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I R ES CE NC
Y FL U O
X-RA R F )
S IS (X
ANALY
USER’S MANUAL
TRAINING
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Authors: Dr. Reinhold Schlotz, Dr. Stefan Uhlig. Layout: Ingrid Tremmel
Order No. M84-E06001. Issue: July 13, 2004
Table of Contents
Instrumentation....................................................................................................... 45
The Multichannel Spectrometer MRS......................................................................................... 45
Scanners for MRS 400, MRS 404 and MRS 4000.................................................................. 47
The Sequential Spectrometers SRS 3X00 and S4..................................................................... 48
The End-window Tube and Generator .................................................................................... 51
The Primary Beam Filter ......................................................................................................... 51
Sample Cups, the Cup Aperture ............................................................................................. 54
The Vacuum Seal.................................................................................................................... 54
Collimator Masks..................................................................................................................... 55
Collimators, the Soller Slit ....................................................................................................... 55
The Crystal Changer ............................................................................................................... 56
The Flow Counter.................................................................................................................... 56
The Sealed Proportional Counter............................................................................................ 57
The Scintillation Counter ......................................................................................................... 58
Electronic Pulse Processing ....................................................................................................... 59
The Discriminator .................................................................................................................... 59
Main Amplifier, Sine Amplifier ................................................................................................. 59
Dead Time Correction ............................................................................................................. 60
Line-shift Correction ................................................................................................................ 62
Appendix A.............................................................................................................. 63
Supplementary Literature ............................................................................................................ 63
Books....................................................................................................................................... 63
Tables...................................................................................................................................... 65
Journals................................................................................................................................... 65
Appendix B ..............................................................................................................67
Sources of Standard Samples .....................................................................................................67
Appendix C ..............................................................................................................69
Sample Preparation Catalog for XRF Analysis ..........................................................................69
Introduction ..............................................................................................................................69
Preparation of solid samples....................................................................................................74
Metals ...............................................................................................................................74
Pressed pellets .................................................................................................................75
Fused beads .....................................................................................................................76
Preparation of liquid samples...................................................................................................77
Preparation of filter samples .............................................................................................78
Sample preparation equipment for XRF Analysis .....................................................................78
Crushing...................................................................................................................................78
Grinding....................................................................................................................................79
Pelletizing.................................................................................................................................92
Accessories for pressing...................................................................................................99
Desiccator and accessories............................................................................................101
Milling .....................................................................................................................................102
Fusing ....................................................................................................................................103
Accessories for fusing.....................................................................................................115
Fluxes .............................................................................................................................115
Liquid sample measurement accessories..............................................................................115
Liquid cups......................................................................................................................115
Foils for liquid cups .........................................................................................................116
Foils for liquid cells..........................................................................................................116
Paper filters.....................................................................................................................117
Pipettes and accessories................................................................................................117
Index....................................................................................................................... 119
Fundamental Principles
In the following text, the unit nanometre (nm = 10-9 m) is used for the wavelength, O (= Lambda), and
the unit kiloelectronvolts (keV) for energy, E.
Comment
In literature the unit Angström (Å) is often stated for the wavelength:
1 Å = 0,1 nm = 10-10 m
The following relationship (conversion formula) exists between the units E (keV) and O (nm):
1 . 24 1.24
E ( keV ) or O (nm)
O ( nm ) E (keV )
The X-ray fluorescence analysis records the following range of energy or wavelengths:
E = 0,11 - 60 keV
The positively charged nucleus is surrounded by electrons that move within defined areas (”shells”).
The differences in the strength of the electrons‘ bonds to the atomic nucleus are very clear depending
on the area or level they occupy, i.e. they vary in their energy. When we talk about this we refer to
energy levels or energy shells. This means: A clearly defined minimum amount of energy is required to
release an electron of the innermost shell from the atom. To release an electron of the second inner-
most shell from the atom, a clearly defined minimum amount of energy is required that is lower than
that needed to release an innermost electron. An electron’s bond to an atom is weaker the further
away it is from the atom’s nucleus. The minimum amount of energy required to release an electron
from the the atom, and thus the energy with which it is bound to the atom, is also referred to as the
binding energy of the electron to the atom.
The binding energy of an electron in an atom is established mainly by determining the incident. It is for
this reason that the term absorption edge is very often found in literature:
Energy level = binding energy = absorption edge
The individual shells are labelled with the letters K, L, M, N, ...., the innermost shell being the K-shell,
the second innermost the L-shell etc. The K-shell is occupied by 2 electrons. The L-shell has three
sub-levels and can contain up to a total of 8 electrons. The M-shell has five sub-levels and can contain
up to 18 electrons.
Characteristic Radiation
Every element is clearly defined by its atomic number Z in the periodic system of elements or by the
number of its electrons in a neutral state. The binding energies or the energy levels in every element
are different and characteristic for every element as a result of the varying number of electrons (nega-
tive charges) or the number Z of the positive charges in the atomic nucleus (= atomic number).
If an electron of an inner shell is now separated from the atom by the irradiation of energy, an electron
from a higher shell falls into this resultant “hole” which releases an amount of energy equivalent to the
difference between the energy levels involved.
The energy being released can be either be emitted in the form of an X-ray or be transferred to an-
other atomic shell electron (Auger effect). The probability of an X-ray resulting from this process is
called the fluorescence yield Z. This depends on the element’s atomic number and the shell in which
the “hole” occurred. Z is very low for light elements (approx. 10-4 for boron) and almost reaches a
value of 1 for the K-shell of heavier elements (e.g. uranium).
However, decisive is that the energy or wavelength of the X-ray is very characteristic for the element
from which it is emitted; such radiation is called characteristic X-rays.
This provides the basis for determining chemical elements with the aid of X-ray fluorescence analy-
sis.
Nomenclature
The energy of an X-ray corresponds to the difference in energy of the energy levels concerned. K-
radiation is the term given to the radiation released when replenishing the K-shell, L-radiation to that
released when replenishing the L-shell etc. (Fig. 2).
Also needed for the full labelling of the emitted X-ray line is the information telling us which shell the
electron filling the “hole” comes from. The Greek letters D, E, F, ... are used for this with the numbering
1, 2, 3, ... to differentiate between the various shells and sub-levels.
Examples:
KD Electron from sub-level LIII to the K-shell (KD)
KD Electron from sublevel LII to the K-shell (KD)
KD if neither line is resolved by the spectrometer: KD
KE1 Electron from sublevel M to the K-shell (KE1)
LD Electron from sublevel M to the L-shell (LD)
lower, vacant energy levels of the atom, a method must be applied that is suitable for releasing elec-
trons from the innermost shell of an atom. This involves adding to the inner electrons amounts of en-
ergy that are higher than the energy bonding them to the atom.
This can be done in a number ways:
x Irradiation using elementary particles of sufficient energy (electrons, protons, D-particles, ...) that
transfer the energy necessary for release to the atomic shell electrons during collision processes
In addition to the Bremsspektrum, an X-ray tube of course emits the characteristic radiation of the
anode material as well which is of major importance for the X-ray fluorescence analysis (Fig. 3).
housing. The X-rays escape from the housing at a special point that is particularly transparent with a
thin beryllium window.
The main differences between tube types are in the polarity of the anode and cathode and the ar-
rangement of the exit window. The two most significant types are the end-window tubes and the side-
window tubes.
Side-window Tubes
In side-window tubes, a negative high voltage is applied to the cathode. The electrons emanate from
the heated cathode and are accelerated in the direction of the anode. The anode is set on zero volt-
age and thus has no difference in potential to the surrounding housing material and the laterally
mounted beryllium exit window (Fig. 4).
For physical reasons, a proportion of the electrons are always scattered on the surface of the anode.
The extent to which these back-scattering electrons arise depends, amongst other factors, on the
anode material and can be as much as 40%. In the side-window tube, these back-scattering electrons
contribute to the heating up of the surrounding material, especially the exit window. As a conse-
quence, the exit window must withstand high levels of thermal stress any cannot be selected with just
any thickness. The minimum usable thickness of a beryllium window for side-window tubes is 300 µm.
