
%here are a number of different ways to quantitatively
express concentration; at standard state temperature
and pressure (that is, 25 degrees Celsius at 1
atmosphere).
for exampIe: Parts per million ppm:
denotes one particle of a given substance for every
999,999 other particles. 1 part in 10
6
.
Ahmad Mansour
Ahmad Mansour
< raggs Iaw
n physics, raggs Iaw gives the angles for coherent and
incoherent scattering from a crystal lattice.
at certain specific wavelengths and incident angles,
produced intense peaks of reflected radiation (known as
Bragg peaks).
%he concept of Bragg diffraction applies equally to neutron
diffraction and electron diffraction processes. Both neutron
and X-ray wavelengths are comparable with inter-atomic
distances (~150 pm) and thus are an excellent probe for
this length scale.
Ahmad Mansour
%he interference is constructive when the phase shift is a
multiple of 2; this condition can be expressed by Bragg's law,
Where n is an integer, /
is the wavelength of incident
wave, d is the spacing between
the planes in the atomic lattice,
and 0 is the angle between the
incident ray and the scattering planes.
< oseIeys Iaw
Moseley was able to show that the frequencies of certain
characteristic X-rays emitted from chemical elements are
proportional to the square of a number which was close to the
element's atomic number.
Ahmad Mansour
oseley's Law.
where
f is the frequency of the main or x-ray emission line
k
1
and k
2
are constants that depend on the type of
line
Moseley's two given formulae for K-alpha and L-alpha
lines are
Ahmad Mansour
where () is the intensity of a beam of energy after
passing through a thickness d of the material,
o
() is the
initial intensity, a
2
() is the mass attenuation coefficient
(measured in (cm
2
g
-1
)) and pd is the so-called aerial
density with units (g . cm
-2
).
%here are three modes through which X-ray photons
interact with an atom, i.e., photoelectric interaction, elastic
scattering (coherent or Rayleigh scattering) and inelastic
scattering (incoherent or Compton scattering).
Pair production interaction is ignored since the threshold
energy required is greater than (1.02 MeV), while in XRF
we are dealing with energies in the range (2-60 keV).
Ahmad Mansour
photoelectric interaction
%his process requires a minimum energy or "critical energy "
equal to the binding energy of the electron.
Ahmad Mansour
Ahmad Mansour
%here are four X-ray absorption coefficients derived from Beer-
Lambert law
1- Linear absorption coefficient
lin
gives the absorption per unit
thickness (cm
-1
)
2- Mass attenuation coefficient
m
gives the absorption per unit
mass in unit area (cm
2
. g
-l
)
3- Atomic absorption coefficient
a
gives the absorption per atom in
unit area (cm
2
. atom
l
).
Where A is the atomic weight, N is the Avogadros number and n
is the number of atoms per unit volume.
4- Molar absorption coefficient gives the absorption per mole, in
unit area (cm
2
. mole
l
).
Ahmad Mansour
< %he mass absorption coefficient (M) of a complex
matrix M consisting of a mixture of several
chemical elements can be calculated from the
mass attenuation coefficient of the n constituting
elements
(M) = Z
i=1
w
i

i
where
i
is the mass attenuation coefficient of the
i
th
pure element and w
i
its mass fraction in the
sample considered. %his is called the 2ixture rule.
Ahmad Mansour
< %he X-ray absorption coefficient of an element that is, its X-ray "stopping power"
decreases with X-ray energy of the excitation source within certain limits. %he limits
are sharp discontinuities which are observed on absorption curves, and they are
related to the critical energies. A minimum photon energy that can ejact an electron
from a given level in the atom is known as the absorption edge of that element.
