Glass Beads by Borate Fusion - tcm50-54735

XRF SAMPLE PREPARATION
Glass beads by
borate fusion
James P. Willis
ISBN: 978-90-809086-9-7
The Analytical X-ray Company

Glass beads by borate fusions
James P. Willis
About James Willis
Prof. Emeritus James Willis (1937) worked in the Department of Geochemistry
and Geological Sciences at the University of Cape Town from 1960 to 2000, during
which period he also gained his Masters (with distinction) and Doctoral degrees.
He has a very broad experience in many analytical techniques, including DC arc
optical emission spectrometry, atomic absorption spectrophotometry, electron
microprobe analysis, SEM-EDX, instrumental neutron activation analysis, ICP-AES,
ICP-MS, HPIC, particle size analysis, X-ray diffraction and XRFS.
Copyright © 2010 by PANalytical BV, The Netherlands.
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Although diligent care has been used to ensure that the information herein is
accurate, nothing contained herein can be construed to imply any representation
or warrantee as to the accuracy, currency or completeness of this information. The
content hereof is subject to change without further notice. Please contact us for
the latest version of this document or further information.
© PANalytical B.V. [2009]. 9498 707 28814 PN7216
This edition published in 2010 by:

PANalytical B.V.
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ISBN: 978-90-809086-9-7
1st edition. Based on chapter 19 from Understanding XRF spectrometry vol. 2
PANalytical
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1 Undesirable effects of using powders in XRFS . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2 Advantages of using fusion techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2 Preparation of glass disks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1 General procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.1 Typical simplified procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 A limitation to borate fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Fluxes and additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2.1 Fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2.2 Properties of borate fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.3 Impurities in fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.4 Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.5 Non-wetting (releasing) agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3 Preparation before fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.1 Fusion mixture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.2 Crucibles and molds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4 Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.4.1 Heating requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.4.2 Heating steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4.3 Heating steps for oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4.4 Heating steps for fusion and homogenization . . . . . . . . . . . . . . . . . . . . . . . 24
2.4.5 Heating steps for conditioning before casting . . . . . . . . . . . . . . . . . . . . . . . 26
2.5 Casting and cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.5.1 Casting into molds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.5.2 Solidification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.6 Examples of fusions that require special techniques . . . . . . . . . . . . . . . . . . . 31
2.6.1 Sulfide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.6.2 Copper compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.6.3 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.6.4 Metallic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.6.5 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 Pyrosulfate fusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2 Automatic preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.3 Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.4 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.5 Fusions of sulfide concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.6 Analysis of disks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4 Fluxers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.1 Fusion instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3
PANalytical Sample preparation XRF and glass beads by borate fusions
5 Care and use of platinum ware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

5.1 Why platinum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2 Damage to platinum ware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.2.1 Crucibles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.2.2 Molds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.3 Prolonging platinum ware lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.3.1 Cleaning of platinum ware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.3.2 Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.3.3 Polishing and re-shaping kits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.1 Contamination by crucibles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.2 Contamination by W when using WC grinding vessels . . . . . . . . . . . . . . . . . 47
6.3 Blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.4 Loss or gain on ignition (LOI or GOI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
7 Advantages and limitations of fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7.1 Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7.1.1 Reproducibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7.1.2 Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7.1.3 Preparation of standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7.1.4 Versatility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7.1.5 Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
7.2 The Eagon 2 from PANalytical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
7.3 Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
7.4 Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
8 Selection of flux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
10 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4
Introduction PANalytical
1. Introduction
The use of powdered samples in XRFS has a number of undesirable effects
(Figures 1 and 2). The best, and in some instances the only, means of eliminating
these effects is to fuse the sample with a suitable flux and cast it as a glass bead.
Glass beads are the ideal sample form for XRFS (Figure 2).
Emitted X-ray intensity
Particle size (coarser)

Figure 1. Effect of mineralogy on emitted X-ray intensity. Reducing the particle size can either
decrease or increase emitted X-ray intensity.
Pressed powders
200
Corr. count rate (kcps)
100
R2 = 0.9642
0
0 50 100
Conc. SiO2 (wt %)
Fused beads
200
Corr. count rate (kcps)
100
R2 = 0.9996
0
0 50 100
Conc. SiO2 (wt %)
Figure 2. Powder pellets are subject to particle size and mineralogical effects, surface roughness,
preferential orientation and segregation problems, which can give poor quality calibrations. Fused
beads provide the ideal sample for XRF analysis.
5
1.1 Undesirable effects of using powders in XRFS

• Particle size problems
• Mineralogical problems
• Surface roughness
• Segregation problems
• Preferential orientation
• Statistics
However, pressed powers are often, and very successfully, used in production
control, especially if the calibration ranges are short (Figure 3). However, it is
not always easy to obtain suitable standards that have the same particle size,
mineralogy, surface roughness and segregation characteristics as the production
samples. The role of fused beads is extremely important in setting up reference
calibrations for determining in‑house standard compositions for use in production
control calibrations (Figure 3).
Pressed powder, production control calibrations Fused bead reference calibration

200 200
Count rate (kcps)
Count rate (kcps)
C
C
100
B 100 B
A A
0 0
0 50 100 0 50 100
SiO2 (wt %) SiO2 (wt %)
Figure 3. The use of in-house pressed powder standards in setting up calibrations over small
concentration ranges for production control. The in-house standards concentrations were obtained
from fused bead calibrations based on CRMs.
1.2 Advantages of using fusion techniques

• No particle size effects
• ONLY inter-element matrix effects
• All standard methods applicable (internal standards; dilution; double dilution)
• Preparation of artificial standards is relatively easy, and very much easier than
preparing artificial standards for pressed powders
• Accurate application of inter-element corrections (theoretical and empirical)
possible
Fusion is a general name for all kinds of chemical attacks on solid samples to
transform them into compounds that are easily transformed into a solution. These
compounds are an intermediate step between the original sample and the solution
that is used later in an analytical process.
6
Introduction PANalytical
Most fusion processes result in a product that is a mixture of several compounds

which have as a common property that all are soluble in a given solvent. These
processes are regular chemical reactions and the products are crystalline.
Although a borate fusion is also a chemical reaction, its characteristics are

different. At high temperature the flux melts and becomes a solvent for most
oxide compounds. One product only is formed, a homogeneous solution. This
solution may be cooled without crystallizing to yield an amorphous homogeneous
solid which is a glass. The latter is ideal for XRF work. Alternately it may be cooled
drastically by dropping into a solvent, in which case it shatters into fine crystals that
dissolve to yield a solution, which is a fast way to prepare samples for ICP analysis.
This concept of borate fusion helps to understand why high‑temperature

refractories can be fused at temperatures as low as 1000°C, why materials
cannot be mixed with fluxes in any proportion, why some elements are lost by
volatilization if heated at too high temperatures, etc.
Application of the borate fusion to make glass beads for X‑ray fluorescence is
generally simple, but more complex than for the preparation of solutions for ICP.
Borate fusions are discussed in this booklet.
7
Preparation of glass disks PANalytical
2. Preparation of glass disks

2.1 General procedure
The general procedure for preparing fused beads for XRF analysis is shown in
Figure 4. The sample, undried, dried at 100, 105 or 110 °C (105 °C is the norm for
geological samples) and/or roasted at ~1000 °C, is weighed with flux into a Pt
crucible, pretreated if necessary, melted, mixed, cast into a Pt mold and cooled to
form a stable glass bead. It is important to note that sulfates are dried at 40 °C to
avoid the formation of hemihydrates.
Accurate
data
Figure 4. The general procedure for preparing stable fused beads for XRF analysis
2.1.1 Typical simplified procedure

Essentially a fusion procedure consists of (Figure 5):
a) heating a mixture of sample and borate flux until the flux melts;
b) continuing heating until the sample dissolves into the molten flux, and
agitating to homogenize the melt;
c) pouring into a hot mold;
d) cooling to obtain a solid glass bead, ready for X‑ray measurement with no
further treatment.
9
Temperature (°C)
Time
Figure 5. Temperature-time curve for a full fusion cycle during which oxidation, decomposition and
fusion take place, and the melt is cooled to form a solid, stable glass bead.
In discussing the fusion procedure for glass beads one must consider the
ingredients, their preparation, the utensils, and the fusion process itself. All of
these will be considered.
Making a glass bead today is a simple process thanks to the availability of

automatic fusion instruments, such as PANalytical’s, compact, high-performance
Eagon 2 (Figure 6).
Figure 6. PANalytical’s fully automatic, high-performance Eagon 2 fusion machine for XRF sample
preparation
It is true that fusion is sometimes perceived to be a complex problem. The reason

for this is that one wants to make better glass beads for greater analytical accuracy
and to apply the technique to a larger diversity of samples. This means that more
10
versatility is necessary in the parameters involved such as composition of flux,

temperature of fusion and cooling rate. The cost-effective Eagon 2 provides all the
necessary versatility and optimum fusion conditions combined with unparalleled
safety, together with a pre-loaded set of basic fusion programs.
2.1.2 A limitation to borate fusion

A molten borate is a good solvent for oxides, but for oxides only. This includes
hydrates, carbonates, sulfates and nitrates that are also soluble because they are a
combination of two oxides, one of which is either volatile (H2O, CO2, N2O5) or partly
volatile (SO3). SO42– (≡ SO3) is retained in the flux. Halides are not really soluble as
shown by the volatility of the halogen atom that increases rapidly with the atomic
number; fluorine is rather marginal, being slightly volatile. Metals, carbides,
nitrides and sulfides are insoluble in borate but they can be dissolved after an
oxidation treatment. Consequently, the fusion technique will be described as if the
sample were in its highest oxidation state, but the modifications required when the
sample is in a reduced condition will be added when appropriate.
2.2 Fluxes and additives