This causes an excessively high absorption of the low-energy characteristic L radiation of the anode
material in the exit window and thus a restriction of the excitation of lighter elements in a sample.
End-window Tubes
The distinguishing feature of the end-window tubes is that the anode has a positive high voltage and
the beryllium exit window is located on the front end of the housing (Fig.5).
The cathode is set around the anode in a ring (anular cathode) and is set at zero voltage. The elec-
trons emanate from the heated cathode and are accelerated towards the electrical field lines on the
anode. Due to the fact that there is a difference in potential between the positively charged anode and
the surrounding material, including the beryllium window, the back-scattering electrons are guided
back to the anode and thus do not contribute to the rise in the exit window’s temperature. The beryl-
lium window remains “cold” and can therefore be thinner than in the side-window tube. Windows are
used with a thickness of 125 µm and 75 µm. This provide a prerequisite for exciting light elements with
the characteristic L radiation of the anode material (e.g. rhodium).
Due to the high voltage applied, non-conductive, de-ionised water must be used for cooling. Instru-
ments with end-window tubes are therefore equipped with a closed, internal circulation system con-
taining de-ionised water that cools the tube head as well.
End-window tubes have been implemented by all renowned manufacturers of wavelength dispersive
X-ray fluorescence spectrometers since the early 80‘s.
Generator
Current and high voltage for the X-ray tubes as well as the heating current for the cathode are pro-
duced in a so-called X-ray generator. The generators available today supply a maximum tube current
of 150 mA and a maximum high voltage of 60 kV at a maximum output of 4 kW, i.e. current and volt-
age must be selected in such a way that 4 kW is not exceeded. The architecture of modern control
electronics and software ensures that damage to the tube resulting from maladjustment is impossible.
The reason for restricting the maximum excitation power to 1 kW is that cooling with external coolant
can be dispensed with which simplifies installation requirements.
All renowned manufacturers use rhodium (Rh) as the standard anode material as the characteristic
energies of this element are simultaneously suitable for exciting both heavy and light elements.
Energies and wavelengths of rhodium’s characteristic lines, and the heaviest element that can be ex-
cited with the appropriate line in each case, are listed in Table 2.
x The K lines of the heavy elements from rhodium to tantalum (Ta) can, on principle, only be excited
with the Bremsstrahlung of the rhodium tube as the energy of the rhodium lines is insufficient to
do it. A generator setting of 60 kV is recommended for such cases.
x The elements as far as molybdenum are excited by the Rh K radiation. The Rh-KE1 radiation can
even excite the element ruthenium but is of lower intensity than the K-alpha radiation.
x The light elements up to sulphur are excited very effectively by the Rh L radiation.
x The Rh-LE1 radiation can excite the element chlorine but is of a lower intensity. Decisive for the
available intensity of the Rh L radiation is the thickness of the tube’s beryllium exit window.
Instead of rhodium, other elements can be used as an anode material for special applications. Tung-
sten (W) and gold (Au) are particularly suitable for exciting heavier elements with the Bremsspektrum.
Chromium (Cr) was often used in side-window tubes for exciting lighter elements. Molybdenum (Mo)
was frequently used for the interference-free measurement of rhodium and, for example, cadmium.
The use of the rhodium end-window tube as a “universal tube” is justified as the light elements can be
excited far more effectively with the Rh L radiation than with the K radiation of a chromium anode.
Moreover, instrument technology is so advanced nowadays that measuring rhodium itself (or cad-
mium) presents no problem. Please also refer to the tecnique of the primary beam filter, page 51.
I I 0 e Px
x The overall progression of the coefficient decreases as energy increases, i.e. the higher the en-
ergy of the X-ray quants, the less they are absorbed.
x The rapid changes in the mass attenuation coefficient reveal the binding energies of the electrons
in the appropriate shells. If an X-ray quant has a level of energy that is equivalent to the binding
energy of an atomic shell electron in an appropriate shell, it is then able to transfer all its energy to
this electron and displace it from the atom. In this case, absorption increases sharply. Quants
whose energy is only slightly below the absorption edge are absorbed far less readily.
Example:
The K radiation of iron (Fe) is absorbed less by its neighbouring element manganese (Mn) than by the
element chromium (Cr) as Fe KD1,2 is below the absorption edge of Mn but above that of Cr.
Secondary Enhancement
Secondary enhancement, i.e. those X-ray quants that are produced as a result of the effect of the
sample elements‘ absorbed radiation, is closely linked to produced X-rays‘ absorption in the sample.
Example:
An Si KD1 quant is produced in a sample by the effect of an X-ray tube’s radiation. Inside the sample, it
can be absorbed again by transferring its energy to an Al K electron. This can then emit an X-ray
quant itself. The silicon radiation thus contributes to the X-ray emission of the aluminium. This is re-
ferred to as secondary enhancement (Fig. 7).
In quantitative analyses, the effects of absorption and secondary enhancement may have to be cor-
rected. Modern software packages offer a selection of correction models (matrix correction or inter-
element correction) for this purpose.
Background and characteristic scattering can be very effectively reduced by inserting a suitable
absorption material between tube and sample (cf. primary beam filter, page 51).
There are two types of scattering whose physical scattering processes differ from each other and are
referred to in literature as follows:
Rayleigh scattering = elastic scattering = classic scattering
Compton scattering = inelastic scattering
We will use the bold terms from now on and elaborate upon the effects of scattered characteristic
radiation of the anode material.
Rayleigh scattering
The Rh quants coming from the tube change their direction in the sample material without losing en-
ergy and can thus enter the detector and be measured. The peaks of the anode material (e.g. rho-
dium) appear in the line spectrum. If the element rhodium in the sample material is to be analysed
using an Rh tube then the characteristic radiation coming from the tube must be absorbed by a pri-
mary beam filter before it reaches the sample (cf. Fig. 2, page 52).
Compton scattering
The Rh quants coming from the tube strike the sample elements‘ electrons. In this process, some a
quant’s energy is transferred to an electron. The X-ray quant therefore loses energy. The intensity of
the quants scattered by the Compton effect depends, amongst other factors, on the tube radiation’s
angle of incidence to the sample and on the take-off angle of the radiation in the spectrometer. As
these angle settings are fixed in a spectrometer (cf. beam path), a somewhat wider peak appears on
the low-energy side of the appropriate Rh peak. These peaks are called “Compton peaks” (cf. Fig. 2,
page 53).
Measuring X-rays
Detectors, Pulse Height Spectrum
When measuring X-rays, use is made of their ability to ionize atoms and molecules, i.e. to displace
electrons from their bonds by energy transference. In suitable detector materials, pulses whose
strengths are proportional to the energy of the respective X-ray quants are produced by the effect of X-
rays. The information about the X-ray quants‘ energy is contained in the registration of the pulse
heigth. The number of X-ray quants per unit of time , e.g. pulses per second (cps = counts per second,
KCps = kilocounts per second), is called their intensity and contains in a first approximation the in-
formation about the concentration of the emitting elements in the sample. Two main types of detectors
are used in wavelength dispersive X-ray fluorescence spectrometers: the gas proportional counter
and the scintillation counter.
The way these quant counters function is described in the following:
An X-ray quant penetrates the window into the counter’s gas chamber where it is absorbed by ionizing
the gas atoms and molecules. The resultant positive ions move to the cathode (tube), the free elec-
trons to the anode, the wire. The number of electron-ion pairs created is proportional to the energy of
the X-ray quant. To produce an electron-ion pair, approx. 0.03 keV are necessary, i.e. the radiation of
the element boron (0.185 keV) produces approx. 6 pairs and the K-alpha radiation of molybdenum
(17.5 keV) produces approx. 583 pairs. Due to the cylinder-geometric arrangement, the primary elec-
trons created in this way “see” an increasing electrical field on route to the wire. The high voltage in
the counting tube is now set so high that the electrons can obtain enough energy from the electrical
field in the vicinity of the wire to ionize additional gas particles. An individual electron can thus create
up to 10.000 secondary electron-ion pairs.