Ahmad Mansour
ENERGY
%
T
R
A
N
S
T
T
E
D
Low energy x-rays
are absorbed
Absorption
Edge
Very high energy
x-rays are transmitted
X-rays above the absorption
edge energy are absorbed
< %he energies of X-ray photons are of the same order
of magnitude as the binding levels of inner shell
electrons (K, L, M, . levels)
< %he wavelength / of an X-ray photon is inversely
related to its energy according to
< X-ray analysis methods most commonly employ
radiation in the 1-50 keV (1 - 0.02 nm) range.
Ahmad Mansour
< ach electron in an atom can be defined by four
quantum numbers.( n,l,s,m)
< no two electrons within a given atom can have the same
set of quantum numbers.
< %he selection rules for the production of normal
(diagram) lines require that the principal quantum
number must change by at least one (An _ 1), the
angular quantum number must change by only one (Al
= 1), and the J quantum number must change by zero
or one (AJ=0,1).
Ahmad Mansour
< All ionizations do not result in x-ray emission. %he Auger effect is
a competing mechanism of atomic relaxation.
< %he ratio of the number of emitted x rays to the total number of
ionizations is called the fluorescence yield w
i
,where i designates
the shell involved. Fluorescence yield increases with atomic
number and is greater than 95% for K x rays of elements with Z
>78.
< For a given element, the fluorescence yield decreases from the
K series to the L and M series. %he fluorescence yield can be
approximated by
Where A
i
is approximately 10
6
for the K shell and 10
8
for the L
shell.
Ahmad Mansour
< For a photon to eject an electron, the photon energy
must be greater than or equal to the electron binding
energy. For example, to ionize K electrons of
plutonium, the energy of the excitation photon must
be at least 121.82 keV.
< %he fraction of photons, F, that interact with the
atomic electrons of a particular material is given by
Ahmad Mansour
< A typical WDXRF system consists of an X-ray tube, a
specimen support holder, a primary collimator, an
analyzing crystal and a tandem detector.
< Wavelength-dispersive spectrometers employ
diffraction by a single crystal to separate
characteristic wavelengths emitted by the sample.
< ach wavelength / will diffract at a specific angle 0,
given by Braggs law
n/ = 2d sin0
Ahmad Mansour
Ahmad Mansour
%he smaller the d-spacing of the crystal, the better the separation of the lines, but
the smaller the wavelength range that can be covered.
< DXRF instruments have a much simpler mechanical
design than WDXRF instruments, as the detection
system does not include any moving parts and the
solid-state detector itself acts as a dispersion agent.
< Fluorescence generates a current in the detector.
n a detector intended for energy dispersive XRF,
the height of the pulse produced is proportional to
the energy of the respective incoming X-ray.
Ahmad Mansour
< %his micro analytical variant of bulk DXRF is based on the
localized excitation and analysis of a microscopically small
area on the surface of a larger sample, providing information
on the lateral distribution of major, minor and trace elements in
the material under study.
< A beam of primary X-rays with (microscopically) small cross
section irradiates the sample and induces the emission of
fluorescent X-rays from a micro-spot.
Ahmad Mansour
< it generally consists of four basic components
1. An excitation source
2. A sample
3. A detector
4. A data collection and analyzing system
< An XRF measurement essentially gives two pieces
of information %he energy of an x-ray, and how
many x-rays were received (count number or
intensity for that energy).
Ahmad Mansour
Ahmad Mansour
%wo particular systematic errors First, the instrument is not perfect and
tends to drift from previous calibrations, and second, characteristic x-ray
energies are not totally unique to an element and often overlap with
other characteristic x-rays.
< %he external force/energy required for excitation of an atom and
ejection of its electrons is supplied by either an X-ray tube or a
radioisotope source in an XRF system.
< X-ray tubes provide a continuous x-ray spectrum where both the
energy and the output intensity are adjustable. %he output
energy and intensity of an x-ray tube are functions of applied
high voltage and amperage to its filament respectively.
< Radioisotopes are generally used for their physical size and their
ability to provide gamma or x-ray photons with specific energy
that come from their natural decay. A radioisotope, unlike an x-
ray tube, can not be turned off and its energy is not adjustable.