2.2.1 Fluxes
The more commonly used fluxes are lithium tetraborate, lithium metaborate and
sodium tetraborate.
Lithium tetraborate (LiT), Li2B4O7, was the more commonly used flux in XRF
analysis; it is transparent to light element X-rays, it is barely hygroscopic, but it has
a tendency to crystallize. With a melting point of 930 °C it is the more difficult flux
to fuse among the common ones. It is a suitable flux for basic materials, e.g. Ca and
Mg oxides. It is a very good flux for carbonates, because carbonates decompose
before or when the flux starts to melt. Therefore, the CO2 gas escapes easily thus
minimizing the trapping of gas in the flux mixture which would cause foaming and
loss of material.
Lithium metaborate (LiM), LiBO2, is very susceptible to crystallization, more than

the tetraborate, but has a better solubility for several elements. Its melting point
is 849 °C and it has a low viscosity. It is the preferred flux for the preparation of
solutions. Mixed with Li2B4O7 it is a useful flux for acidic materials.
Anhydrous sodium tetraborate, Na2B4O7, would be the more desirable flux for
glass beads if it were not so hygroscopic. The glass beads have almost no tendency
to crystallize or to crack but they must be kept in a desiccator to prevent the
formation of a white layer of hydrated borate. The melting point is 741 °C. Using
Borax (Na2B4O7  10 H2O) for XRF fusions is not recommended due to its large
content of water that yields such a large volume of gas when heated fast that
part of the fusion mixture might be blown out of the crucible. Obviously, the large
amount of sodium in the flux precludes analysis of sodium in the samples.
11
A combination of borates is useful and many mixtures are now available

commercially (Figure 7). Such fluxes are more fluid and have a lower melting
point than pure Li tetraborate. The so‑called ‘12‑22’ flux, melting point 825 °C
and strongly favoured in Australia, contains 12 parts LiT and 22 parts LiM and is
recommended for high silica rocks. A 66:34 mixture of LiT:LiM, melting point 875 °C,
is the best general purpose flux. A 50:50 mix of LiT:LiM is also a good general
purpose flux for most geological rock types, including silicate (acidic material) and
carbonate (alkaline material) rocks.
Figure 7. A typical set of pure and mixed borate fluxes with non-wetting agent and platinum ware
available from PANalytical
The Norrish and Hutton (1969) mixture, Li2B4O7 + Li2CO3 (or NaNO3) + La2O3 , was
commonly used for fusing silicate rocks in the 1970s and 1980s. The addition
of La2O3 as a heavy absorber reduces matrix effects and increases the range of
concentrations over which linear calibration curves can be obtained. The fusion
must be rapidly quenched after casting otherwise crystallization is likely to occur.
The introduction of modern software packages for the accurate correction of inter-
element matrix effects (absorption and enhancement) using influence coefficients
or fundamental parameters has made the use of heavy absorbers unnecessary, and
their use is no longer recommended.
Lithium and sodium hexametaphosphates are lesser known fluxes that can be used
in the same way as borate fluxes. Melting points are in the 600 °C range, they fuse
easily, the beads separate easily from the molds, and they have a better solubility
than borates for certain oxides such as chromium and copper oxides (Banerjee
and Olsen, 1978). It has been reported that copper samples do not stick to the
molds as is often the case when borate fluxes are used. Problems experienced with
metaphosphate fluxes is that although the beads may be dry when humidity is low,
they become sticky when humidity is high.
12
2.2.2 Properties of borate fluxes

Their properties are as important as their composition; the effect of purity is
explained in section 2.2.3. Fluxes are available as pure compounds or mixtures,
as fine powders, agglomerates of fine powders, vitreous granular or spherical
particles.
Powder mixtures are not recommended on account of the segregation that may
occur while stored in containers. The risk is larger when the mixed components
differ in density or in particle shape and size.
Very fine powders have a large specific surface area (Figure 8), and, since most
borate fluxes have some affinity for water, they absorb humidity from the
atmosphere to a variable and sometimes significant extent. Sodium tetraborate is
the worst case, being able to absorb nearly 100% of its weight. Lithium tetraborate
has a low affinity for water and only a thin layer on the surface of the particles
becomes hydrated. As a result the very fine powders may contain up to 4 or 5%
water depending on their exposure to the atmosphere, but the (larger) vitreous
particles usually do not contain more than 0.1% by weight adsorbed water. A
major inconvenience of the absorbed water obviously is a loss of accuracy in
the analysis, and a lesser inconvenience is the volatilization of the water that
sometimes carries away a fraction of the flux and sample.
Fluxes
Crystals Powders
30
µm
Weight P = C
# Particles P = 1000 × C
300 µm
Surface area P = 100 × C
Water absorbed C = 0.05% P ~ 5%
Figure 8. Specific surface area of fine and coarse fluxes
An advantage of the granular, pre-fused fluxes (0.3 to 0.5 mm diameter) is their

high apparent density of about 1.3 as compared to about 0.3 for very fine fluxes.
As a result, a standard 25 ml crucible is filled to the top with 8 g of fine flux (only
80% of the quantity required to make a 40 mm fused disk) but is only half‑filled
with 10 g of granular flux. Granular fluxes are most advantageous. Pre-fused fluxes
are more homogeneous (especially mixed fluxes), are easier to weigh and tend
to be more anhydrous and less hygroscopic than non pre-fused fluxes. Due to
electrostatic forces, dusty fluxes stick to weighing pans, funnels and crucible walls,
resulting in a small loss of flux and the formation of small droplets of flux on the
13
wall of the crucible when fusing; granular fluxes do not stick to any surface and
leave the crucible wall clean after fusion.
2.2.3 Impurities in fluxes

Any impurity in the flux is interpreted as a much higher concentration in the
sample, proportionately to the dilution factor. For a fusion mixture of 1 part sample
and 9 parts flux, any impurity in the flux will be equivalent to a 10× concentration
in the sample. For example, 10 ppm in the flux is the same as 100 ppm (or 0.01%) in
a sample. Batch to batch impurity differences may need to be accounted for.
2.2.4 Additives
Chemicals are sometimes added to fluxes to modify their properties, namely:
Heavy absorbers, for example La2O3, BaO2 or SrO, are added to decrease the matrix
effects by increasing the X‑ray absorption of the flux. It has been reported that
La2O3 in Li tetraborate at a concentration of the order of 16% as currently used,
yields a homogeneous melt that separates in two liquid phases on cooling. Since,
by definition, these phases have different compositions, the glass bead is not
homogeneous. As stated earlier, the use of heavy absorbers is no longer necessary
nor recommended.
Fluidizers, for example LiF, is used to ensure a better transfer of the molten glass
into the mold. A concentration of 10% seems to be a maximum. LiF is also a
releasing agent (see below), but is much less efficient than other releasing agents
so that it must be used in larger quantities.
Internal standards are added as oxides if required in the analytical technique.
Oxidizers, for example NH4NO3, NaNO3, LiNO3 or SrNO3, are added at a

concentration of a few percent to oxidize small amounts of organic material or
partially oxidized elements, occasionally present in a sample, that may corrode
the crucible. LiNO3 is a very good low-temperature oxidant. Li2CO3 is a high-
temperature oxidant, efficient with metallic particles.
In practice the number of additives should be kept to a minimum to save time in

the preparation procedure and to minimize errors. The analyst should keep in mind
that some of them (oxidants) change the composition of the sample. Unfortunately
most of the additives cannot be added during the process of manufacturing fluxes
because they lose their particular property if they are fused; they must be added in
each sample.
2.2.5 Non-wetting (releasing) agents

Depending on their composition, borate glasses vary widely in their tendency to
stick to the crucibles and molds in the liquid and solid states. In most cases, the use
of a non-wetting or releasing agent is beneficial. Iodine and bromine are the only
two elements that are known to be efficient for that purpose. They can be added
into the fusion mixture before or during the fusion, usually in the form of one of
14
their salts, for example, NaBr, LiBr, KI, CsI, NH4I, etc; the crystals of iodine and even
the acid HBr have been reported to be successful. Ammonium iodide cannot be
used when sulfur is an analyte because ammonium and sulfur react and escape
together. Sometimes releasing agents cannot be used with copper because in high
Cu samples the cation combines with oxygen, and I or Br combine with Cu forming
volatile compounds (Equation 1), so that both Cu and I or Br are lost. However, a
small amount of releasing agent can be used just before casting. An oxidant should
not be used with releasing agents because an oxidation reaction takes place and I
or Br evaporates very rapidly.
2KBr + Cu + O K2O + CuBr2

(1)
2KI + Cu + O K2O + CuI2
Usually, the halogens are added in the crucible on top of the fusion mixture in
a quantity of about 0.2% of the weight of the flux. Less than 5% of the iodine
remains in the melt after a normal fusion (Figure 9), but this quantity is usually
sufficient to ensure essentially complete transfer of the melt into the mold.
Bromine volatilizes at a considerably slower rate than iodine but is slightly less
efficient. To avoid weighing the small quantity of releasing agent, a solution
containing about 250 g per liter can be prepared and a drop or two is added to
the fusion mixture in the crucible. Preferably the releasing agent can be added
in solid form as a tablet. The innovative design and exceptional flexibility of the
fully automatic Eagon 2 fusion machine allows a pellet of NH4I to be automatically,
repetitively, uniformly, reliably and safely dispensed into the molten fusion mixture
at the optimum point in the fusion cycle.
Concentration
Br
0 2 4 6 8 10 12
Time (minutes)
Figure 9. Volatilization of I and Br as a function of fusion time
The optimal quantity of releasing agent depends on the sample, the flux and the
sample:flux ratio. A convenient way to determine the right quantity is to look at
the shape of the bead in the mold after cooling (Figure 10): if the top surface is flat
15
or slightly convex, the quantity is right; if it is concave at the edge, the quantity is
too small; if it is convex, the quantity may be too large.
Ideal Insufficient Too much Excess
Figure 10. Effect of the amount of releasing agent on the shape of fusion beads. The use of excess
releasing agent makes ideal fusions for dissolution in acids for ICP analysis.
Some fusion instruments need larger quantities of releasing agent to avoid the
need to clean the crucibles after fusion. Also, some elements in the sample seem
to increase the rate of volatilization of iodine and bromine, so that it is sometimes
desirable to add a fraction of the releasing agent just before pouring the melt
into the mold. Cracking of beads in the mold during cooling is often caused by
the adherence of the glass to the mold, and this can be prevented by injecting the
releasing agent just before casting.
The negative ions of releasing agents are insoluble in borate glasses, so that they
must remain on the surface, preventing the sample-flux mixture from coming in
contact with the platinum. However, the positive ions can diffuse into the molten
glass, and positive ions of the dissolved sample may replace them. Then, the halide
film becomes nearly a film of sample that is a strong absorber of lighter element
radiations. Variations in halide content affect the line intensities. Use the lowest
possible quantity of releasing agent.
The volatility of releasing agents has not been explained fully yet but some
observations indicate that the evaporation rate of releasing agents depends on
their oxidation state. For example, one analyst who used to measure the Br Kα
line on the finished glass disks observed that the intensity of this line decreased
by a factor of 10 when one gram of LiNO3 was added in the fusion mixture before
heating. The following chemical equations may represent what happens:
2KBr + 2LiNO3 K2O + Li2O + 2NO2 + Br2

(2)
2KI + 2LiNO3 K2O + Li2O + 2NO2 + Br2
Releasing agents may interfere with analyte lines of elements of the sample: the
Br Kβ line interferes with the Rb Kα line, the Br Lα line interferes with the Al Kα
line, and the Br Lη line interferes with Mg Kα when using a ~5 nm LSM (Layered
Synthetic Microstructure) analyzing crystal and coarse collimator; similarly, the I Kβ
line interferes with the Ba Kα line. However it is seldom possible to use the Ba Kα
line for the analysis of Ba due to difficulties in achieving infinite thickness (critical
depth) in fusion beads. It is essential to make corrections for spectral overlap when
Br or I are used as releasing agents, because the amount of Br or I remaining after
fusion is not constant, and in many instances is dependent on sample composition.
16
2.3 Preparation before fusion

2.3.1 Fusion mixture
As mentioned above, the following procedure applies to fully oxidized specimens
only; special procedures are described in section 2.6 for other types of specimens.
1. Take a representative sample from the material to be analyzed. To ensure the

sample is representative, the material should be ground fine. Since a borate
fusion is a dissolution, the finer the particles the faster the dissolution; grinding
the material to less than 200 mesh (<75 μm) or finer is recommended.
2. Choose the most appropriate flux for the sample. Obviously, the flux
composition cannot be changed for each sample because correlation with
standards would no longer apply, but one flux composition can be chosen for
a great variety of samples. For example, lithium tetraborate with or without
5% lithium fluoride is a good flux for cements and most geological materials;
a 1:1 mixture of lithium tetraborate and metaborate works well for all low
acidity oxides such as most of the transition metals; a 1:2 mixture of lithium
tetraborate and metaborate is excellent for pure silica and alumina. The
addition of lithium nitrate to a flux is excellent to get rid of carbon often found
in cement raw mix. See Table 1 for recommended fluxes for selected materials.
3. Choose a convenient sample:flux weight ratio, taking into consideration the

following observations:
‑ a low ratio, for example 1:100, results in line intensities directly proportional
to concentrations, and calibration curves are nearly free of inter-element
matrix effects (Figure 11). However, the line/background intensity ratio is low
and the limit of detection is relatively high.
Very high sample:flux ratio (1:3)