The secondary ions moving towards the cathode produce a measurable signal. Without this process of
gas amplification, signals from boron, for example, with 6 or molybdenum with 583 pairs of charges
would not be able to be measured as they would not be sufficiently discernible from the electronic
“noise”. Gas amplification is adjustable via high voltage in the counting tube and is set higher for
measuring boron than for measuring molybdenum. The subsequent pulse electronics supply pulses of
voltage whose height depends, amongst other factors, on the energy of the X-ray quants.
There are two models of gas proportional counters: the flow counter (“FC”) and the sealed propor-
tional counter (“PC”). The flow counter is connected to a continuous supply of counting gas (Ar +
10% CH4) and has the advantage of being able to be equipped with a very thin window (< 0,6 µm).
The FC is therefore also suitable for measuring the very light elements and is very stable. The propor-
tional counter, on the other hand, has a closed volume a requires a thick window normally made of
beryllium. The absorption in this "thick" beryllium window prevented the measurement of the very light
elements (Be to Na).
Since innovative, highly transparent organic materials have been in use, there has now been success
in developing sealed proportional counters that are just as sensitive to the very light elements (Be to
Na) as flow counters are.
Scintillation Counters
The scintillation counter, “SC”, used in XRF comprises a sodium iodide crystal in which thallium atoms
are homogeneously distributed 'NaI(Tl)'. The density of the crystal is sufficiently high to absorb all the
XRF high-energy quants. The energy of the pervading X-ray quants is transferred step by step to the
crystal atoms that then radiate light and cumulatively produce a flash. The amount of light in this scin-
tillation flash is proportional to the energy that the X-ray quant has passed to the crystal. The resulting
light strikes a photocathode from which electrons can be detached very easily. These electrons are
accelerated in a photomultiplier and, within an arrangement of dynodes, produce so-called secondary
electrons giving a measurable signal once they have become a veritable “avalanche” (Fig. 9). The
height of the pulse of voltage produced is, as in the case of the gas proportional counter, proportional
to the energy of the detected X-ray quant.
Fig. 10a: Pulse height distribution (S) Fig. 10b: Pulse height distribution (Fe)
Gas proportional counter Scintillation counter
If argon is used as the counting-gas component in gas proportional counters (flow counters or sealed
counters), an additional peak, the escape peak (Fig. 11), appears when X-ray energies are irradiated
that are higher than the absorption edge of argon.
radiation (Kr, Xe). Using neon as the counting-gas component produces no recognisable escape peak
as the Ne K-radiation, with an energy of 0,85 keV, is almost completely absorbed in the counter. Also,
the energy difference to the incident energy of 0,85 keV and the fluorescence yield are very small.
Diffraction in crystals
Interference
Electromagnetic radiation displays interference and diffraction effects due to the nature of its waves.
“Interference” is the property of waves to overlap each other and, under certain circumstances, to
cancel out or amplify each other.
Amplification always takes place, for example, when waves of identical wavelength have zero phase
difference (coherence), i.e. when "wave maxima" and "wave minima" overlap in such a way that min-
ima meets minima and maxima meets maxima. This is precisely the case when the phase difference
'O is zero or a multiple of the wavelength O, i.e.:
'O nO n = 0, 1, 2, ....
Where the phase difference is one half of the wavelength: n = 1/2, 3/2, 5/2, ...... wave maxima coin-
cide with wave minima resulting in total cancellation (Fig. 13). When a number of waves of the same
wavelength propagating in the same direction interfere with each other under continuous phase shift,
only the coherent among them will be amplified. In total, the rest will almost completely cancel each
other out.
Diffraction
From what we experience every day we know that light generally travels in straight lines. This corre-
sponds with the image of light as a beam of particles (photons, quants). We know from waves that
when a wave series (e.g. water waves) travels through a hole smaller than the wavelength, the waves
exiting the hole spread out to the sides. Light displays the same characteristics due to its nature of
waves. The deviation of light from its travel in a straight line is called diffraction, also when it is not
reflected or refracted.
There are numerous applications for the effects of diffraction. In wavelength dispersive XRF we are
mainly interested in diffraction in reflection grids. Often used in the optical range (O = 380 - 750 nm)
are mirror lattices produced by spacing grooves at equal distances in reflecting metal surfaces. This is
no longer possible in the X-ray field for technical reasons as the wavelengths involved are around 2 to
5 orders of magnitude smaller (O = 0,02 - 11 nm). Very much smaller lattice distances such as are
found in natural crystals, are required for X-ray diffraction in the reflexion grid.
The effects of diffraction are a prerequisite for wavelength dispersive XRF. After excitation of the ele-
ments in the sample (by X-rays), a blend of element-characteristic wavelengths (fluorescence radia-
tion) leaves the sample. There are now two methods ( or procedures) in XRF of identifying these vari-
ous wavelengths. The energy dispersive XRF calls on the assistance of an energy dispersive detec-
tor that is able to resolve the different energies. Wavelength dispersive XRF utilises the diffraction
effects to split up (or separate) the various wavelengths in an analyzer crystal. The detector subse-
quently determines the intensity of a particular wavelength. The procedure will be covered in detail in
the following sections.
To Fig. 14 :
Under amplification conditions, parallel, coherent X-ray light (1,2) falls on a crystal with a lattice plane
distanced 'd' and is scattered below the angle T (theta) (1', 2'). The proportion of the beam that is scat-
tered on the second plane has a phase difference of 'ACB' to the proportion of the beam that was scat-
tered at the first plane. Following the definition of the sine:
' AC '
sin T or ' AC ' d sin T
d
The amplification condition is fulfilled when the phase difference is a whole multiple of the wavelength
O , so:
Fig. 15a, 15b, 15c (page 27) illustrate Bragg's Law for the reflection orders n = 1, 2, 3.
On the basis of Bragg's Law, by measuring the angle Tyou can determine either the wavelength O,
and thus chemical elements, if the lattice plane distance 'd' is known or, if the wavelength O is known,
the lattice plane distance 'd' and thus the crystalline structure.
This provides the basis for two measuring techniques for the quantitative and qualitative determination
of chemical elements (XRF) and crystalline structures (molecules, XRD), depending on whether the
wavelength O or the 2d-value is identified by measuring the angle T (Table 3).:
In X-ray diffraction (XRD) the sample is excited with monochromatic radiation of a known wavelength
(O) in order to evaluate the lattice plane distances as per Bragg's equation.
In XRF, the 'd'-value of the analyzer crystal is known and we can solve Bragg's equation for the ele-
ment-characteristic wavelength (O).
As the radiation with one half of the wavelength has twice the energy, the radiation with one third of
the wavelength three times the energy etc., peaks of twice, three times the energy etc. can occur in
the pulse height spectrum (=energy spectrum) as long as appropriate radiation sources (elements)
exist. (Fig. 16).
Fig. 16 shows the pulse height distribution of the flow counter using the example of the element haf-
nium (Hf) in a sample with a high proportion of zircon. The Zr KD1 – peak has twice the energy of the
Hf LD1 – peak and appears, when the Hf LD1 – peak is set, at the same angle in the pulse height spec-
trum.
Crystal types
The wavelength dispersive X-ray fluorescence technique can detect every element above the atomic
number 4 (Be). The wavelengths cover the range of values of four magnitudes: 0,01 - 11.3 nm (cf.
Table 1). As the angle T can theoretically only be between 0° and 90° (in practice 2° to 75°), 'sin T'
only accepts values between 0 and +1. When Bragg's equation is applied:
nO
0% sin T % 1
2d
this means that the detectable element range is limited for a crystal with a lattice plane difference 'd'.
Therefore a variety of crystal types with different '2d' values is necessary to detect the whole element
range (from atomic number 4). Table 4 shows a list of the common crystal types.
Lithiumfluoride crystals which also state the lattice planes (200, 220, 420) are identical to the following
names:
LiF(420) = LiF(210)
LiF(220) = LiF(110)
LiF(200) = LiF(100)
Besides the 2d-values, the following selection criteria must be considered when a particular type of
crystal is to be used for a specific application:
x resolution
x reflectivity (--! intensity)
x temperature stability
x suppression of higher orders
x crystal fluorescence
dT n
dO 2d cos T
It can be seen from this equation that the dispersion (or peak separation) increases as the lattice plane
distance 'd' declines.