< Cobalt-57 emits a gamma ray at 122 keV, an efficient energy for
K-shell ionization Of either uranium or plutonium.
Ahmad Mansour
The X-ray tube
x-ray tube containing a source of electrons and two
metal electrodes in a vacuum tube. %he high voltage
maintained across these electrodes rapidly draws the
electrons to the anode (target).
xtensive cooling is necessary for the x-ray tube
because most of the kinetic energy of electrons is
converted into heat; less than one percent is
transformed into x-rays.
Ahmad Mansour
%he x-ray tube generates the x-ray radiation with a
range of wavelengths starting from a minimum
wavelength /, called continuous xrays or
Bre2sstrahlung.
%he minimum / (with maximum radiation energy)
of continuous x-rays is determined by the
maximum acceleration voltage of electrons in the
x-ray tube.
< ntensity maxima are the characteristic x-rays
coming from a x-ray fluorescence of the anode
material.
Ahmad Mansour
< ffectiveness of a detector which is its ability to
stop the radiation of desired energy is a function of
its material of composition and thickness.
< Because the absorption of radiation is a function
of atomic density, the detector material is chosen
based on the application and the energy of the
desired characteristic x-rays.
< XRF systems with low energy x-ray tubes utilize a
solid state detector and XRF systems with high
energy output such as those with radioisotopes
use a Cd%e or similar detectors.
Ahmad Mansour
< n wavelength dispersive spectrometers, gas flow
proportional counters (for long wavelengths, / > 0.2
nm) and scintillation counters (for wavelengths shorter
than 0.2 nm) are used to count X-rays.
< n case of energy-dispersive spectrometry, solid-state
detectors of higher resolution are used. i.e. lithium
drifted silicon (Si(Li)) and hyperpure germanium (HP-
Ge) detectors are used.
Ahmad Mansour
< lectronics for an XRF system are combinations of
power supplies, pre-amplifiers, amplifiers, filters,
converters, scalaer, multichannel analyzer, memory,
and other necessary components for converting a
detector's pulses to a recognizable data format.
< CentraI Processing Unit CPU:
%he CPU, central processing unit, is the brain of an
XRF system. %his is where data reduction techniques,
analytical algorithms, stability corrections, calibration
data, safety interlocks, and other operation protocols
are stored and executed.
Ahmad Mansour
Ahmad Mansour
Many calibration methods exist. For this work, it suffices to
review three methods. ach method assumes that the
calibration data has at least six data points
Linear and Quadratic Approximations
n cases where the data appear to be linear. %o do this, one
would apply the least-squares regression equations to find the
slope and intercept of the fitted line. %hese equations are
Ahmad Mansour
< quation (1) represents the linear fit where x represents the channel
number (independent variable), and y represents the energy
(dependent variable). %he symbols s
x
and s
y
are the sample standard
deviations of the channel data and the energy data, respectively; 2 is
the slope of the line, - is the y-intercept of the line, r is the correlation
coefficient, and , are the mean x and y values.
< %he most error (about 0.1 keV).
< %his results because the MCA does not have a perfect linear
correlation between energy and channel number.
Ahmad Mansour
Linear and Cubic SpIine nterpoIation
< %he spline interpolation method is used to
interpolate between every data point for a more
accurate calibration (it is also used for
extrapolation near the end points of the graph).
< A linear interpolation involves taking two data
points and fitting a line between those points.
< %he equations for the linear interpolation are the
same as equations (1), (2), and (3), only using two
data points at a time.
Ahmad Mansour
< %he cubic spline interpolation method involves the
same design as the linear interpolation, only creating
polynomials for the curve fitting. %his requires that
three or more points are used for each calculation
< For a cubic spline interpolation;
Ahmad Mansour
< Similar to the linear interpolation, x is the independent
variable (channel number), and y is the dependent
variable (energy). %he functions A, B, C, and D are used
as substitutions to the main equation (4) and are all
functions of x.