Very low sample:flux ratio (1:100)
Intensity
Concentration
Figure 11. Effect of dilution on fluorescence intensities and matrix effects: ■ High sample:flux
ratio; ● very low sample:flux ratio, e.g. 1:100
17
‑ at high sample:flux ratios, for example 1:5, the inter-element matrix effects
are relatively high; it is necessary to make corrections for inter-element
matrix effects.
- the decrease in intensity due to dilution by the flux is not as serious as might
be expected, due to the low MAC of the flux (assuming no heavy absorber
has been added) (Figure 12). The gain in intensity from a sample:flux ratio
of 1:5 to 1:3 (low dilution fusion) is usually not worth the extra problems
encountered in preparing fusion disks, unless the extra intensity is really
necessary, e.g. for trace element analysis.
‑ there is no lower limit on the sample:flux ratio except that lithium
tetraborate tends to crystallize when the concentration of sample is low.
Apart from lithium metaborate, or close to it, crystallization can easily be
prevented. There is, however, an upper limit to which one should not get too
close. Sample:flux ratios that are reasonably high, yet sufficiently under the
solubility limit, are given in Table 1.
Table 1. Recommended upper sample:flux ratio and flux composition for some materials in the
preparation of glass beads. In the case of preparations of solutions, lithium metaborate flux is
recommended because the solubility is greater.
Sample material Flux* Sample/Flux/LiNO3

LiT LiT:LiM (1:1)
Cement** X 2-3 / 6 / 0
Raw mix X 2-3 / 6 / 1
Rocks X 0.5-1 / 6 / 0
Bauxite X 0.5-1 / 6 / 0
Slags X X 0.5-1 / 6 / 0
Sulfide ores X 0.4-0.8 / 6 / 2
Sulfide concentrates X 0.3-0.6 / 6 / 2-3
Sulfate X 1/6/0
Coal ash X 0.6 / 6 / 1
Alumina X 0.6 / 6 / 0
Silica X 1/6/0
Magnesia X 0.6 / 6 / 0
Titania X 0.4-0.6 / 6 / 0
Zirconia X 0.4-0.6 / 6 / 0
Ferric oxide X 0.4 / 6 / 0
Ferrous oxide X 0.4 / 6 / 1
Chrome oxide *** X 0.1 / 10 / 0
* LiT = Li tetraborate LiM = Li metaborate ** Fréchette et al. (1979)
*** Mintek (Randburg, South Africa) has found a flux mixture of 2:1 (LiT:LiM) and a sample:flux
ratio of 1:9 to work well for chromites, which are notoriously difficult to fuse satisfactorily.
No oxidant was used. Potassium hexametaphosphate is also efficient for chromites, but makes
analysis of K and P impossible. However, Sear (1997) found the use of intimate mixtures of sodium
nitrate or sodium peroxide and boric acid to be very beneficial for the dissolution of chromite and
cassiterite, allowing the use of smaller dilution ratios than is normally possible.
18
1.0
slope = 5
IFe
1/3
1/5
0.5 1/10
1/15
1/20
Different sample:flux ratios

0
0 0.5 1.0
CFe O2 3
Figure 12. Intensity of Fe Kα in Li2B4O7 fusion beads for different sample:flux ratios
‑ as mentioned in section 2.2.3, any impurity in the flux appears as if it is an

element of the sample at a concentration equal to its concentration in the
flux multiplied by the flux/sample ratio. As an example, an impurity of about
50 ppm in the flux yields an XRF intensity corresponding to 0.5% in the
sample if the flux:sample ratio is 100:1 and to 0.045% if the ratio is 9:1.
4. Weigh the sample to 1 mg or better (0.1 mg for a 9:0.9 flux to sample mixture).
Weighing the flux to ±5 mg is usually sufficient. It is acceptable to weigh close
to a given predetermined value and make corrections to compensate for the
differences from it. Some XRF software packages can make accurate corrections
for quite large differences in weight, provided the actual sample and flux
weights are specified.
5. Transfer the fusion mixture into a crucible on the fusion apparatus and add
releasing agent.
6. Determine a program for the fusion process. Although many substances

accommodate to a simple program that contains one or two heating steps
followed by casting and a two-step cooling, more complex programs are
necessary for some types of samples. For example: if the sample contains carbon
or sulfide minerals in significant concentration then low-temperature heating
combined with use of an oxidant is a necessary step before the so‑called
fusion is started; a gradual heating might be necessary when dealing with a
carbonate‑rich sample in combination with a finely ground flux. These special
cases are considered in section 2.6.
19
2.3.2 Crucibles and molds

The best material for crucibles and molds is a platinum alloy with 5% gold (Pt-5%
Au); it is strong, stable and long lasting. However, a Pt/Au/Rh alloy crucible
(Figure 13) available from PANalytical provides even greater durability. Carbon
crucibles do not last long in a gas flame (high-temperature oxidizing environment),
but do last slightly longer in a furnace. Pt-Au crucibles cost less per analysis than
graphite crucibles. Zirconium oxidizes and dissolves in the flux at the temperatures
prevailing during a borate fusion, but zirconium-stabilized crucibles can be used for
other kinds of low-temperature fusion.
Figure 13. A 40 g highly durable Pt/Au/Rh alloy crucible and long-lasting 100 g Pt-Au alloy casting
dish (mold) available from PANalytical
A mirror‑polished crucible or mold is only slightly, if at all, wetted by the molten

glass, but, as the number of fusions increases, the surface becomes rough on
account of corrosion and aging. Then the molten glass tends to stick more strongly,
and a larger quantity of releasing agent is needed to compensate for that. Please
refer to chapters 5 and 6 for care of platinum ware.
With a granular flux, a 20 to 25 ml capacity crucible is large enough to

accommodate the fusion mixture to make a 40 mm diameter glass disk. If a fusion
apparatus is used the crucible must be held safely in its holder and a crucible with a
flat rim or equivalent is necessary (Figure 14). With all fusion instruments, a crucible
with a mixing‑enhancer hump in the bottom (Figure 15) enhances mixing and
ensures homogeneity of the melt in a short time by forcing the molten glass to pass
through a narrow gap (Figures 15, 20) which produces strong convection currents.
20
Figure 14. Crucible with a flat rim for safe Figure 15. Crucible with a mixing-enhancer
holding in a fusion apparatus hump in the base
2.4 Heating
The fusion process consists of four operations: heating the sample‑flux mixture,
homogenization of the melt, pouring the molten glass into molds, and
solidification of the glass. The first two operations are considered in this section.
2.4.1 Heating requirements

Basically, any means of heating can be used to bring the flux above its melting
point to dissolve the sample, but in practice some means are more apt to meet
the requirements of a good fusion. Whether heating is manual or automatic, the
desirable requirements are:
• temperature with a minimum in the 200 or 300 °C range for oxidation of
sulfides and metallic samples when necessary, and up to 1100 °C for fusion.
Higher temperatures may cause excessive volatilization of flux and also some
elements such as sodium, potassium and sulfur (Figure 16), and particularly
releasing agents;
• easy and fast adjustment to any level of heat;
• reproducibility of heating conditions for maximum precision and accuracy;
• oxidizing conditions to minimize reduction of some elements;
• availability of agitation in the melt for homogenization;
• availability of injection of releasing agent just before pouring, to clean the
crucible and to release the disk from the mold.
In addition to all of the above features the Eagon 2 has very sophisticated and
accurate temperature control by means of thermocouples to within ±5 °C between
300 - 1200 °C.
21
Flux melts
Rate of volatilization
Na, Li
I Br S
(as SO2) (Flux)
800 900 1000 1100 1200 1300 1400 1500 1600

Temperature (°C)
Figure 16. Rate of volatilization of some elements as a function of temperature (qualitative)
Electric furnace heating is the best means of heating, providing thermal

equilibrium of both crucible and mold during the full fusion and casting cycle,
and ensuring that crucible and mold are always at the same temperature prior to
casting. In the past electric furnace heating was slow, required frequent manual
agitation of the crucibles and was not convenient when more than one level of
heat was required in the process. Manual agitation while standing in front of
an open furnace at only 1000 °C is an uncomfortable and potentially dangerous
procedure for any operator, and is obviously much worse at higher temperatures.
The high level of operational flexibility built into the Eagon 2 allows automatic
agitation to be carried out in the furnace behind closed furnace doors with
complete safety, and with full control over crucible angle and agitation speed.
Electric resistive or induction coil fusion instruments are also available. Induction
heating is excellent if agitation is provided. Its main disadvantage is high cost.Their
advantages are close to those of propane gas instruments, and in some cases far
superior.
Propane gas burner is a simple and efficient means of heating:

• temperature range is optimal (Figure 17); very low heating is obtainable
because the gas flow can be controlled even when the flow is small. The
maximum temperature that can be obtained is more than sufficient for any
type of sample, yet there is no risk of damage to the crucibles when empty;
22
1050
With O2 booster
With venturi open
1000
Temperature (°C) in melt

950
900
850
0.5 1.0 1.5 psi

800
0 10 20 30 40 50 p
Setting on controller
Figure 17. Typical controller settings and temperatures for Fisher standard grid-top adjustable
burners. Temperatures were obtained using thermocouples in the melt and are probably accurate.
• control of gas flow is easy and ensures reproducible heating conditions with
temperature, independent of the number of burners used. However, the
heating conditions are not as reproducible with gas burners as they are with
muffle furnaces. Different burner settings, easily blocked jets, the effect of
air pressure and of moisture in compressed air lines can all lead to different
temperatures and temperature instability;
• temperature can be changed rapidly and set independently for each heating
step which is particularly important when dealing with sulfides and metals (for
complete oxidation) and carbonates (when foaming occurs);
• maintaining oxidizing conditions in an open gas flame is not easy and great
care must be taken to avoid reducing conditions that will damage the crucible;
• several samples can be processed at the same time but achieving and
maintaining identical temperature conditions in multiple flames is exceedingly
difficult;
• cost is low, but can be expensive per fusion when using an oxygen-enriched
flame.
Propane‑oxygen gas burner has a workable range of temperatures a few hundred

degrees higher than the propane gas burner (Figure 17), which is unnecessary
for borate fusions and increases the risk of damage to the crucibles and loss of
some elements from the molten glass. At higher altitudes, however, the propane
oxygen burner with its extra oxygen might be essential to achieve optimal
fusion temperatures. Additional benefits of adding oxygen to the flame are less
gas usage, reduced flame ‘volume’ and a very much reduced heat load into the
laboratory, with the accompanying advantage of lower cooling costs.
Temperature measurement during fusion is not really necessary. As a matter of

fact, such measurements have very limited significance when one observes that in
gas burner machines the color of a hot crucible may vary considerably from top to
23
bottom. In practice what counts is to ensure that the temperature does not exceed
a level at which the elements of interest (essentially sulfur, halogens and alkalis,
including the flux) volatilize at a non‑acceptable rate. A correct temperature is
difficult to define since volatilization increases exponentially with temperature,
so that it always takes place (Figure 16). The object is to operate at reproducible
conditions (difficult with gas burners), with the temperature not too high, so that
the loss by evaporation is small and ‘constant’. Take note that releasing agents are
particularly volatile and that variations in their concentration affects light elements
significantly. As a rule of thumb: “a long fusion at a low temperature is preferable
to a short fusion at a high temperature”. Apart from the lower loss of sample and
flux, the halogen element of the releasing agent should evaporate less and lead to
a cleaner crucible and easier releasing of the bead.
2.4.2 Heating steps

