NON DESTRUCTIVE CHEMICAL ANALYSIS

Wavelength dispersive
(WDXRF) and energy dispersive
(EDXRF) X- ray fluorescence

Notes by:
Dr Ivan Greti, 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 Braggs Law) the X-Rays in
different directions according to
their wavelengths (energies).

Braggs 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, semiconductors, 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., VK and TiK).
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. Fe 2+ 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
Specificallydesig
ned for the
rigorous demands
of nondestructive
elemental
analysis in the
field.

Detection limit for handheld

EDXRF

-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 10m. 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 (XRF) 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.

-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 1. Low spectral resolution (130-155
eV)
eV)
2. Low collection efficiency
2. High collection efficiency (faster)
(slower)
3. Higher P/B
3. Lower P/B
4. Highly sensitive to geometric 4. Low sensitivity to sample
effects
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
8. Lower beam current feasible
typical
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)

WD-XRF
Wave (X-rays or -rays) induced X-rays
No coating necessary

Spot, line or surface analysis (scanning

system)
Small excitation energy 0,06 W !! (up to 2 A
beam current, up to 30 kV excitation
potential)

Mainly surface analysis (spot in case of 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 surface layers (shallow
penetration up to 2 m)

Excellent energy resolution

Analysis of dipper layers real bulk analysis
(penetration up to 3mm)

Longer time for quali- and quanti-tative

analysis
Good detection limit
Analysis of elements from Beryllium (Be) to
Uranium (U)

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

ppm-level.

Concentration range from 100 % down to the

sub-ppm-level.

Manual to semiautomatic procedures

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

ED-XRF
Wave (X-rays or -rays) induced X-rays
No coating necessary

Small excitation energy 0,06 W !! (up to 2 A beam

current, up to 30 kV excitation potential)
Fair energy resolution
Analysis of surface layers (shallow penetration up to
2 m)
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 ppmlevel (not valid for light elements).

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 ppmlevel (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

Analysis of solid samples

Manual to semiautomatic procedures

Mainly surface analysis (spot in case of -XRF)

Vacuum not necessary but it can work with vacuum

THE END