The 2Tvalues of the KD1-peaks of sulphur (S) and phosphorus (P) are further apart when measuring
with the Ge crystal than when doing so with the PET crystal (cf. e.g.: Bruker AXS table-top periodic
table).
Table 5: Explanatory details for dispersion
Crystal type 2d-value (nm) 2T (El1) (degrees) 2T (El2) (degrees) Difference (degrees)
LiF(220) 0.2848 107.11 (Cr) 123.17 (V) 16.06
LiF(200) 0.4028 69.34 (Cr) 76.92 (V) 7.58
Ge 0.653 110.69 (S) 141.03 (P) 30.34
PET 0.874 75.85 (S) 89.56 (P) 13.71
The following describes the characteristics of the individual crystal types divided into “standard crys-
tals”, “multilayers” and “special crystals”.
LiF crystal types exist in a variety of lattice planes (200/220/420). In the sequence (200) --! (220) --!
(420), resolution increases and reflectivity decreases (Fig. 17).
Fig. 17: Intensities of the crystals Lif(220) and Lif(420) in relation to Lif(200). (Intensity
LiF(200) = 1)
LiF(200):
A universally usable crystal for the element range atomic number 19 (K) onwards; high reflectivity,
high sensitivity (HS).
LiF(220):
Lower reflectivity than the LiF(200) but higher resolution (HR); can be used for the element range
atomic number 23 (V) onwards; particularly suitable for better peak separation where peaks overlap.
Examples for the application of the LiF(220) for reducing peak overlaps:
Cr KD1,2 - V KE1
Mn KD1,2 - Cr KE1
U LD1 - Rb KD1,2
LiF(420):
One of the special crystals; can be used for the element range atomic number 28 (Ni or Co KE1) on-
wards; best resolution but low reflectivity;
Fig. 17 shows a reflectivity of only 10% of that of the Lif(200) for the Lif(420) in the energy range
around 10 keV.
PET:
A universal crystal for the elements Al to Ti (K-peaks) and Rb to I (L-peaks).
ATTENTION
The PET is the crystal with the greatest heat-expansion coefficients, i.e. temperature fluctuations are
most noticeable here.
OVO-55:
The most commonly used multilayer with a 2d-value of 5.5 nm for analysing the elements N (C) to Si;
standard application for measuring the elements F, Na, Mg.
Special Crystals
The term 'special crystals' refers to crystal types and multilayers that are not used universally but are
employed in special applications.
LiF(420):
Cf. 'standard types', description of the LiF crystals (200, 220, 420).
Ge:
A very good crystal for measuring the elements S, P, Cl. In comparison to PET, Ge is characterised by
a higher dispersion and a more stable temperature behaviour. Ge suppresses the peaks of the 2nd and
4th order, in particular.
Ge is especially suitable for differentiating between sulphide/sulphate e.g. in samples of cement.
AdP:
In practice, AdP is only used for the analysis of Mg and has a higher resolution with a significantly
lower reflectivity compared to the multilayer OVO-55. AdP is therefore required where interference
peaks can occur such as in the case of low Mg concentrations in an Al matrix.
TlAP:
TlAP has high resolution but low reflectivity and is recommended for analysing F and Na if the resolu-
tion of OVO-55 is insufficient (e.g. where Na is overlapped by the Zn-L peaks in Zn-rich samples).
DANGER
Disadvantages are the limited lifetime, toxicity, and high price.
InSb:
InSb is a very good crystal for analysing Si in traces as well as in higher concentrations (e.g. glass). It
replaces PET and is used wherever high precision and great stability is required. The disadvantages
are the limited use (only Si) and the high price.
OVO-C:
OVO-C is a multilayer with a 2d value of 12 nm, specially optimized for carbon.
OVO-N:
OVO-N is multilayer with a 2d-value of 11 nm, specially optimized for nitrogen.
OVO-B:
OVO-B is multilayer with a 2d-value of 20 nm, specially optimized for boron and is equally suitable for
the analysis of Be.
Which multilayer crystal is the most suitable for analysing the very light elements?
Fig. 19a shows that the OVO-B is the best one for analysing Boron (B), naturally with the correspond-
ing coarse collimator (at least 2° opening). A compromise for analysing Boron can be the OVO-160
when Carbon (C) should be also measured with the same crystal.
For the analysis of Carbon (C) the OVO-C provides a sharper peak and a better ratio of the peak /
background intensities, which means that better sensitivies can be achieved (Fig. 19b). To apply the
OVO-55 for analysing Carbon should be exceptional in case of having no OVO-C or OVO-160. Only
very high concentrations (several tens of per cent) of Carbon can be determined with the OVO-C. In
case of determining Carbon with the OVO-55 using the „standardless“ precalibrated XRF routine,
please don´t forget to select a very slow scanning speed (long measuring time) for Carbon or to select
the peak/background measurement mode.
Nitrogen (N) is best analysed using the OVO-N. If needed, the OVO-55 can be applied also (Fig. 19c).
OVO-B, OVO-C and OVO-160 are not suitable to analyse Nitrogen.
Oxigen (O) and all further „heavier“ light elements have to be analysed with the OVO-55 which gives
the best resolution and the best peak/background ratio (Fig. 19d).
4,0 4,0
3,9 3,9
3,8 3,8
OVO-B
3,7 3,7
3,6 3,6
3,5 3,5
3,4 3,4
3,3 3,3
3,2 3,2
3,1 3,1
3,0 3,0
2,9 2,9
2,8 2,8
2,7 2,7
2,6 2,6
2,5 2,5
2,4 2,4
2,3 2,3
2,2 2,2
Lin (KCps)
Lin (KCps)
2,1 2,1
2,0
OVO-160 2,0
1,9 1,9
1,8 1,8
1,7 1,7
1,6 1,6
1,5 1,5
1,4 1,4
1,3 1,3
1,2 1,2
1,1
OVO-C 1,1
1,0 1,0
0,9 0,9
0,8 0,8
0,7 0,7
0,6 0,6
OVO-N
0,5 0,5
0,4 0,4
0,3 0,3
0,2 0,2
0,1 0,1
0 0
SqE - Scale
Immediate Measurement - Crystal: OVO-B - 2T h.0: 1 05 (#) - B - - - - - -
Operations: Import [001]
Immediate Measurement - Crystal: OVO-160 - 2T h.0
Operations: Import [002]
Immediate Measurement - Crystal: OVO-C - 2T h.0: 4
Operations: Import [003]
Immediate Measurement - Crystal: OVO-N - 2T h.0: 5
Operations: Import [004]
Fig. 19a: OVO-B is the best multilayer crystal for analysing Boron (B).
40 40
39 39
38 38
37 37
36
OVO-160 36
35 35
34 34
33 33
32 32
31 31
30 30
29 29
28 28
27 27
26 26
25 25
24 24
23 23
22 22
OVO-C
Lin (KCps)
Lin (KCps)
21 21
20 20
19 19
18 18
17 17
16 16
15 15
14 14
13 13
12 12
11 11
10 OVO-N 10
9 9
8 8
7 7
6 6
5 OVO-B 5
4 4
3
OVO-55 3
2 2
1 1
0 0
6,90 6,91 6,92 6,93 6,94 6,95 6,96 6,97 6,98 6,99 7,00 7,01 7,02 7,03
SqE - Scale
Immediate Measurement - Crystal: OVO-C - 2T h.0: 3 Immediate Measurement - Crystal: OVO-55 - 2T h.0:
Operations: Import [001] Operations: Import [005]
Immediate Measurement - Crystal: OVO-N - 2T h.0: 3 06 (#) - C - - - - - -
Operations: Import [002]
Immediate Measurement - Crystal: OVO-160 - 2T h.0
Operations: Import [003]
Immediate Measurement - Crystal: OVO-B - 2T h.0: 1
Operations: Import [004]
Fig. 19b: The OVO-C multilayer crystal is suitable for the determination of Carbon.