A complex fusion procedure may involve several heating steps (Figure 4). Simpler
procedures can be adopted but since versatile programmable fusion apparatuses
are available why not strive for the best operating conditions. The following
heating steps should be considered.
2.4.3 Heating steps for oxidation

Oxidants are used as an additive to the flux to oxidize components of the sample
in a reduced state, for example metal sulfides or sub‑oxides such as Cu2O, FeO or
carbon bearing samples. Usually the oxidant is a nitrate, such as NaNO3 or LiNO3,
that melts before the flux melts. If the temperature at the beginning of the process
is increased slowly, the oxidant melts first, wets the reduced component and reacts
with it to yield an oxide that can dissolve into the flux. The temperature should
be increased slowly enough to allow the reaction to reach the center of each
oxidizable particle. Depending on the concentration of the material to be oxidized,
one or two or perhaps three heating steps should be considered. The first at the
lowest temperature for 2 or 3 minutes which allows the material at the edges
of the crucible to react; the second at a higher temperature to allow the inner
material to react also; and a third step at still higher temperature to make sure
that the reaction is complete. Incidentally, the flux will have started to melt at the
edges of the crucible when the third heating step is reached. During the oxidation
procedure agitation of the crucible is not recommended.
2.4.4 Heating steps for fusion and homogenization

When oxidation is not part of the fusion procedure, the fusion itself may consist of
two steps, one without or with very little agitation, so that no particle of the flux is
projected onto the wall of the crucible where it would form fine droplets that may
not join the rest of the fusion mixture. This first step lasts until about two thirds of
the flux has melted and is usually at a temperature lower than that of the fusion
itself. This step is obviously not necessary when fusion is preceded by oxidation
involving a high temperature step as described above.
24
The second step is accomplished at the ‘cruising’ temperature for fusion

and is accompanied with agitation to hasten homogenization. Convection
currents produced by thermal gradients during fusion should be sufficient for
homogenization but the process would be slow. In addition, just after the flux has
melted, the sample is still nearly intact and dissolves extremely slowly unless it is
agitated vigorously.
Although most fusion mixtures will dissolve without agitation, agitation (provided
as a flexible option by the Eagon 2 fusion machine) can greatly increase the
efficiency and speed of dissolution. The reason agitation is so effective is that
agitation helps to remove the saturated layer of fusion mixture surrounding
mineral grains, thus promoting further dissolution. An example of a similar
procedure in everyday life is the stirring of coffee or tea to ensure that added
sugar grains dissolve completely. Often, even after some time has elapsed, partially
dissolved sugar grains remain at the bottom of a cup of tea or coffee that has
not been properly stirred. All kinds of agitation that produce friction between
adjacent layers in the melt should be efficient. Those that produce a mere rotation
or displacement of the molten mass as a whole are not efficient. Here are two
examples.
The effect of rocking of a standard crucible containing a liquid is shown in

Figure 18. Changing the inclination of the crucible from A to B results in the liquid
not staying level; trying to become level again and considering that molten fluxes
are somewhat viscous, the liquid mass rotates about its center instead of flowing
from left to right, with the result that almost no convection occurs. The situation
is very different when a crucible with a hump in the bottom is used instead of a
standard crucible, as shown in Figure 19. When changing the inclination of the
crucible the hump in the crucible prevents the liquid mass from moving as a whole;
instead, the two halves of the liquid must separate and move rapidly through the
narrow gaps on each side of the hump; these currents are very efficient for mixing.
Figure 18. Motion of glass during rocking in a standard crucible. Dots represent the motion of a
liquid element.
25
Figure 19. Motion of glass during rocking in a crucible with a hump in the base. Dots represent the
motion of a liquid element.
A similar situation arises in systems where the motion of the crucible is a rotation
about its axis (Figure 20). With a standard crucible the liquid essentially rolls about
its center but with a hump in the crucible the same tendency to roll produces
currents that move in opposite directions in the narrow pass because the liquid is
squeezed between the hump and the wall of the crucible.
Top view Hump

Standard
flat bottom
Standard Hump
flat bottom
Figure 20. Motion of glass during rocking in a crucible with a hump in the base. Dots represent the
motion of a liquid element.
Continuous agitation, even in the partially molten content of the crucible, during
fusion is much more efficient for mixing as compared to short occasional agitation
periods. In addition, the samples may eventually contain small quantities of
particles likely to corrode the crucible; keeping these particles floating minimizes
the reaction with the platinum.
Another reason for strong agitation is the elimination of bubbles that sometimes
form in the melt. Occasionally one finds very small bubbles floating on the melt
that are not eliminated after long agitation; after casting they cause cracking of
the glass disk. These bubbles are sometimes caused by carbon particles present in
the sample; they stick to fine bubbles and prevent them from agglomerating into
larger bubbles that would burst and disappear. The easiest way to get rid of them
is to burn off the carbon by adding an oxidant into the flux or by injecting air into
the crucible during the fusion.
2.4.5 Heating steps for conditioning before casting

When using gas burner type fusion machines two extra short heating steps may
be desirable before casting, one for adding a releasing agent tablet and one
for adjusting the temperature of the mold or molten glass. Such extra steps are
unnecessary when using the Eagon 2.
26
Some elements, those too acidic, seem to be allergic to the bromine or iodine of
the releasing agent and reject it fast during fusion, with consequent adherence
of the glass to the mold and to the crucible. The injection of a small crystal or a
tablet of the releasing agent followed by a mixing period of one to twenty seconds
before casting can help prevent sticking.
In some fusion instruments the mold is heated above the crucible and is partly
shielded from the flame. If, as a result of the shielding, the temperature of the
mold is too low, crystallization in the bead will sometimes occur. To prevent that,
one may increase the temperature for a period of about 10 seconds immediately
before casting; the mold will heat up fast because it is thin while the molten glass
will heat up just a little because it is more massive and less conductive. Fusion
instruments that provide separate heatings for the mold do not require this step.
PANalytical’s Eagon 2 fusion machine obviates the need for these extra heating
steps and allows the releasing agent tablet to be added at any time that is
appropriate for a particular fusion program.
2.5 Casting and cooling

2.5.1 Casting into molds
When the hot melt is ready for casting it is merely poured into the mold. To
prevent crystallization during cooling a few conditions must be met:
• the mold should contain no solid residue from the preceding fusion; any
particle that has not melted while the mold was heated during fusion, and
still does not melt when the hot glass is poured into the mold, is a seed for
crystallization;
• the mold should be hot enough to avoid sudden crystallization of the glass that
would lead to the same problem as in the preceding case.
2.5.2 Solidification
This operation is a critical step in the production of fusion beads on account of its
influence on the quality of the beads. Glass is a supercooled liquid; hence it is an
unstable material that tends to crystallize, and does, if it is given a chance.
The time required for a glass specimen to crystallize varies as a function of

temperature (Figure 21). At temperatures above the melting point of the stable
crystalline state, the material remains liquid indefinitely. Just below the melting
point, the tendency to crystallize is low and the viscosity of the glass slows down
the atoms in their attempt to form crystals; crystallization is very slow. As the
temperature decreases both viscosity and tendency to crystallize increase, but the
latter predominates so that the time before onset of crystallization decreases.
Eventually a temperature is reached where the viscosity becomes so high that the
atoms have a lower and lower possibility to move and form crystals; then the glass
state becomes the stable state, but in appearance only and for a limited time that,
fortunately for the XRF analyst, is very long at room temperature.
27
Glass
Temperature (°C)
Crystals
Time
Figure 21. The crystallization curve of borate glass
In simple terms, the secret of a successful glass disk lies in working out a cooling
curve that avoids crossing the crystallization curve of the glass. In practice, the
situation is complex because the cooling curve varies with the overall composition
of the glass and the position in the mold. The analyst has limited means to change
the shape of that curve, and one must take into account that forced cooling
produces stresses that may lead to cracking, the more so when the glass does not
release easily from the mold.
A few types of cooling curves are shown in Figure 22:

• Cooling curve A crosses the crystallization curve above the nose usually a only
short time after pouring into the mold; crystallization starts at several points on
the periphery of the bead where the temperature is lower, and moves rapidly
towards the center. The heat generated by the reaction, the volume change
and the viscosity all together produce bubbling at the solid‑liquid interface so
that, after cooling, the aspect of the bead is similar to a mountainous area with
scattered peaks. The surface of the bead in contact with the mold is flat and
porous with clearly visible dendrites. Such a disk is likely a mixture of several
phases and is not suitable for accurate XRF work. This situation is typical of
fusions with lithium tetraborate. The remedy to this type of crystallization is to
move the crystallization curve to the right by changing the composition of the
glass, i.e. by using a higher sample:flux ratio, adding a compound to stabilize
the glass, or using a more basic flux, but not pure lithium metaborate. The
latter usually crystallizes at all times, except in rare cases. It only differs from
the tetraborate in that crystallization appears at the beginning of cooling and
is uniform all over the surface of the bead. It is avoided by using a less basic
flux. This suggests another fusion rule: “Avoid the stoichiometric compounds
tetraborate and metaborate as fluxes, except with highly acidic or highly basic
samples. Prefer intermediate compositions.”
• Cooling curve B is typical of a glass composition associated with a crystallization
curve more to the right compared to A. The cooling curve intersects the
latter at a much lower temperature so that crystallization can only just start.
It is usually observed as small whitish opaque spots that form either at the
periphery or wherever the surface is in contact with the mold. The resulting
28
beads are not useful; if the crystallized area is small the influence on the
emitted fluorescence intensity may be small but the stresses around the crystals
may induce shattering. A small modification of the composition of the glass is
often sufficient to avoid crystallization, for example adding a little LiF to the
flux. Another possibility is to modify the cooling curve as described below for D.
1000 Liquid glass

Area of
crystallization
800
A
Temperature (°C)
High-temp. crystals (LiBO2)
600
400 B Low-temp. crystals

