NON DESTRUCTIVE CHEMICAL ANALYSIS

Wavelength dispersive (WDXRF)

and energy dispersive (EDXRF)
X- ray fluorescence

Notes by:
Dr Ivan Gržetić, professor
University of Belgrade – Faculty of Chemistry
 XRF detection system

 No mater how the secondary X-ray radiation

(X-Ray fluorescence) is produced in XRF
machines there are TWO WAYS to detect this
radiation:
◦ Wavelength Dispersive System (WDS) and
◦ Energy Dispersive System (EDS).
Wavelength Dispersive System
(WDS)
PRINCIPLE
 A wavelength dispersive detection system
physically separates the X-Rays according
to their wavelengths.
 The x-rays are directed to a crystal, which
diffracts (according to Bragg´s Law) the
X-Rays in different directions according
to their wavelengths (energies).
Bragg´s Law
 Geometry of the spectrometer
SPOT
SOURCE
of X-RAYS

No need for
collimators

Good for
SEM-WDX
Geometry of the spectrometer
SURFACE AS A
SOURCE of X-RAYS

Collimators necessary

Good for
WD-XRF
Characteristics and Strengths
 WDS is used for non-destructive quantitative analyses of
spots as small as a few micrometers, at detection levels as
low as a few 10s of ppm, and for elements from atomic
number 5 (boron) and higher.
 WDS works well in a variety of natural and synthetic solid
materials, including minerals, glasses, tooth enamel, semi-
conductors, ceramics, metals, etc.
 The high spatial resolution of WDS not only allows
quantitative analyses to be performed on small phases but
also to detect chemical zoning on a small scale within a
material (e.g. mineral).
 When the electron beam is restored, the WD spectrometers
can allow x-ray image maps of individual elements to be
constructed.
 When compared to EDS, WDS exhibits superior peak
resolution of elements and sensitivity of trace elements.
Characteristics and Limitations
 Because WDS cannot determine elements below atomic
number 5 (boron), several geologically important elements
cannot be measured with WDS (e.g., H, Li, and Be).
 Despite the improved spectral resolution of elemental peaks,
some peaks exhibit significant overlaps that result in
analytical challenges (e.g., VKα and TiKβ).
 WDS technique is slower then EDS technique, but WDS DL
is much better then EDS DL.
 WDS analyses are not able to distinguish among the valence
states of elements (e.g. Fe2+ vs. Fe3+) such that this
information must be obtained by other techniques (e.g.
Mossbauer spectroscopy).
 The multiple masses of an element (i.e. isotopes) cannot be
determined by WDS, but rather are most commonly
obtained with a mass spectrometer (see stable and
radiogenic isotope techniques).
 Detection limit for WDS
 The range of detectable elements varies
according to instrument configuration and set
up, but typically WDXRF covers all elements
from beryllium (Be) to uranium (U).
 Concentrations can range from 100% down to
ppm and in some cases sub-ppm levels. Limits
of detection depend upon the specific element
and the sample matrix, but as a general rule,
heavier elements will have better detection
limits.
Energy Dispersive System
(EDS)
 PRINCIPLE
 EDS is an analytical technique used for the elemental analysis or
chemical characterization of a sample.
 The secondary x-rays (X-ray florescence) are directed to a
detector. A detector is used to convert X-ray energy into voltage
signals; this information is sent to a pulse processor, which
measures the energy of the signals and passes them onto an
analyzer. The analyzer converts the analog into a digital signal which
is proportional to the energy of the incoming pulse. Received pulses
are actually amplified, converted into digital signals and then sorted
by energy with help of multi-channel analyzer (energy is
characteristic for each element) and frequency of appearance
(characteristic for concentration) and sent to data display and
analysis.The most common detector now is Si(Li) detector cooled
to cryogenic temperatures with liquid nitrogen; however newer
systems are often equipped with silicon drift detectors (SDD) with
Peltier cooling systems.
EDS spectrometer

ED-XRF

SEM-EDX
Si(Li) detector with LN cooling
Si(Li) detector with Peltier cooling
 Detection limit for EDXRF
 Analysis of elements from Sodium (Na) to
Uranium (U).
 Concentration range from 100 % down to the
ppm-level (not valid for light elements). Limits
of detection depend upon the specific element
and the sample matrix, but as a general rule,
heavier elements will have better detection
limits.
HANDHELD XRF
Specifically designed
for the rigorous
demands of
nondestructive
elemental analysis in
the field.
Detection limit for handheld EDXRF
 μ-XRF with polycapillary focusing optics