OVO-N
3 3
2 2
OVO-B
OVO-160
Sqr (KCps)
Sqr (KCps)
1 1
0,6 0,6
0,5
OVO-55 0,5
0,3 0,3
0,2 0,2
0,1 0,1
0,01 0,01
0,001 0,001
0 0
SqE - Scale
Immediate Measurement - Crystal: OVO-N - 2T h.0: 2 Immediate Measurement - Crystal: OVO-55 - 2T h.0:
Operations: Import [001] Operations: Import [005]
Immediate Measurement - Crystal: OVO-160 - 2T h.0 07 (#) - N - - - - - -
Operations: Import [002]
Immediate Measurement - Crystal: OVO-C - 2T h.0: 2
Operations: Import [003]
Immediate Measurement - Crystal: OVO-B - 2T h.0: 1
Operations: Import [004]
4,0 4,0
3,9 3,9
3,8 3,8
3,7 3,7
3,6 3,6
3,5 3,5
3,4 3,4
3,3 3,3
3,2 3,2
3,1 3,1
3,0 3,0
2,9 2,9
2,8 2,8
2,7 2,7
2,6 2,6
2,5 2,5
2,4 2,4
2,3 2,3
2,2 2,2
Lin (KCps)
Lin (KCps)
2,1 2,1
2,0 2,0
1,9 1,9
1,8 1,8
1,7 1,7
1,6 1,6
1,5 1,5
1,4 1,4
1,3 1,3
1,1 1,1
1,0 1,0
0,9 0,9
0,8 0,8
OVO-160
0,7 0,7
0,6 0,6
0,5 0,5
0,4
OVO-N 0,4
0,3 0,3
0,2
OVO-55 0,2
0,1 0,1
0 0
6,712 6,72 6,73 6,74 6,75 6,76 6,77 6,78 6,79 6,80 6,81 6,82
SqE - Scale
Immediate Measurement - Crystal: OVO-55 - 2T h.0: 08 (#) - O - - - - - -
Operations: Import [001]
Immediate Measurement - Crystal: OVO-160 - 2T h.0
Operations: Import [002]
Immediate Measurement - Crystal: OVO-N - 2T h.0: 1
Operations: Import [003]
Immediate Measurement - Crystal: OVO-C - 2T h.0: 1
Operations: Import [004]
Fig. 19d: Oxigen (O) and all further „heavier“ light elements have to be analysed with the OVO-55.
Curved Crystals
Whereas flat crystals are used in sequence spectrometers, multichannel spectrometers principally
employ curved crystals (cf. instrumentation, Fig. 21 - 23).
The curvature of the crystals is selected in such a way that by applying a slit optics the X-ray entrance
slit is focussed by the curved crystals onto the exit slit. This allows higher intensities in a space-saving
geometric arrangement.
Different types of crystal curvature are used for focussing. The most commonly used are the curva-
tures that follow a logarithmic spiral (Fig. 20a) and the Johansson curvature (including grinding)
(Fig. 20b).
Instrumentation
The following explains the instrumentation in the Bruker AXS X-ray fluorescence spectrometer. The
first three sections contain brief summaries on the multichannel X-ray spectrometer MRS, the older
side-window sequential spectrometer SRS 200 and the SRS 30X. The fourth section deals in detail
with the technology of the sequential spectrometers SRS 3X00 and S4.
As all elements are measured simultaneously, a generator setting (kV/mA) must be selected that pro-
vides the best compromise in each case for the components to be measured. The measurement pe-
riod depends on statistical accuracy requirements of the element with the lowest intensity and is typi-
cally around 20 – 60 seconds. No background positions can be measured as the monochromators are
at a fixed setting to the angle of the appropriate line.
When measuring trace and major elements simultaneously, the generator is normally set so that the
trace elements can be measured with the highest possible intensity. This means that the major ele-
ments are usually of very high intensity that cannot be processed by the detectors. For cases such as
these, the MRS can be fitted with absorbers (attenuator) for the major elements whose intensities are
reduced sufficiently for them to then lie in the operational range of the detectors.
Besides extending the adjustment parameters of the primary beam filter, the crystal and collimator
changer beyond those possible on the SRS 303, the detector high-voltages, too, are set via the analy-
sis computer.
The separate TTgoniometer drive with two independent stepper motors allows a precise TTangle
alignmentvia the analysis computer’s software.
The flow counter is situated inside the spectrometer chamber and has an angle scope of 2° to 148°.
Located behind the flow counter and outside the chamber, separated by a 0.1 mm Al foil, is the scintil-
lation counter with an angle scope of 2° to 110°. Both detectors can be used individually or in tandem.
In tandem operation, the intensity in the flow counter is measured as well as the radiation that passes
through the flow counter and the radiation that is absorbed by the scintillation counter.
Tandem operation was excluded from the S4 EXPLORER and the S4 PIONEER to save space and
the scintillation counter located in the spectrometer chamber next to the proportional counting tube.
Integrating temperature measuring points allows this stability-relevant factor to be checked in the in-
strument. Furthermore, the temperature of the water in the internal deionised cooling system is kept
constant.
An optional protractable/retractable foil screen can be installed between the sample chamber and the
spectrometer chamber for measuring, for example, liquids in an He atmosphere.
Fig. 24 shows the beam path and the adjustable factors of the S4 basically contains the same compo-
nents.
A flexible, modifiable sample changer with a robot arm that moves in the directions X and Y allows
fully automatic transport of:
x combinations of both
stack operation without time-loss through transporting samples, i.e. while one sample is being meas-
ured, the next is being inserted into the pre-vacuum chamber.
Sample
Vacuum Seal
Analyzer Crystals
X-ray Tube
Proportional Scintillation
Counter Counter
Problem-free docking on to a conveyor belt allows easy integration into an automated environment.
The function and possible settings for the various parameters will now be described in the order they
are encountered by the beam propagating from the tube to the scintillation counter.
x 27 kV / 150 mA = 4,05 kW
x 30 kV / 134 mA = 4,02 kW
x 40 kV / 100 mA = 4,00 kW
x 50 kV / 80 mA = 4,00 kW
x 60 kV / 67 mA = 4,02 kW
Minimum settings: 20 kV / 5 mA = 0,1 kW
NOTE
The control and analysis software SPECTRA AT / SPECTRA 3000 / SPECTRAplus checks the settings
and prevents the maximum permissible values being exceeded.
Rhodium is used as the standard anode material. The light elements Be to Cl are effectively excited by
the Rh-L beam’s high transmission rate through the 75 µm Be tube window. The characteristic Rh-K
radiation excites the elements up to Mo (Ru) (cf. also Table 2, page 9). The elements from Rh on-
wards are excited by the Bremsstrahlung’s high-energy “tail”.
4 kW-Tubes with other anode materials can be used for special applications (e.g. Mo, W, Au, Cr)
of thickness as absorbers. The one fitted can be selected to suit individual requirements when pur-
chasing the instrument.
When measuring Rh K with the Rh tube, the characteristic Rh radiation coming from the tube must be
filtered out because it would otherwise be measured as a result of elastic scattering on the sample (cf.
page 15). By using a 0.2 mm-thick Cu filter, the characteristic Rh tube radiation is largely absorbed
prior to reaching the sample. The measurement must be taken with a tube high-voltage of 60 kV as
the Rh in the sample is only excited by the high-energy Bremsstrahlung.
Fig. 25 illustrates the tube spectrum acting on the sample without a primary beam filter and tube high-
voltage of 60 kV.
Fig. 26 shows the reduction in Rh radiation scattering on a plant sample using different primary beam
filters made of copper or aluminium.
Fig. 25: Cd- and Rh-peak without a copper primary beam filter
Fig. 26: Cd- and Rh-peak with 0.2 or 0.3 copper primary-beam filter
Fig. 27: The effect of the aluminium primary beam filter for optimizing the peak-background ratio
When analysing a sample of very pure graphite, peaks of the elements Cr, Fe, Ni und Cu can occur
and in the 2T-spectrum although the sample contains none of the elements. The Cu peak originates
from the excitation of the collimator material that mainly consists of copper.