Still-air cool & high-T
C annealing (no fans)
200 Still-air cool & low-T
D annealing (fans on)
Supercooled liquid E Still-air cool (Na2B4O7)
0
Time
Figure 22. Effect of cooling rate on the bead. In practice the cooling curve is rather constant and
the crystallization curve is the variable. Cooling must be fast enough to keep the cooling curve of the
bead below the crystallization curve.
• Curve E is typical of very stable glasses. Most beads based on Na tetraborate

are of this type. Cooling in still air to room temperature is not too slow. It is not
recommended to anneal these disks because they will behave as in B, i.e. they
will crystallize and crack.
• Curve D is typical of the conditions necessary to avoid crystallization of most
glass beads. It is obtained by letting the glass solidify in still air for a short time,
then cooling faster to prevent the onset of crystallization. A cooling period of
about one to two minutes in still air followed by cooling with fans has been
found to be satisfactory.
A few practical observations that may facilitate the work of the analyst are given
here:
• the crystallization curve of Li metaborate is close to the origin of the time scale
(Figure 23), that of Li tetraborate is more towards the right and that of Na
tetraborate is still more to the right; this seems related to the viscosity of the
flux: the more fluid it is, the easier it crystallizes;
• the dissolution of a sample into a flux usually displaces the crystallization curve
to the right (Figure 24); this seems related to the more complex composition of
the liquid phase, making it more difficult for the atoms to find their partners in
forming a crystal;
• after the hot molten glass has been poured into a mold, cooling the latter
immediately by means of an air jet is certainly efficient to avoid the nose of
the crystallization curve but creates large stresses in the glass bead; such beads
29
have been observed to shatter in the hands of the analyst and there is a risk
of damage to the eyes. If the glass is not left to cool in still air at least for a
fraction of a minute before applying the air jet, then it should be done when
the bead has reached a lower temperature to minimize the residual stresses.
A useful tip (Mark Ingham, pers. comm.) for checking for residual stress in a
bead is as follows: two squares of polarized plastic film are hinged together
so that the polarizing planes are perpendicular to one another. When a bead
is sandwiched between the films and held up to the light a non-stressed bead
gives a ‘Maltese cross’ interference figure, while stressed beads have bent or
wavey interference figures.
LiM
Temperature (°C)
LiT NaT
Cooling curve
Crystallization
curves
Time
Figure 23. Crystallization curves of three common fluxes (qualitative). The cooling curve crosses the
lithium metaborate (LiM) curve but not that of lithium tetraborate (LiT). Crystals will form in LiM but
not in LiT or sodium tetraborate.
Temperature (°C)
a
c
b
Cooling curve Crystallization

curves
Time
Figure 24. Crystallization curves of: a) pure flux - no sample; b) low sample:flux ratio; c) high
sample:flux ratio. Note that because the cooling curve crosses the pure flux crystallization curve it is
very difficult to make an uncrystallized bead of pure flux.
• heating the crucible and the mold to a higher temperature just before
pouring the glass into the mold increases the cooling rate at the beginning of
solidification and may prevent several cases of the so‑called high temperature
crystallization.
30
• annealing the fusion bead after cooling is normally not necessary if the initial
period of solidification in still air has lasted about one minute or longer.
Annealing for a few minutes in the 200 to 400 °C range is not wrong but longer
annealing may lead to beginning of crystallization with consequent shattering
of the bead (cooling curve C in Figure 22).
• during cooling, while the temperature is still in the neighborhood of 200 °C,
a glass bead should not be touched with a metallic object such as tongs; the
faster cooling at the point of contact may lead to cracking.
• a freshly made glass bead should not be polished. If streaks or scratches are
found on its surface, the mold instead should be well polished. Polishing a bead
provides a risk of contamination by Si or Al, two commonly used abrasives.
The Eagon 2 has all the necessary cooling flexibility required to navigate the phase
transition space and thereby produces good, stable glass beads on a regular basis
(Figure 25).
• Critical stage
• Quenching
- Viscosity increases faster than diffusion required for crystal formation
- Molten liquid ðsolid ‘liquid’
• Too slow ð crystallization
Temperature (°C)
• Too fast ð stressed beads

• Cooling trajectory depends on sample and flux type
• Cooling flexibility needed to navigate the phase transition
space
- Passsive cooling
- Forced cooling (2 flow-rate options)
Time
Figure 25. The Eagon 2 has all the necessary cooling flexibility required to navigate the phase
transition space and thereby produce good glass beads on a regular basis.
2.6 Examples of fusions that require special techniques

As mentioned above, only oxides can be dissolved into molten borate glasses. All
other compounds must be oxidized prior to fusion. Ideally the oxidation and the
fusion operations should be combined in a single procedure.
Materials frequently considered as more difficult cases are sulfides, carbon, metallic
materials and copper‑bearing samples. These and other interesting cases will now
be considered.
31
2.6.1 Sulfide minerals

Sulfide minerals are risky to process in platinum crucibles unless a safe technique is
used; a crucible can be ruined in a single fusion.
There are two problems to overcome in processing sulfides. The first is to make
sure the sample oxidizes totally as a sulfate and the second that sulfur (from sulfide
or sulfate) is not lost as a gas.
Oxidation done by heating the sample in air or in oxygen does not retain SO2
totally. Heating the sample with an oxidant as part of the fusion process is more
efficient. Suitable oxidants are potassium pyrosulfate (if K and S are not analyzed)
or a nitrate of lithium or sodium.
To retain sulfur during a fusion, the oxidation must be done at a temperature as

low as possible to transform the sulfide into a sulfate instead of forming an oxide
and SO2 gas. The oxidation temperature should not exceed about 300 °C. It can be
increased to 1000 °C, but preferably lower, after oxidation.
When sulfur has to be analysed, ammonium iodide cannot be used as releasing

agent because sulfur evaporates with ammonium. However, other iodides can be
used.
A technique that meets the above conditions has been described by Norrish and
Thompson (1990). It has been applied to the preparation of fusion beads for X‑ray
fluorescence. It consists of heating a mixture of 0.25 to 0.66 g of sample, 6.8 g of
12‑22 flux and 1.0 g of NaNO3 in a muffle furnace at 700 °C for 10 minutes, then
fusing as for oxides at a temperature not exceeding 1050 °C.
Another procedure for sulfide concentrates using a fusion machine is the following.
Mix about 0.3 g of sample with one or two grams of Li or Na nitrate and 0.5 g
Li tetraborate, and put into the crucible. Cover with 6 g Li tetraborate and the
releasing agent. Heat at a low temperature with slow agitation for oxidation, then
below 1000 °C with stronger agitation for complete melting and homogenisation.
Sodium nitrate is a more efficient oxidizing agent than lithium nitrate, but absorbs
X‑rays somewhat more and prevents analysis of sodium.
2.6.2 Copper compounds

If copper is present in a partially oxidized state, metallic copper precipitates during
fusion and alloys with the crucible. It is a safer practice to calcine such samples and
to always add some oxidant to the fusion mixture.
Releasing agents sometimes react with samples containing copper and copper
halides volatilize (Equation 1).
Loss of copper with consequent loss of accuracy is only part of the problem; copper
being an element that sticks to crucibles and molds, a thin layer of glass remains
all over the surface of the crucible after pouring, and the glass disk is very difficult
32
to release from the mold without breaking it. The injection of a 10 mg crystal of KI
into the molten glass one second before casting has been observed to improve the
problem of sticking, but not to full satisfaction; the loss of Cu by volatilization is
small due to the short time of reaction.
A simple successful technique for the fusion for CuO, and even for Cu metal, has
been described by Blanchette (2001). Pure CuO is mixed 1:10 in a flux consisting of
50:50 mixture of lithium tetraborate and metaborate and 0.5 % LiBr and fused as
usual. It might be possible, depending on the fusion apparatus used, to add LiBr as
a solution and mix it well into the unfused mixture.
2.6.3 Carbon
Carbon is often found in small concentrations in raw mix cement, fly ash and
limestone. The addition of 0.1 g NaNO3 in the fusion mixture is usually sufficient
to eliminate it. Ammonium nitrate can also be added in any unweighed quantity
because the unused portion volatilizes completely on heating. Heat at the lowest
possible temperature (ammonium nitrate melts at 170 °C) and allow enough time
for the reaction to take place. Injection of air into the crucible during fusion is also
efficient.
2.6.4 Metallic materials

As a general procedure, metallic materials can be processed similarly as sulfides
except for a few differences. Metallic particles are usually compact and dense as
compared to sulfides which are generally porous, so that the oxidation of metals
is more difficult and slower. Nitrates are not efficient for oxidizing metals, but,
surprisingly, Li carbonate is very efficient. Metallic particles should be very, very
fine.
A practical method with fusion machines is the following. Use 5 g of Li tetraborate
in a crucible to make a protection coating all over its surface, by melting the flux
and rotating the crucible in an inclined position. Then let cool while rotating until
the coating solidifies. Put a mixture of 0.5 g metal powder and 1.25 g Li carbonate
in the coated crucible. Level and add a layer of 1.25 g Li carbonate, and then add
a layer of 1.8 g B2O3 (boron oxide, not boric acid!). Heat at a medium temperature
to make the oxidation and to melt the boron oxide that will prevent the CO2 gas
from ejecting material out of the crucible. When oxidation is finished, increase the
temperature and continue as in a normal fusion. This technique works well even
with ferroalloys, but it is important to follow the procedure very carefully with
‘ferrosilicon’ because the reaction is a highly exothermic chain reaction, capable of
piercing the crucible.
2.6.5 Carbonates
Samples that contain a large amount of carbonate sometimes are reported to foam
and run over the crucible during fusion. The reason is that the flux has a melting
point below that of the carbonate, so that the gas from the decomposition of the
carbonate escapes through a viscous liquid. In the case of calcium carbonate that
decomposes at 900 °C, only lithium tetraborate flux has a higher melting point. This
33
allows the gas to escape through a porous solid without any foaming, provided
that the flux is also a rather coarse powder; otherwise the flow of gas would blow
the fine particles out of the crucible.
34
Pyrosulfate fusions PANalytical
3. Pyrosulfate fusions
3.1 Procedure
Pyrosulfate is a good fluxing agent to break up most minerals by transforming
them into sulfates that are soluble in water or mild acids. Silica is a major
exception. Powdered rocks are mixed with about 10 times their weight of
potassium pyrosulfate, and the mixture is heated over a gas burner at low
temperature until the molten pyrosulfate has dissolved the minerals. At the
start of heating the reaction is rapid and a large amount of gas is formed; the
effervescence must be kept low by moving the crucible in and out of the flame.
After about three minutes of heating the effervescence has vanished, the liquid
product is poured into a room temperature container (a mortar, for example) in
which it immediately solidifies. To make a solution for wet chemical analysis, the
solid is ground and dissolved in a suitable solvent. For XRF analysis, the solid is
ground, a binder is mixed with the powder and the mixture is pressed as a disk.
Detailed procedures for making beads for analysis by XRF have been described
by Cullen (1960, 1962), Sear (1997) and O’Neill and Fitzsimons. The first author
used the loose powder as sample and obtained quite satisfactory results. Sear
(1997) discussed the fusion of difficult materials such as chromite, cassiterite
and sulfides. He made use of intimate mixtures of sodium nitrate and boric acid
resulting in a sodium borate flux of very high oxidizing power. The process of low-
temperature oxidation followed by fusion at normal high temperatures provided
strong oxidation conditions with no damage to the crucible. It was possible to
completely retain pyritic sulfur with lithium carbonate-tetraborate fluxes. The use
of pure alumina crucibles allowed the use of sodium peroxide for the fusion of
ferro-chrome and ferro-niobium. The third authors poured the molten sample-
pyrosulfate mixture into a mold to obtain a solid disk, but had serious problems
of cracking that necessitated adding powdered silica into the melt, and making
only one disk at a time in the furnace because the heat generated in one crucible
influenced the temperature of the crucible next to it.
3.2 Automatic preparation