 Polycapillary focusing optics collect a large solid angle

of X rays from an X-ray source and focus them to a
spot as small as 10µm. The X-ray flux density obtained
is a few orders of magnitude higher (100x-10000x)
than that obtained with a conventional pinhole
collimator. The main application of these optics is micro
X-ray fluorescence (µXRF) analysis, which has been
widely used for thin film and plating analysis, precious
metal evaluation, alloy measurement, and monitoring of
electric circuit board coatings.
 Polycapillary optics are arrays of small hollow glass
tubes (fibers). X rays are guided down these curved
and tapered tubes by multiple reflections in a manner
analogous to the way fiber optics guide light.
μ-XRF with polycapillary focusing optics
WDS vs EDS
Differences in WDS and EDS
Differences in WDS and EDS
WDS EDS
1. High spectral resolution (2-6 eV) 1. Low spectral resolution (130-155 eV)
2. Low collection efficiency (slower) 2. High collection efficiency (faster)
3. Higher P/B 3. Lower P/B
4. Highly sensitive to geometric effects 4. Low sensitivity to sample geometry
5. Few spectral artifacts 5. Several spectral artifacts
6. No LN required 6. LN required*
7. Moving mechanical parts 7. No moving mechanical parts**
8. Relatively high beam current typical 8. Lower beam current feasible
9. Great for majors and traces 9. Great for majors, poor for traces
10. Very expensive to purchase 11. Less expensive to purchase
* Some recent claims of LN-free new models
** Except for retractable models
WDS vs EDS spectrum
 SEM-WDS vs WD-XRF
SEM-WDS
Corpuscular (electron) induced X-rays
NECESSARY for nonconductive samples
surface coating with electro conductive thin
film (carbon, gold…)
Spot, line or surface analysis (scanning
system)
Small excitation energy 0,06 W !! (up to 2 μA
beam current, up to 30 kV excitation
potential)
Excellent energy resolution
Analysis of surface layers (shallow
penetration up to 2 μm)
Longer time for quali- and quanti-tative
analysis
Good detection limit
Analysis of elements from Beryllium (Be) to
Uranium (U)
Concentration range from 100 % down to the
ppm-level.
Manual to semiautomatic procedures
WD-XRF
Wave (X-rays or γ-rays) induced X-rays
No coating necessary
Mainly surface analysis (spot in case of μ-
XRF)
High excitation energies up to 4 kW (up to
120 mA beam current, up to 80 kV excitation
potential)
Excellent energy resolution
Analysis of dipper layers – real bulk analysis
(penetration up to 3mm)
Longer time for quali- and quanti-tative
analysis
Excellent detection limit
Analysis of elements from Beryllium (Be) to
Uranium (U)
Concentration range from 100 % down to the
sub-ppm-level.
Possible full automatic procedures
 SEM-EDS vs ED-XRF
SEM-EDS
Corpuscular (electron) induced X-rays
NECESSARY for nonconductive samples surface
coating with electro conductive thin film (carbon,
gold…)
Spot, line or surface analysis (scanning system)
Can work only with vacuum
Small excitation energy 0,06 W !! (up to 2 μA beam
current, up to 30 kV excitation potential)
Fair energy resolution
Analysis of surface layers (shallow penetration up to
2 μm)
Short time for quali- and quanti-tative analysis
Good detection limit. Less optimal for light elements.
Analysis of elements from Sodium (Na) to Uranium
(U)
Concentration range from 100 % down to the ppm-
level (not valid for light elements).
Analysis of solid samples
Manual to semiautomatic procedures
ED-XRF
Wave (X-rays or γ-rays) induced X-rays
No coating necessary
Mainly surface analysis (spot in case of μ-XRF)
Vacuum not necessary but it can work with vacuum
High excitation energies up to 4 kW (up to 120 mA
beam current, up to 80 kV excitation potential)
Fair energy resolution
Analysis of dipper layers – real bulk analysis
(penetration up to 3mm)
Short time for quali- and quanti-tative analysis
Good detection limit in vacuum. Less optimal for
light elements.
Analysis of elements from Sodium (Na) to Uranium
(U)
Concentration range from 100 % down to the ppm-
level (not valid for light elements).
Concentration range from 100 % down to the 10 or
100 ppm-level with no vacuum.
Analysis of solids and liquids
Possible full automatic procedures
HANDHELD instruments available
THE END