The Cr, Fe and Ni peaks are called “spectral impurities” of the tube. If the elements Cr, Fe and Ni are
to be measured as traces, it may be advantageous to use the 0.2 mm Al filter to absorb these compo-
nents.
For alternate measurements of samples in a vacuum and helium, this technique considerably quickens
the change from one operating mode to another as a result of the smaller sluicing volume and reduces
the helium consumption.
Collimator Masks
The collimator masks are situated between the sample and collimator and serve the purpose of cutting
out the radiation coming from the edge of the cup aperture. The size of the mask is generally adapted
to suit of the cup aperture being used. The SRS 3X00’s changer has 4 positions, the SRS 300/303 is
equipped with a 3-position changer. The S4 EXPLORER employs a new collimator mask that is set
very close to the sample and therefore optimally screens the sample cup aperture.
Fig. 28: The influence of collimator resolution on the intensity for light elements
ATTENTION
As the plastic foils have a high proportion of carbon, the absorption of the nitrogen radiation close to
the C absorption edge is very high. This means that even the 1 µm foil only has an approx. 10% per-
meability. For this reason, the measured intensities for the element N are relatively low. The newer 0.6
µm and especially the 0.3 µm foils are more permeable to nitrogen radiation.
Generally, Ar + 10% CH4 is used as the counting gas (P10). The flow of counting gas is held constant
in the instrument as a fluctuating counting-gas density in the counting tube would cause fluctuations in
the absorption depth as well as fluctuations in the gas amplification and thus in the position of the
peaks in the pulse height spectrum, too (cf. Fundamental Principles: The gas proportional counter
Fig. 8).
The high voltage at the counting wire is set higher for light elements (OVO Multilayer) than for measur-
ing the K-radiation (e.g. LiF crystals) of medium and heavy elements. In sequential spectrometers the
detector high voltage is set separately for each element range (energy range) and thus for each in-
stalled crystal (cf. also Fig. 8 ).
approx. 4.5 keV (Cr KD1) as the lower ones are absorbed mainly in the flow counter (cf. Fundamental
Principle: The scintillation counter Fig. 9).
The SC’s angle scope ranges from 4° to 110° (SRS 30X: 4° to 90°).
In the S4 EXPLORER the scintillation counter is directly beside the proportional counter in the spec-
trometer chamber and can be moved from 0° to 115°.
The Discriminator
Depending on the application, higher order peaks or other sources of interference appear in the pulse
height distribution, or the detectors‘ energy spectrum (cf. also Fig. 10a, b and Fig. 11) with different
levels of energy. A discriminator window is used to set a lower and an upper pulse-height threshold.
Only the pulse heights that lie within these limits are counted In this way, higher order peaks or inter-
ference radiation with pulse heights beyond the window are supressed (cf. Fig. 16). Discriminating
undesirable pulses reduces the background.
V a sin T
This is the only way of ensuring that a discriminator window once set for a crystal will be applicable for
all detectable energies (element peaks).
A main amplifier coupled in this way is called a sine amplifier.
Line-shift Correction
Line-shift correction is only important for the flow counter and the proportional counter at high intensi-
ties. It makes itself noticeable when the peak in the pulse height spectrum shifts to lower values at
high counting rates. The reason for this is that high counting rates in the detector volume between the
flow counter’s cathode and counting wire build up a space charge that causes a temporary reduction
of the effective high voltage and thus the reduction of gas amplication.
This shift of pulse heights to lower values is automatically corrected by the electronics. The correction
can be switched on and off in the software (SPECTRA 3000 / SPECTRAplus).
Appendix A
Supplementary Literature
Books
P. Hahn-Weinheimer Röntgenfluoreszenzanalytische
A. Hirner Methoden, Grundlagen und praktische Anwendung in den Geo-,
K. Weber-Diefenbach Material- und Umweltwissenschaften
Friedrich Vieweg & Sohn, Braunschweig / Wiesbaden 1995
ISBN 3-528-06579-6
Tables
Journals
Appendix B
Appendix C
Introduction
X-ray fluorescence (XRF) analysis is a fast, non-destructive and environmentally friendly analysis
method with very high accuracy and reproducibility. All elements of the periodic system from beryllium
to uranium can be measured qualitatively, semiquantitatively and quantitatively in powders, solids and
liquids. Concentrations of up to 100 % are analysed directly and without any dilution – with reproduci-
bilities better than ± 0.1 %. Typical limits of detection are from 0.1 to 10 ppm. Most modern X-ray
spectrometers with modular sample changer concepts enable a fast, flexible sample handling and
adaptation to customer specific automation processes without any problems.
XRF analysis is a physical method which directly analyses almost all chemical elements of the periodic
system in solids, powders or liquids. These materials may be solids such as glass, ceramics, metal,
rocks, coal, plastic or liquids, like petrol, oils, paints, solutions, blood or even wine. With an X-ray fluo-
rescence spectrometer both very small concentrations of very few ppm and very high concentrations
of up to 100 % can directly be analysed without any dilution process. Therefore XRF analysis is a very
universal analysis method, which, – based on simple and fast sample preparation – has been widely
accepted and has found a large number of users in the field of research and above all in industry.
Especially in the extremely complex environmental analysis and in production and quality control of
intermediate and end products, there are increasing possibilities for XRF analysis.
The quality of sample preparation in X-ray fluorescence analysis is at least as important as the quality
of measurements.
An ideal sample would be prepared so that it is:
Elemental analysis using XRF provides a non-destructive and environmentally friendly analysis
method without having to bring solid samples into solution and without having to dispose of solution
residues, as is the case with all wet-chemical methods. Basic prerequisite for an exact and reproduci-
ble analysis is a plane, homogeneous and clean analysis surface. For analysis of very light elements,
e.g. beryllium, boron and carbon, the fluorescence radiation to be analysed originates from a layer,
whose thickness is of only a few atom layers up to a few tenths of micrometer and which strongly de-
pends on the sample material (Tab. 1). Therefore especially for analysis of light elements, sample
preparation has to be carried out extremely carefully.
Tab. 1: Layer thickness (in Pm), where 90 % of the fluorescence radiation originate from
Sample matrix Graphite Glass Iron Lead
Line h_(90%,Pm) h_(90%,Pm) h_(90%,Pm) h_(90%,Pm)
U LD1 28000 1735 154 22.4
Pb LE1 22200 1398 125 63.9
Hg LD1 10750 709 65.6 34.9
W LD1 6289 429 40.9 22.4
Ce LE1 1484 113 96.1 6.72
Ba LD1 893 71.3 61.3 4.4
Sn LD1 399 44.8 30.2 3.34
144600 8197 701 77.3
Cd KD1
60580 3600 314 36.7
Mo KD1
44130 2668 235 28.9
Zr KD1
31620 1947 173 24.6
Sr KD1
18580 1183 106 55.1
Br KD1,2
17773 1132 102 53
As KE1
6861 466 44.1 24
Zn KD1,2
5512 380 36.4 20
Cu KD1,2 4394 307 29.8 16.6
Ni KD1,2 2720 196 164 11.1
Fe KD1,2 2110 155 131 9.01
Mn KD1,2 1619 122 104 7.23
Cr KD1,2 920 73.3 63 4.52
Ti KD1,2 495 54.3 36.5 3.41
Ca KD1,2 355 40.2 27.2 3.04
K KD1,2 172 20.9 14.3 2.19
Cl KD1,2 116 14.8 10.1 4.83
S KD1,2 48.9 16.1 4.69 2.47
Massive materials, such as rocks, soils, slags and similar samples have to be crushed, e.g. in a crush-
ing device. The crushed material, as well as pieces thereof, are afterwards very finely pulverized in a
vibrating disk mill or planetary ball mill in order to be suitable for analysis. The grain size diameter
should then be inferior to 50 Pm. In earlier times, in the cement industry, milling in suspension was
preferred (nowadays – in fully automatic sample preparation – it is dry milling using milling and binding
agents), in order to reach grain sizes smaller than 15 Pm. The smaller and more equally grain-sized
the sample, the more homogeneous the pressed powder sample will be. Through pressing under 10 to
20 t with pressing times of 5 to 10 seconds, the sample powder is pressed into aluminium cups, steel
rings or directly freely with or without a binding agent. By rotating the sample holder in the spectrome-
ter (with 30 r/min), inhomogeneities of the sample can be compensated.