Fusion machines can be adapted easily to make pyrosulfate fusions. The molds are
the same as those for making borate glass beads. Although theoretically platinum
crucibles could be used, they are not convenient because their heat conductivity is
high so that the effervescence is difficult to control. Silica crucibles work very well
and require only a modified crucible holder. At the end of the fusion process, the
solidified bead separates easily from the mold, leaving the mold clean. The crucible
retains a residue that is easily cleaned by washing in water.
35
3.3 Requirements
Fusion and casting of pyrosulfate disks is done essentially in the same manner as
borate beads, but the experimental conditions are rather different because the
physical properties are different.
1. The reaction of the pyrosulfate with the specimen is accompanied by
effervescence. The temperature must be kept low, just above the melting point
of the pyrosulfate (~300 °C), so that the burners must be set at their lower limit
of heating and a low heat conductivity crucible must be used.
2. Molten pyrosulfate is very fluid, so that pouring must be done slowly, otherwise
splashing occurs outside of the depressed part of the mold.
3. The solidified disks are not vitreous as are borate disks. Since they are
crystallized, they are weaker and more prone to cracking. If they are cooled
slowly, they are rather hard and solid.
3.4 Problems
Pyrosulfate fusions suffer from two problems, but it seems that solutions to these
have been found.
The first problem is that of indissoluble silica. When silica originates from a silicate
that has reacted, the particles are very fine and stay in the melt as a dispersion.
During cooling they tend not to segregate. If silica is from original quartz crystals,
it is usually coarse enough to segregate at the bottom of the mold before the melt
has started to crystallize. This problem apparently has been solved by agitating
the melt rapidly before pouring and by a short period of fast cooling in the mold
to form a thin solid layer in the mold immediately on pouring, then letting the
rest of the melt crystallize and cool more slowly. In this way the surface of the disk
exposed to X-rays has the average composition, and the disk maintains its solidity.
The second problem is similar. It is due to the fact that lead sulfate, if present in
large concentration, apparently crystallizes first and settles at the bottom of the
mold at the start of crystallization. The remedy is the same as that for quartz.
3.5 Fusions of sulfide concentrates

The Norrish method using Li2B4O7 uses 0.2 g LiNO3 + 1 g sulfide. This is not enough
oxygen to completely oxidize the S2–. Adding too much LiNO3, i.e. Li2O, changes
Li2B4O7 to LiBO2 which gives problems of crystallization. Pyrosulfate, however, has
excess oxygen which reacts well with the S2–:
(3)
36
Pyrosulfate fusions PANalytical
Pyrosulfate fusion of sulfide ores is probably a better method than using borate
fluxes with plenty of oxidant, provided that sulfur needs not to be analysed.
3.6 Analysis of disks

During the fusion, some SO3 escapes from the pyrosulfate, some SO3 moves from
the pyrosulfate to the metallic elements of the specimen, some elemental sulfur
escapes because there is an excess, etc. As a result, the composition of the specimen
has changed, the flux is no longer the same, the sample:flux ratio has changed. If
one wants to apply the Lachance-Traill equation to calculate the concentrations,
the problem seems extremely complex; for example, it is observed that the loss
of weight during fusion is about equal to the weight of the sample, which is
considerable. However, a closer look at the situation indicates that such calculations
are actually very simple. In the meantime, concentrations can be obtained by
regression analysis on a sufficient number of specimens, and the results are very
encouraging.
3.7 Conclusion
The above details are given for information only. There has been much less effort
spent on studying the pyrosulfate fluxes compared to the borates.
37
Fluxers PANalytical
4. Fluxers
Many different types of fluxers or fusion instruments are available commercially,
and are either of the gas burning, induction heating or muffle furnace type.
4.1 Fusion instruments

A modern fusion instrument is usually a fully automatic instrument with
microprocessor control. It is capable of the preparation of glass disks for analysis
by X-ray fluorescence, and can make borate, hexametaphosphate or pyrosulfate
fusions without alteration of the equipment.
The main features of a typical fusion apparatus are:

• simultaneous processing of 1 to 6 samples;
• several programs adaptable to all kinds of fusion, including several heating
steps, pouring, cooling, stirring of solutions;
• programmable heat levels, agitation and time;
• agitation can be by rotation of the crucible about its axis at an angle of
~60 degrees with the vertical or rocking back and forth;
• may need only propane, but some machines need air and/or oxygen (gas burner
type);
• stable reproducible gas flow, independent of the number of burners (gas
burner type);
• very low temperatures obtainable for oxidation;
• uniform crucible temperature top to bottom;
• heating of molds either simultaneously with or separately from heating of the
crucible;
• non-wetting agent injector to prevent sticking of glass to Pt ware;
• optional injection of oxygen into the crucibles;
• optional injection of oxygen into the flame (temperature booster, gas burner
type).
With the exception of optional injection of oxygen into the crucible, something
which is hardly ever necessary and the need for which can be removed by the use
of additional oxidant, and the additional requirements pertaining only to gas
burner type fusion instruments, the Eagon 2 more than meets all of the above
criteria.
39
Care and use of platinum ware PANalytical
5. Care and use of platinum ware

5.1 Why platinum
Modern chemical analysis would not be possible without the wide range of
platinum apparatus and laboratory ware. Platinum is used, because it is essentially
inert, does not contaminate the sample for normal analytical purposes and shows
no significant weight loss even over prolonged periods of heating at temperatures
over 1000 ºC in air. The use of crucibles and molds of platinum and its alloys in the
preparation of samples has become an essential feature of XRF analysis. Its broad
application results from its near perfect oxidation resistance and its excellent
resistance to corrosive attack by metal oxide melts such as XRF fluxing agents.
Simple basic precautions and good laboratory practice can result in obtaining the
full benefits of using platinum.
Newly manufactured
platinum ware
Platinum ware cleaning and maintenance
Distilled water rinse
Re-polish crucible Sample preparation

Sample fusion
Re-polish mold
Platinum maintenance
Dented or
Re-shape crucible mis-shaped
crucible
Mold scratched
or damaged?
Re-press mold
Figure 26. Care and use of platinum labware
41
5.2 Damage to platinum ware

The effect commonly referred to as ‘platinum corrosion’ is not corrosion in the
normal sense of aqueous corrosion and rusting. It is usually the reaction of
platinum with another element to form a compound with a lower melting point
and the subsequent formation of a eutectic with an even lower melting point
between the compounds of platinum. Some of examples of poison elements
for platinum ware are: Arsenic, phosphorus, boron, bismuth, silicon, sulfur and
a number of heavy metals, e.g. lead, zinc, tin, antimony. Even if these elements
are only present at low concentrations they can diffuse gradually into the grain
boundaries of the platinum where they lead to a loss of high-temperature strength.
5.2.1 Crucibles
Do not heat non‑fully oxidized materials in Pt-Au crucibles unless an efficient
oxidant is mixed with the material and heated slowly from low temperature until
the non‑oxidized material has been completely oxidized. The oxidizing process
can take place in a chemical laboratory, outside the fusion instrument. One single
mistake may be fatal for the crucible (Figure 27). The most frequent non‑oxidized
materials are sulfide minerals, sub‑oxides such as FeO, MnO, Cu2O (instead of Fe2O3,
MnO2, CuO), metallic elements and organic materials.
When sulfides are present in low concentrations, add 0.1 to 0.3 g of Li or Na nitrate
in the flux and start heating at very low temperatures for one minute before
proceeding to a regular fusion. If the concentration is much higher, increase nitrate
to 2 or 3 g and heat for a few minutes. Platinum reacts with sulfides forming
platinum sulfide that makes the crucible very brittle.
When metallic particles are present, proceed as for sulfides but take note that
oxidation is slower and more difficult. A reaction of metals with platinum usually
causes less damage than sulfides because they form an alloy that is less brittle.
Organic materials are simply heated at very low temperatures; they burn easily.
After fusion has been completed the dissolved elements do not react any
more with the crucible while still at high temperature, unless the surrounding
atmosphere is reducing which may cause a few elements, such as Fe and Cu, to
partially reduce and produce some free metal atoms that coat the surface of the
crucible.
Do not scrape a residue from a crucible by means of a hard tool, for example a
screwdriver or metal spatula. Scratches on the crucible retain more residue in
subsequent fusions.
42
Figure 27. Pt alloy crucibles are easily destroyed when trying to fuse reduced (not fully oxidized)
substances, or by bad handling.
5.2.2 Molds
Never tap hard on a mold to release a stuck glass disk, rather use the ‘whack’
technique (Figure 28). Place the cold mold with stuck bead in the middle of a thick
wad of loose sheets of paper. Close the sheets and ‘whack’ them on the table,
desk or bench top. The disk will usually come away from the mold which will be
undamaged.
If the whack technique does not succeed, heat the mold for a few seconds only so
that the mold expands without heating the fused bead too much, then turn the
mold upside down and let the disk fall. If that is not successful, put some KI on
the disk, heat until the KI and the disk melt, then pour the molten glass. Clean the
mold as for crucibles. The surface of the glass disk is an exact replica of the surface
of the mold, so keep the mold flat, well polished and free from scratches. Polishing
can be done as discussed in 5.3.2.
Figure 28. The ‘whack’ technique for releasing fusion beads stuck in molds
43
5.3 Prolonging platinum ware lifetime

5.3.1 Cleaning of platinum ware
A crucible or casting mold should never be hit or tapped with any implement to
remove residual fused sample stuck to the surface. Any residual material should be
removed by one of the following methods:
• Place the laboratory platinum ware in a 25% citric acid solution in an ultrasonic
bath and keep it at 60 ºC for up to 30 minutes until clean and rinse with distilled
or de-ionized water;
• To shorten the cleaning cycle, use a 20% w/v citric acid in a beaker at 80 ºC;
• For a more aggressive method use 10% HCl. The use of orthophosphoric acid
should be avoided;
• A simple way to clean the crucibles is the following: put about 2 g of flux (purity
is not important, a chip of a broken glass disk is acceptable) and 0.2 g of KI in
the crucible, heat until fused, then cast.
After acid cleaning, wash thoroughly with distilled or de-ionized water and dry.
If a residue is still present after both these alternatives of cleaning, it is likely that a
reaction has taken place between the platinum and sample and that the crucible is
damaged permanently.
WARNING: Never use a mixture of nitric acid and hydrochloric acid.
5.3.2 Maintenance
Damaged casting molds can have a direct effect on the analysis of the fused beads.
The figure below illustrates how a mold appears when manufactured and at the
end of its life.
Perfect Damaged
casting dish
Figure 29. Difference between a perfect mold and a dish with damaged surface
Microscope analysis of the casting mold can be useful in more effectively

determining the conditions of the mold, than just visual inspection.
44
Another method to check for damaged casting molds is illustrated in Figure 30;

take two beads and place the ‘to be measured’ sides of the beads together and
check for the perfect fit.
Beads - convex (common) Beads - concave Beads - perfect
Figure 30. Checking the molds for damages
In general the crucibles will be more difficult to clean and deformations in the
casting mold may cause difficulty in releasing the bead and will increase errors in
the reported result. The mold can also be re-shaped, this can also help to prolong
the useful life of the casting mold.
Dented and deformed crucibles typically pour the fused sample badly, increasing
the probability of a less homogeneous or cracked bead.
Using a dedicated crucible re-shaper for the specific crucible type ensures continued
efficient bead production. Regular re-shaping can help to prolong the useful life of
the crucible.
The most effective form of maintenance after re-shaping crucibles and re-pressing
molds is to re-polish. The life of platinum ware can be considerably extended
by careful use and polishing but it should be noted that polishing will reduce
the weight of the platinum, subsequently reducing the amount of credit on
replacement time.
5.3.3 Polishing and re-shaping kits