< %he error is reduced to about 0.02 keV.
Ahmad Mansour
Optimization ethod
< n principle, the optimization method would provide the
most accurate calibration by using the whole data set taken
from the calibration sample.
< n the optimization method, the calibration spectrum is
compared point by point with a predicted spectrum which
simulates what the calibration spectrum should look like. As
the two spectra are compared, the calibration spectrum is
adjusted to achieve minimum error with respect to the
predicted spectrum.
< %he optimization method could reduce the error to 0.01
keV or better
Ahmad Mansour
< CaIibration SampIe
< %he calibration sample preferably contains an adequate number of
elements to provide sufficient peaks for calibration; typically, there are
at least six to eight peaks in the spectrum.
< A calibration sample made from a variety of compounds should be
homogeneous.
< Because the anode in the x-ray tube is composed of copper, many of
the characteristic x-rays of copper are reflected off the sample to the
detector. As a result, copper peaks are present in every XRF
measurement.
Ahmad Mansour
< assume that the fluorescent element is not enhanced
by any other element in the sample.
< So that its emission is due solely to the excitation by
the primary energy.
< %he fluorescent intensity is simply given by
Ahmad Mansour
< A
i
()known as the absorption factor, S
i
() is the
sensitivity of the system, C
i
is the concentration of the
element i in the sample and a () is the average
absorption correction factor which is given by
Where
o
is the incident energy of the photon,
i
is the
emergent energy, +
1
is the incident angle and +
2
is
the emergent angle. For thin samples the absorption
is negligible and the relation between the
concentration and the intensity is linear therefore
simplifies to
Ahmad Mansour
< For infinitely thick samples pd in the absorption term
shown in
< %he equation that relates the intensity and the
concentration becomes
Ahmad Mansour
< t occurs when the radiation from another element in
the specimen excites the analyte.
< %his contributes more to the characteristic lines of the
target that are excited by the primary X-rays.
< %he enhancement factor H
i
() the intensity should be
given by
Ahmad Mansour
< Absorption Any element can absorb or scatter the fluorescence of
the element of interest.
< nhancement Characteristic x-rays of one element excite
another element in the sample.
ncoming source X-ray fluoresces Fe.
Fe fluorescence is sufficient in energy to fluoresce Ca.
Ca is detected, Fe is not. Response is proportional to
concentrations of each element.
Ahmad Mansour
Source X-ray
X-Ray Captured
by the detector
Red = Fe, absorbed
Iue = Ca, enhanced
SampIe
< For the energy of the K
d
-lines a relation is given to the
atomic number of the excited element (Moseleys
law)
< Using Moseleys law in the spectra after an energy
calibration the elements in the sample can be
identified. For heavy elements, additionally, the L-lines
can be used taking the intensity ratios into account
Ahmad Mansour
< %he intensity of a fluorescence line is proportional to the amount
of the element in the sample. %his intensity is influenced by
other effects
%he excitation efficiency changes with the difference of the
energies of the excitation.
As the exciting and the emission radiation are absorbed in the
sample material (matrix effect absorption).
Fluorescence radiation can excite another elements (matrix
effect enhancement).
< %herefore, it is necessary to calibrate the system with reference
samples (samples with known elemental concentrations) and to
plot calibration curves (intensity in relation to the concentration)
for each element.
Ahmad Mansour
< XRF is a reference method,
standards are required for
quantitative results.
< Standards are analysed,
intensities obtained, and a
calibration plot is generated
(intensities vs. concentration).
< XRF instruments compare
the spectral intensities of
unknown samples to those of
known standards.
Ahmad Mansour
C
o
n
c
e
n
t
r
a
t
i
o
n
Standards (such as certified reference materials)
are required for Quantitative Analysis.
Standard concentrations should be known to a
better degree of precision and accuracy than is
required for the analysis.
Standards should be of the same matrix as
samples to be analyzed.
Ahmad Mansour

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