Important for XRF analysis of powder samples is the homogeneity and the fineness of the sample
powder, not only in the case of very light elements, but also e.g. for analysis of Si in samples contain-
ing quartz. At the same time, reproducibility of the samples is very important, as XRF analysis is a
comparing analysis method; this means that all unknown samples measured in comparison to a cali-
bration curve should show the same grain size distribution as the standard samples used for calibra-
tion. The importance of this requirement is often easily underestimated.
With high requirements in respect to sample homogeneity, fused beads are produced from the sample
powder at 1100 up to 1200 °C. The melting process of the sample powder is supported by melting
agents (e.g. lithium tetraborate) and, if necessary, also by oxidation agents, which are mixed into the
sample in different ratios. In earlier times, the melting method was preferred, because of the de-
creased influence of the matrix effects due to the dilution of the sample matrix with the “lighter” melting
agents. Nowadays very efficient PC programs are available for calculation of the correction coeffi-
cients (“theoretical alphas”) for matrix correction, these, too, are successfully used for pressed pellets.
For this reason, only the excessive requirement for a very high analytical accuracy nowadays speaks
against quicker and more inexpensive pressing of sample powder. With careful sample preparation
(milling), a sufficient accuracy even with pressed pellets can often be reached. For this reason, sample
preparation systems should be selected very carefully.
Since X-ray spectrometry is essentially a comparative method of analysis, it is vital that all standards
and unknown samples are presented to the spectrometer in a reproducible and identical manner. Any
method of sample preparation must give specimens which are reproducible and which, for a certain
calibration range, have similar physical properties including mass absorption coefficient, density and
particle size. In addition, the sample preparation method must be rapid and inexpensive and must not
introduce extra significant systematic errors, for example, the introduction of trace elements from con-
taminants in a diluent.
Metals
The preparation must be simple, rapid and reproducible. Usually, metallic samples are prepared as
solid disks by conventional methods of machining: cutting, milling and polishing; grinding is used in the
case of hard alloys and brittle materials such as ceramics.
The best polishing operation requires very fine abrasives to produce the scratch-free surfacing neces-
sary for most analyses, and a mirror-like surface if the sample is to be analysed for light elements. The
surface finish is of prime importance, because the polishing striations give rise to the so-called shield-
ing effect which results in a decrease in fluorescence intensities. As expected, the decrease in inten-
sity is more important for lighter elements when the primary radiation is perpendicular to the striations
and weaker when they are parallel to them. For that reason, modern spectrometers are equipped with
spinning sample holders to smooth out the influence of sample orientation, resulting in observed in-
tensities 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 production samples; this requires that the stria-
tion be of the same size and that the sample composition be similar (same effective wavelength).
In practice, striation depths of 100 Pm are acceptable for elements with characteristic lines of short
wavelengths, but striations deeper than few Pm may impair significantly the accuracy of Si, Al and Mg
determinations.
Very fine grits of Al2O3, SiC, B6C (80 to 120 grits) 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 even during milling and
especially in the final polishing operation (Pb, Cu, Al, Zn and Sn bases).
Polishing may be the 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 neces-
sary to remove contamination as well as grease stains and handling residue.
Pressed pellets
Where powders are not affected by particle size limitations, the quickest and simplest method of
preparation is to press them directly into pellets of equal density, with or without the additional use of a
binder. In general, provided that the powder particles are less than about 50 Pm in diameter, the sam-
ple will pelletize at around 10 to 30 t. Where the self-bonding properties of the powder are poor, higher
pressure may have to be employed or in extreme cases a binder will be used. It is sometimes neces-
sary to add a binder before pelletizing and the choice of the binding agent must be made with care. As
well as having good self-bonding properties the binder must be free from significant contaminant ele-
ments and must have low absorption. It must also be stable under vacuum and irradiation conditions
and it must not introduce significant interelement interferences. Of the large number of binding agents
which have been successfully employed probably the most useful are wax and ethyl cellulose.
The analysis of powder is invariably more complex than that of metallic samples, since the addition to
interelement interferences and macroscale heterogeneity, particle size effects are also important. Al-
though inhomogeneity and particle size can often be minimized by grinding and pelletizing at high
pressure, often the effects cannot be completely removed because the harder compounds present in a
particular matrix are not broken down. These effects produce systematic errors in the analysis of spe-
cific type of material, e.g. siliceous compounds in slags, sinters and certain minerals.
Analytical data for longer wavelengths will sometimes be improved if a finely ground powder is com-
pacted at higher pressures (say up to 30 t), thus a 40 ton press should be considered if light element
analysis is required in pressed powder samples. A good quality die set is required to produce good
quality pressed powder samples. A choice can be made between pressing into aluminium cups or
steel rings. Alternatively boric acid backing can be used, or free pressing if a binder is used.
We gently grind the sample containing Moviol by using a mortar and pestle, so that no more clumps
are visible. Afterwards, the sample is transferred to a press. If the sample doesn’t bind firmly, then the
amount of Moviol needs to be raised (quartzite or very quartz rich samples may need up to 50 drops /
10 g). Due to the volume of 150 ml = 1 drop, the concentration of C, H and O can be neglected.
User Tips
Depending on the sample type (e.g. TiO2 or other “pasty” substances), it is helpful to cover the surface
of the sample with a thick Mylar foil before pressing. A standard 12-Pm foil has proven to be success-
ful for this purpose. The use of the foil keeps the sample from sticking to the plunger of the press and
ensures an even smoother surface.
In the case of smaller amounts of a sample substance, one can prepare the sample by using the
sandwich method:
Sample material
Boric acid
The afore mentioned sample will be pressed onto approx. 2 spatulas full of boric acid. The use of non-
backscattering may is hereby be recommended. In all areas of application (XRD/XRF) it is necessary
to make the sample layer on the boric acid so thick, that the sample appears to be infinitely thick. As a
general rule, the thickness should be at least 1,5 mm.
For samples containing higher amounts of Moviol, the sample should be dried before measurement
with the SRS or MRS; otherwise the evacuation time lasts too long.
Fused beads
The best way of completely removing these effects is to use the fusion technique. The dissolution or
decomposition of a portion of the sample by a flux and the production of an homogeneous glass elimi-
nates particle size and mineralogical effects entirely. The fusion technique also has additional advan-
tages:
x Possibility of high or low specimen dilution for the purpose of decreasing matrix effects
Grinding
Weight Approx. 83 kg
Grinding vessel, chrome steel, 100 cm3, for HSM 100H 7KP9001-8AG
Grinding vessel, tungsten carbide, 100 cm3, for HSM 100H 7KP9001-8AJ
Grinding vessel, titanium carbide, 100 cm3, for HSM 100H 7KP9001-8AK
30-position magazine, for automatic mill HP-MA, with 100-ml cups 7KP9000-8AP
Grinding vessel, chrome steel, for automatic Herzog grinding devices 7KP9001-8AD
Grinding vessel, tungsten carbide, for automatic Herzog grinding devices 7KP9001-8AE
Grinding aid dosage device, for automatic Herzog grinding devices 7KP9001-8BY
machine is designed according to the highest safety standards. The operator uses a menu at the input
terminal. A manual vessel clamping mechanism and grinding vessel made by chrome steel is part of
the basic configuration. As an option the mill could be tuned for all sample materials by selectable
grinding speed and grinding vessel made out of a different material.
Swinging mill type PAL-M100M with pelletizing press type PAL-P40M 7KP9000-8BN
Vibrating disk mill HK 40 incl. grinding vessel (100 ml, Corundum) 7KP9000-8AV
x Powerful swing mill for desktop operation
x Standard grinding vessel of sintered corundum, 100 cm³
x Reproducible setting of milling time by electronic timer
x Wellbalanced construction for stable desktop positioning
Minimill, 40 g 7KP9000-8AL
The bench-top ring mill is designed for laboratories pulverizing samples from 2 to 40 g.