A range of platinum ware care products are available from PANalytical to prolong
the useful lifetime of crucibles and casting molds. These include; plastic cleaning
baskets to avoid scratching and abrasion during ultrasonic cleaning, re-shapers and
a polishing lathe.
45
Miscellaneous PANalytical
6. Miscellaneous
6.1 Contamination by crucibles
Residues left in a crucible before a fusion do contaminate the next fusion.
However, the contamination is often so small that it is not necessary to clean the
crucible after each fusion, and it is better to leave the crucible untouched on the
fluxing machine as long as possible. Remember that manipulation of a crucible is
one of the two most efficient ways of shortening the useful life of a crucible; the
other one is corrosion.
The amount of contamination resulting from not cleaning a crucible can be
estimated by the following equation:
Contamination (absolute %) = (Weight of residue)/(Weight of total fusion) × (C2 – C1 )
where (C2 – C1 ) = difference of concentration of the component in the two samples
Example: A sample with a calculated concentration of 26.35% Fe is fused after one

that contains 17.84% Fe. The residue of the first sample in the crucible is about
10 mg in a total fusion of 7.5 g.
The contamination is: 10/7500 × (26.35% – 17.84%) = 0.01%
which means that the calculated concentration of 26.35% is 0.01% too low and the
corrected concentration is 26.36%. Cleaning is obviously not necessary.
However, if the residue was 12 mg, the total mass of fusion 7000 mg, and the
concentrations in the two samples 30% and 10%, respectively, then the absolute
contamination would be
12/7000 × (30% – 10%) = 0.03%
The analyst would have to decide whether or not this degree of contamination is
acceptable. For Al2O3 at 15% it probably would be acceptable. For TiO2 at 0.3% it
would not be acceptable.
6.2 Contamination by W when using WC grinding vessels

Tungsten carbide (WC) can be introduced into samples during the grinding process
of sample preparation with WC mortars. In addition to W and C, the alloying
component of the WC grinding vessel, usually about 10% Co, is also introduced
into the sample. The amount of contaminant added is generally very small
(approximately 0.1 - 0.5%), because of the hardness of WC and the relatively
softer sample. However, when the accuracy of the final analysis is really important,
then corrections have to be made for dilution of the sample and the effect on
the measured loss on ignition (LOI). The mathematics of the corrections is quite
47
complex, but Bennett and Oliver (1992, pp. 180-184) give an excellent description
of the equations and correction procedures necessary to correct for contamination
by WC in pure tungsten carbide mortars, and by WC, Co and Ni in Co and Ni
bonded WC mortars.
6.3 Blanks
Pure LiT and 66:34 LiT:LiM can be cast as a blank bead. Pure LiM and 12:22
LiT:LiM always crystallize. The addition of about 10 mg KI a few seconds before
casting stabilizes the vitreous state but the bead will not be a blank for K. Other
non‑wetting agents are also likely to be efficient. Alternately, add a small amount
of Li carbonate. That will make the tetraborate not perfectly stoichiometric, and
crystallization will be more difficult.
6.4 Loss or gain on ignition (LOI or GOI)

Loss of sample by volatilization (H2O, CO2) or gain of weight by oxidation changes
the total weight of a fusion mixture and yields apparent concentrations that are
too high or too low respectively.
Methods are available to correct for this:

1. The change of weight is measured by heating the sample (without flux) and
comparing its weight before and after heating. Then the change of weight is
calculated as a percentage of the sample and is considered in the same way as
any element in an algorithm such as the Lachance‑Traill algorithm. The product
of the alpha factor and the concentration of LOI or GOI being known, the
concentration of each element can thus be corrected.
2. Using an algorithm as above, the concentration of LOI or GOI is assumed to be

zero at first. The concentration of each element is calculated and the difference
between the sum and 100% is taken as a first approximation of the LOI or GOI.
The latter value is used in the next iteration and so on, to eventually yield the
correct concentration of each element and an approximate, but adequate,
value of the LOI or GOI (LeHouiller et al., 1977; Norrish and Thompson, 1990).
LOI and GOI values can be ignored totally if the XRF software uses a Fundamental
Parameter (FP) algorithm for matrix correction (for example in PANalytical
software). The fundamental parameter equation can be used in a manner such that
the result is the concentration of each element in the flux (Claisse, 2007).
48
Advantages and limitations of fusion PANalytical
7. Advantages and limitations of fusion

7.1 Advantages
The fusion technique has many advantages over most other techniques of sample
preparation. Apart from the elimination of particle size effect and mineralogical
effect, the main ones are the following.
7.1.1 Reproducibility
The fact that a quality glass disk is close to perfection as a specimen can be, i.e.
it has a flat surface, no porosity, and good homogeneity (LeHouiller et al., 1974),
the fluorescent intensities should be constant for replicate preparations of the
same sample. Table 2 shows compositional variations and errors for 10 glass
disk replicates of a cement sample made with an Eagon 2 fusion machine. The
preparations were made on successive days over a ten days period and the errors
listed unclude errors on weighing, fusion reproducibility, XRF instrument stability
and counting statistics. The glass disks were prepared using 1 g cement mixed with
10 g of a mixed Li2B4O7 : LiBO2 flux (66:34), and 65 mg NH4I.
Table 2. Maximum compositional variations from mean values of ten fused glass disks
Sample Al2O3 CaO Fe2O3 K2O MgO Na2O P2O5 SO3 SiO2
name (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %)
Day 1 4.42 62.93 3.51 0.613 1.771 0.040 0.049 2.83 19.64
Day 2 4.38 62.80 3.51 0.613 1.744 0.052 0.051 2.82 19.53
Day 3 4.40 62.78 3.50 0.607 1.760 0.044 0.049 2.82 19.63
Day 4 4.40 62.83 3.49 0.607 1.751 0.043 0.050 2.80 19.60
Day 5 4.42 62.86 3.51 0.614 1.758 0.041 0.051 2.82 19.58
Day 6 4.39 62.93 3.51 0.594 1.742 0.048 0.049 2.83 19.57
Day 7 4.38 62.77 3.50 0.594 1.751 0.036 0.049 2.82 19.57
Day 8 4.40 62.75 3.51 0.594 1.748 0.041 0.051 2.80 19.55
Day 9 4.40 62.83 3.50 0.588 1.750 0.036 0.050 2.79 19.53
Day 10 4.40 63.05 3.51 0.596 1.754 0.043 0.049 2.81 19.57
Average over 10 beads made over 10 days
Mean 4.40 62.85 3.51 0.602 1.753 0.042 0.050 2.81 19.58
Min 4.38 62.75 3.49 0.588 1.742 0.036 0.049 2.79 19.53
Max 4.42 63.05 3.51 0.614 1.771 0.052 0.051 2.83 19.64
StDev 0.01 0.09 0.01 0.010 0.008 0.005 0.001 0.013 0.04
RSD % 0.29 0.14 0.21 1.62 0.48 11.62 1.85 0.46 0.19
3 sigma 0.04 0.27 0.02 0.03 0.03 0.01 0.003 0.04 0.11
49
7.1.2 Accuracy
On account of high homogeneity and ideal shape, fusion beads meet the
requirements of the hypotheses made in the development of the theory of X‑ray
fluorescence emission. As a consequence, the application of software packages
based on fundamental parameter calculations or theoretical influence coefficients
should yield the most accurate analytical results that XRF analysis can reach. Many
such software packages are available commercially.
7.1.3 Preparation of standards

Standards of any composition are easily prepared by mixing pure oxides in the
desired proportions. Preparation of fusion beads is the same as for the unknown
samples and ensures full reliability of calibration.
Giles et al. (1995) recommended the use synthetic ‘standards’, for the easy
calibration in fused glass beads of the 13 most commonly occurring oxides, plus
six others, in oxides, silicates and carbonates, using a single sample for each
calibration.
PANalytical supplies primarily synthetic standards for the calibration of cement

(CEMOXI) and wide-range oxide (WROXI) applications. These standards are easily
traceable to the pure compounds used in their manufacture, such that resulting
analytical accuracy is as good, if not better, than applications calibrated with
certified reference materials (CRM).
Figure 31. Synthetic standards, such as the sets of CEMOXI (cements) and WROXI (wide-range
oxides) standards, are available from PANalytical. The standards are supplied as powders and
are made of oxides traceable to 99.999% pure compounds. They are ideal for fused reference
calibrations.
7.1.4 Versatility
Although the more reliable method of analysis is using a few standards in
combination with a fundamental parameter software package, all the other
analytical techniques are still applicable using fusion beads instead of powders:
internal standard, spiking, double dilution, etc. Since particle size effects are
absent in fusion beads and since matrix effects are smaller than in powders, these
techniques work better than usual.
50
Advantages and limitations of fusion PANalytical
7.1.5 Cost
The purchase of a fusion apparatus with platinum crucibles and molds may seem
expensive at first sight, but there are several other aspects to consider when a
comparison is made with other techniques:
• crucibles and molds are consumables but the scrap metal value should be
subtracted from the cost of new ones;
• essentially the only other consumables are fluxes (and propane gas for a gas
flame fusion apparatus or electricity for an induction heating fusion apparatus
or a muffle furnace), and the quantity used per analysis is small;
• labor is reduced to a minimum if a fusion machine is used;
• labor is reduced to a minimum if LOI and GOI can be ignored, or if weights of
ingredients of the fusion need not be constant;
• after the operating conditions have been set in the machine, no particular skill
is required to operate it;
• installation costs of fusion machines vary; some are very low.
7.2 The Eagon 2 from PANalytical

PANalytical’s Eagon 2 (Figure 32) fusion machine for XRF sample preparation with
an innovative design, high performance and safe operation provides the perfect
solution to prepare fused beads for XRF analysis of a wide variety of materials.
Figure 32. From start to finish of the fusion process PANalytical’s Eagon 2 provides the perfect
solution to obtaining in a safe, reproducible and cost-effective procedure, stable, homogeneous glass
beads for accurate XRF analysis of a very wide variety of materials.
51
7.3 Limitations
Limitations of the fusion technique concern materials, undetectable elements and
low concentrations.
The materials that cannot or are not recommended to be processed are those that
are explosive, radioactive, poisonous (As, Hg), insoluble (Pt, Ag, Au), volatile (Cl, Br, I),
those that are not soluble in fluxes and those that are difficult to transform into a
soluble form (carbides, nitrides).
The fact that fusion implies dilution means that the fluorescence intensities
are decreased, but not as much as the dilution ratio predicts. The diluent is
composed of light elements that have low mass attenuation coefficients for X‑rays.
Consequently it appears almost as if no dilution was made, when the wavelength
of analyte X-rays is short. In the case of light elements such as Mg and Al, the
effect of dilution is still smaller than that expected from the dilution ratio but not
negligible, so that the detection limit is increased somewhat.
7.4 Environment
Borate fusion is one of the cleaner analytical techniques: no corrosive gas; total
fused material and waste is small; use of acids for cleaning can be avoided. The
only undesirable product is NO2 gas when sulfides and metallics are processed, but
the quantity is very small.
52
Selection of flux PANalytical
8. Selection of flux
• Successful fusion beads are only obtainable in a limited range of glass acidity
(Figure 33).
• The probability of obtaining stable glass of Li borate varies with the
composition, more specifically with the acidity of the borate.
• The acidity index (A.I.) is defined as the ratio of the number of oxygen atoms to
that of metal atoms.
• Some typical acidity indices:
LiT ( Li2B4O7 ) = 7/6 = 1.17
LiM ( LiBO2 ) = 1.0
50:50 LiT:LiM = 1.11
65:35 LiT:LiM = 1.13
• When oxides are dissolved in Li borate fluxes the acidity index is the average of
those of the flux and dissolved oxides (on a mole basis), e.g. for SiO2:LiT 1:9 the
acidity index is 1.21, which is too high to make glass beads easily.
• At glass compositions where the probability of obtaining a glass bead is low,
fused beads of pure flux always crystallize.
Probability of making
stable glass beads
Oxigen/metal atom ratio (acidity index)
Figure 33. Figure relating the probability of making good glass beads with the acidity index of the
flux mixture. The fraction of lithium tetraborate in a flux mixture with lithium metaborate is also
indicated.
The solubility of a number of different oxides in different flux compositions is