Pelletizing
Pressure Max. 40 t
Pressure holding time 0 to 1000 s, continu-
ously adjustable
Standard power supply 400 V, 50 Hz, 3 phases
Power consumption 1.2 kVA
Dimensions (hxwxd) 1250x670x690mm
Floor load 800 kg/m2
Weight Approx. 400 kg
30-position magazine for automatic sample press HP-PA, with 100-ml cups 7KP9000-8AR
Grain size (input) Max. 0.1 mm
Time per sample Typ. 60 s
Number of programs 8
Pressure 5 to 40 t
Pressure holding time 1 to 99 s
Pressed air 5 to 10 bar
Pressed air Approx. 1000 liter per
sampleconsumption
Standard dimensions of 35/40 mm dia, 14 mm
the steel rings height or 35/51.5 mm
dia, 8.5 mm eight
Standard power supply 400 V, 50 Hz, 3 phases
Power consumption 2.5 kVA
Dimensions (hxwxd) 1558x1050x900 mm
Weight 750 kg
Outside diameter 40 mm
Inside diameter 32 mm
Height 14 mm
x easy handling - wide space for die set positioning and removal
Boric acid is a binder material to be added to milled powder samples to achieve compact pressed
powder pellets for XRF analysis. Boric acid can also be used as a base for free pressed powder pel-
lets.
Sample cassette for fused bead process samples (40 mm x 14 mm) C79298-A3173-B23
Sample cassette for fused bead process samples (51.5 mm x 8.5 mm) C79298-A3173-B22
x Magnetic lock
x With 4 shelves
x Integrated hygrometer
Milling
Fusing
ISP mini fusion manual furnace 7KP9000-8BS
x High performance and reliability
x Completely electronic
Casting mould, Pt/Au (for 40 mm beads, aprox. 80 g), for ISP manual furnaces 7KP9001-8DP
VAA2 automatic fusing device, with 2 burners, incl. 2 crucibles and molds 7KP9000-8CE
VAA4 automatic fusing device, with 4 burners, incl. 4 crucibles and molds 7KP9000-8CF
x Fully automatic sample preparation for any mineral, ore, ferro-ally etc.
x Highest flexibility in melting and colling parameter setting for each station
x Effective oscillationg agitation of crucible with setting of oscillation rate and time
x Air cooling of hot mold via pre-warmed nozzle with air volume and time control
x Gas leakage control with automatic gas and oxygen smut off and LED-indicator
x Pilot burner control and air pressure control with water trap
x Solid state mechanics, one printed circuit card only, easily accessible components
x Reliable, safe and proven machine, code programming not required, simple operation
The above data for consumption of air, gas and oxygen is maximum volume for burners at highest
temperature.
x user can manually operate the instrument and record its actions in realtime in an automatic pro-
gram for future use
x programs can be saved to a floppy or hard disk when fluxer is connected to a computer
x all parameters can be modified: gas flow, mixing speed, function duration, crucible angle, cooling
air flow, solution stirring speed...
x independent mold holder allowing low-temperature fusions - useful for fluor-bearing samples
x three burners that only use propane gas: no compressed air or oxygen is required
Casting mold AGS-40 for LINN Lifumat-2.0-OX (ca. 45g, for 40 mm beads) HER-87001439
Temperature 1 600 °C
Supply pressures
Gas 0,2 to 1 bar
Oxygen 6 bar
Air 6 bar
Mains voltage 1 10 or 240 VAC
Mains frequency 50/60 Hz
Power consumption 75 W
Dimensions (hxwxd) 330 x 880 x 630 mm
Weight 90 kg
No. of burners 8
Beads produced 4per cycle
Beads produced 384 per 24-h cycle (as-
suming a cycle time of
15 min.)
Fluxes
Liquid cups
Strength
Mylar is a relatively very strong material. Polycarbonate is strong enough for most applications, how-
ever not as strong and resistant to chemical attack.
Transmission
Generalizing, transmission increases from Mylar to Polypropylene and from Polypropylene to Polycar-
bonate. Polypropylene is often used for general purposes and shows good transmission.
Purity
Mylar foils contain ppm levels of Ca, P, Fe, Cu, Zn or Sb. Polypropylene foils contain ppm levels of Ca,
Zr, P, Fe, Zn, Cu, Ti and Al.
Paper filters
Whatman paper filter, 50 mm diameter with 25 mm diameter ink ring, 100 off 7KP1901-8BH
Whatman paper filter, 50 mm diameter with 32 mm diameter ink ring, 100 off 7KP1901-8BJ
Pipette point for ml pipette, 1-200 ml, for Roth pipettes, 1000 off 7KP9001-8CN
Pipette point for ml pipette, 1-200 ml, for Eppendorf pipettes, 1000 off 7KP9001-8CP
Index
Collimators.................................................... 55
Compton scattering....................................... 16
counter plateau ............................................. 22
A crystal changer ............................................. 56
absorption......................................................12 crystal types.................................................. 30
absorption edge...............................................3 cup aperture.................................................. 54
Angström (Å) ...................................................1 curved crystals.............................................. 43
anode...............................................................8
anode material.................................................6
atomic number.................................................4
D
atomic shell......................................................2
Auger effect .....................................................4 dead time correction ..................................... 60
detectors ....................................................... 16
diffraction ...................................................... 23
discriminator ................................................. 59
B Dispersion..................................................... 32
back-scattering electrons ................................8
binding energy .................................................3
Bohr's atomic model ........................................2
E
Bragg's equation............................................25
Bremsspektrum ...............................................6 electromagnetic radiation............................ 1, 2
electron shells................................................. 2
electronic pulse processing................................ 59
end-window tube....................................... 9, 51
C energy levels................................................... 3
cathode............................................................8 energy shells................................................... 3
characteristic radiation ....................................4 exit window ..................................................... 8
of the elements in the sample material......10
collimator masks............................................55
F M
flow counter .................................................. 56 main amplifier................................................ 59
fluorescence yield ............................................4 mass attenuation coefficient ............................. 12
multichannel spectrometer
scanner...................................................... 47
multichannel spectrometer
G MRS........................................................... 45
gamma radiation ..............................................1 multilayer
generator ................................................ 10, 51 OVO-55, OVO-N, OVO-C, OVO-B............ 35
multilayers ..................................................... 33
H
N
high voltage .................................................. 10
Nomenclature.................................................. 4
I
O
intensity............................................................2
interference................................................... 23 output ............................................................ 10
K P
KCps ................................................................2 photon ............................................................. 2
kiloelectronvolts primary beam filter ........................................ 51
keV ...............................................................1 proportional counter
sealed ........................................................ 57
pulse height analysis (PHA).......................... 19
pulse height distribution ................................ 19
L pulse height spectrum................................... 16
layer thickness .............................................. 14
LiF(200), LiF(220), LiF(420) ......................... 33
line separation .............................................. 32 Q
line-shift correction........................................ 62
quants ............................................................. 1
R standard samples
sources...................................................... 67
radiation intensity ............................................2 standard types .............................................. 33
Rayleigh scattering........................................16 sub-levels........................................................ 4
Reflexionen Supplementary literature............................... 63
höherer Ordnung .......................................29
T
S
tube current................................................... 10
Sample cups..................................................54 Tube types ...................................................... 7
saturation thickness.......................................14 Tube-spectrum scattering
scintillation counter........................................58 at the sample material ................................. 15
Secondary enhancement ..............................14
sequential spectrometers
SRS 3X00 and S4......................................48
side-window tube.............................................8
V
sine amplifier .................................................60 vacuum seal.................................................. 54
Soller slit ........................................................55
Sources of standard samples........................67
special crystals
InSb............................................................37
W
special crystals ..............................................36 wavelengths.................................................... 1
AdP ............................................................37
Ge ..............................................................37
LiF(420)......................................................36
TIAP ...........................................................37 X
special crystals X-ray fluorescence spectrometer
OVO-C .......................................................37 instrumentation.......................................... 45
special crystals X-ray generator............................................. 10
OVO-N .......................................................37 X-ray quants ................................................... 2
special crystals X-ray tube ....................................................... 6
OVO-B .......................................................37