illustrated in Figure 34. Note that 6 g of a 50:50 mixture of LiT and LiM will dissolve
0.6-0.7 g of all the compounds shown, except for PbO, MoO2 and possibly TiO2.
Typical fusion times and temperatures for some common materials are shown in
Figure 35.
53
Solubility in grams oxide / 6 grams flux
Figure 34. Oxide solubility in different flux compositions
1200
Metal oxides
Ferro-alloys
1100 Sulfides
Silicates
Cements
900
Temperature (°C)
700
500
300
0
0 5 10
Time (minutes)
Figure 35. Typical fusion times and temperatures for different types of materials.
54
References PANalytical
9. References
Banerjee S. and Olsen, B.G. (1978) Rapid Analysis of Chrome Ores, Chrome‑Magnesia and
Magnesia‑Chrome Materials by XRF. Appl. Spectr., 32, 376‑379.
Bennett H. and Oliver G.J. (1992) XRF analysis of ceramics, minerals and allied materials. John Wiley
& Sons Ltd.
Blanchette, J. (2001) Borate Fusion of Copper and its Compounds. Canadian Mineral Analysts
Conference, Ontario, Canada.
Claisse F. (1957) Accurate X‑Ray Fluorescence Analysis without Internal Standard. Norelco Reporter III,
no. 1, 3.
Claisse F. (2007) www.fernandclaisse.com/software.
Cullen, T.J. (1960) Potassium Pyrosulphate Fusion Technique - Determination of Copper in Mattes and
Slags by X-ray Spectroscopy. Anal. Chem., 32, 516-517.
Cullen, T.J. (1962) Addition of Sodium Fluoride to Potassium Pyrosulphate Fusions for X-ray
Spectroscopic Analysis of Siliceous Samples. Anal. Chem., 34, 862.
Fréchette G., Hébert J.C., Thinh T.P., Rousseau R. and Claisse F. (1979) X‑Ray Fluorescence Analysis of
Cements. Anal. Chem., 51, 1957‑1961.
Giles H.L., Hurley P.W. and Webster, H.W. (1995) Simple approach to the analysis of oxides, silicate
and carbonates using X-ray fluorescence spectrometry. X-ray Spectrom., 24, 205-218.
LeHouiller R., Turmel S. and Claisse F. (1974) Bead Homogeneity in the Fusion Technique for X‑Ray
Spectrochemical Analysis. Anal. Chem., 46, 734‑736.
LeHouiller R., Turmel S. and Claisse F. (1977) Loss on Ignition in Fused Glass Buttons. Adv. in X‑Ray
Anal., 20, 459‑469.
Norrish K. and Hutton J.T. (1969) An accurate X-ray spectrographic method for the analysis of a wide
range of geological samples. Geochim. Cosmochim. Acta, 33, 431‑453.
Norrish K. and Thompson G.M. (1990) XRS Analysis of Sulphides by Fusion Methods. X‑Ray Spectrom.,
19, 67‑71.
Sear L.G. (1997) The fusion of difficult materials including chromite, cassiterite and reduced sulphur.
X-Ray Spectrom., 26, 105-110.
Turmel S., LeHouiller R. and Claisse F. (1978) X‑Ray Fluorescence Analysis of Borate Fusion Buttons
with Unknown Sample/Flux Ratio. Can. J. Spectrosc., 23, 125‑129.
55
Index PANalytical
10. Index
A Internal standards......................... 14
Lithium hexametaphosphate....... 12
Acidity index........................................ 53
Lithium metaborate...................... 11
Additives.............................................. 14
Lithium tetraborate...................... 11
Heavy absorbers .......................... 14
Oxide solubility in different......... 54
Advantages and limitations of .......... 49
flux compositions
fusion
Oxidizers........................................ 14
Accuracy......................................... 50
Properties of borate fluxes........... 13
Cost................................................ 51
Releasing agents........................... 14
Environment.................................. 52
Sample:flux ratio and flux............ 18
Limitations..................................... 52
composition
Preparation of standards.............. 50
Selection of flux............................ 53
Reproducibility.............................. 49
Sodium hexametaphosphate........ 12
Versatility....................................... 50
Sodium tetraborate....................... 11
Advantages of using fusion.................. 6
Fusion instruments.............................. 39
techniques
Fusions
Acidity index.................................. 53
B Advantages and limitations of..... 49
Blanks................................................... 48 fusion
Blanks............................................. 48
C Carbon........................................... 33
Carbonates..................................... 33
Carbon................................................. 33 Care of crucibles and molds.......... 41
Carbonates........................................... 33 Casting and cooling...................... 27
Care of crucibles.................................. 41 Contamination by unclean........... 47
Care of crucibles and molds................ 41 crucibles
Casting and cooling............................ 27 Cooling curves............................... 29
Contamination by unclean crucibles.. 47 Copper compounds....................... 32
Cooling curves..................................... 29 Crucibles and molds...................... 20
Copper compounds............................. 32 Crucibles - care of.......................... 42
Crucibles............................................... 42 Crystallization curves.................... 30
Contamination by unclean .......... 47 Fluxers and fusion instruments.... 39
crucibles Fluxes and additives...................... 11
Crucibles and molds ........................... 20 Heating during fusion................... 21
Crystallization curves.......................... 30 Limitation to borate fusion.......... 11
Loss or gain on ignition................ 48
F (LOI or GOI)
Fluidizers.............................................. 14 Metallic materials.......................... 33
Fluxers and fusion instruments.......... 39 Molds - care of............................... 43
Fluxes and additives............................ 11 Norrish and Hutton method......... 12
Acidity Index.................................. 53 Oxide solubility in different......... 54
Additives........................................ 14 flux compositions
Fluidizers........................................ 14 Preparation of glass disks............... 9
Heavy absorbers............................ 14 Pyrosulfate fusions........................ 35
57
Selection of flux............................ 53 O
Sulfide concentrates...................... 36
Oxide solubility in different flux........ 54
Sulfide minerals............................. 32
compositions
Typical fusion times and............... 54
Oxidizers.............................................. 14
temperatures
G P
Preparation of glass disks..................... 9
Gain on ignition (GOI). See Loss or gain
Properties of borate fluxes................. 13
on ignition
Pyrosulfate fusions.............................. 35
H R
Heating during fusion......................... 21
Releasing agents................................ 14
Heavy absorbers.................................. 14
I S
Sample:flux ratio and flux.................. 18
Internal standards............................... 14
composition
Sample preparation. See also Fusions
L Fusions
Limitation to borate fusion................ 11 Crucibles and molds................ 20
Lithium hexametaphosphate............. 12 Fluxes and additives................ 11
Lithium metaborate............................ 11 Norrish and Hutton method... 12
Lithium tetraborate............................ 11 Preparation of glass disks......... 9
Loss or gain on ignition...................... 48 Selection of flux.................................. 53
(LOI or GOI) Sodium hexametaphosphate.............. 12
Sodium tetraborate............................. 11
M Sulfide concentrates............................ 36
Metallic materials................................ 33 Sulfide minerals................................... 32
Molds................................................... 43
T
N Typical fusion times and..................... 54
Norrish and Hutton fusion method... 12 temperatures
58
Glass beads by
borate fusion
James P. Willis
ISBN: 978-90-809086-9-7
The Analytical X-ray Company

Glass Beads by Borate Fusion - tcm50-54735

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XRF SAMPLE PREPARATION

The Analytical X-ray Company

Glass beads by borate fusions

Copyright © 2010 by PANalytical BV, The Netherlands.

All rights reserved. No part of this publication may be reproduced, stored in a

This edition published in 2010 by:

5 Care and use of platinum ware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Particle size (coarser)

1.1 Undesirable effects of using powders in XRFS

Pressed powder, production control calibrations Fused bead reference calibration

1.2 Advantages of using fusion techniques

Most fusion processes result in a product that is a mixture of several compounds

Although a borate fusion is also a chemical reaction, its characteristics are

This concept of borate fusion helps to understand why high‑temperature

2. Preparation of glass disks

2.1.1 Typical simplified procedure

Making a glass bead today is a simple process thanks to the availability of

It is true that fusion is sometimes perceived to be a complex problem. The reason

versatility is necessary in the parameters involved such as composition of flux,

2.1.2 A limitation to borate fusion

2.2 Fluxes and additives

Lithium metaborate (LiM), LiBO2, is very susceptible to crystallization, more than

A combination of borates is useful and many mixtures are now available

2.2.2 Properties of borate fluxes

An advantage of the granular, pre-fused fluxes (0.3 to 0.5 mm diameter) is their

2.2.3 Impurities in fluxes

Internal standards are added as oxides if required in the analytical technique.

Oxidizers, for example NH4NO3, NaNO3, LiNO3 or SrNO3, are added at a

In practice the number of additives should be kept to a minimum to save time in

2.2.5 Non-wetting (releasing) agents

2KBr + Cu + O K2O + CuBr2

Figure 9. Volatilization of I and Br as a function of fusion time

Ideal Insufficient Too much Excess

2KBr + 2LiNO3 K2O + Li2O + 2NO2 + Br2

2.3 Preparation before fusion

1. Take a representative sample from the material to be analyzed. To ensure the

3. Choose a convenient sample:flux weight ratio, taking into consideration the

Very high sample:flux ratio (1:3)

Sample material Flux* Sample/Flux/LiNO3

Different sample:flux ratios

‑ as mentioned in section 2.2.3, any impurity in the flux appears as if it is an

6. Determine a program for the fusion process. Although many substances

2.3.2 Crucibles and molds

A mirror‑polished crucible or mold is only slightly, if at all, wetted by the molten

With a granular flux, a 20 to 25 ml capacity crucible is large enough to

2.4.1 Heating requirements

800 900 1000 1100 1200 1300 1400 1500 1600

Electric furnace heating is the best means of heating, providing thermal

Propane gas burner is a simple and efficient means of heating:

Temperature (°C) in melt

0.5 1.0 1.5 psi

Propane‑oxygen gas burner has a workable range of temperatures a few hundred

Temperature measurement during fusion is not really necessary. As a matter of

2.4.2 Heating steps

2.4.3 Heating steps for oxidation

2.4.4 Heating steps for fusion and homogenization

The second step is accomplished at the ‘cruising’ temperature for fusion

The effect of rocking of a standard crucible containing a liquid is shown in

Top view Hump

2.4.5 Heating steps for conditioning before casting

2.5 Casting and cooling

The time required for a glass specimen to crystallize varies as a function of

A few types of cooling curves are shown in Figure 22: