X-RAY SPECTROMETRY, VOL.

19, 203-206 (1990)

Glass Disk Fusion Method for the X-Ray

Fluorescence Analysis of Rocks and Silicates
MoisLts Alvarez
Physics Department Universidad Nacional Pedro Henriquez Ureiia, Santo Domingo, Dominican Republic

A study of the physical and practical aspects needed for a successful solid solution method for XRF analysis is
presented in the light of the theory and practice of the glass-making industry. An inexpensive manual glass disk
sample preparation method is proposed that gives a well annealed disk that can he ground and polished without any
losses due to breakage.

INTRODUCTION
Fusion methods have many advantages compared with
powder pressed pellets in the x-ray fluorescence (XRF)
analysis of rocks and silicates, regardless of whether the
solid solution is used directly, powdered or briquetted.-3 The advantages are that the particle size and
heterogeneity effects (i.e. mineralogical effects) are eliminated, the possibility of decreasing matrix effects or
maximizing fluorescence intensities using a high or low
specimen dilution, respectively, the possibility of adding
compounds (e.g. heavy absorbers, standard additions or
internal standards) to decrease or compensate for
matrix effects and easily prepared synthetic standards.
The disadvantages of the fusion method are that
analyte-line intensities from low-2 elements and trace
and minor constituents are reduced by dilution and
absorption, fusion requires considerable time and skill if
manual glass bead disks are attempted and sometimes
there are problems associated with fluxing, crucible
sticking and bead cracking.
Many studies have been made of these problems and
the fusion method has become widely applied. However,
for the x-ray analyst trying to use the fusion procedure
for the first time, contradictory advice in the literature
may result in confusion and disappointment, and the
impression that the method is more an art than a
science. This situation prompted us4 to try to understand and systematize the physical processes behind the
fusion method, using the knowledge accumulated in the
glass-making i n d ~ s t r y . ~

THEORETICAL

Let us first define some useful terms:

Annealing: The operation of removing or reducing
the strains in glass.
force per unit area.
Stress :
Strain :
relative deformation.
Since stress usually accompanies strain, the words are
often used interchangeably, but it is important to
remember that they are not synonymous.

Reason for annealing glass

Our previous work4 has shown that the removal or prevention of excessive stress is the most difficult problem
encountered by the analyst using the glass disk method
in XRF analysis. When glass disks are poorly annealed,
large losses due to breakage may occur during the
cooling process, and even if the glass disks have been
completely cooled without fracturing, they may show an
annoying tendency to breakage when handled or when
attempts are made to grind or to polish them later. It is
hence desirable to consider, in a general way, the creation and release of internal stress.
Glass is an amorphous material which at ordinary
temperature is as hard as a typical solid, but softens
when it is gradually heated, until it becomes viscous and
finally liquid. The reverse process takes place during
cooling. This wide range of temperatures in which continuous solidification occurs is characteristic of undercooled liquids but is never observed with crystalline
solids.
In general, a temperature gradient established by
heating will produce in the outer layers a longitudinal
compression that changes continuously into tension in
the inner layers (with a neutral zone, in the middle, with
no stress), while a gradient established by cooling will
cause the opposite to happen.

Annealing of glass
Temporary and permanent stress
The following discussion is based mainly on the theoretical and practical knowledge acquired in the glassmaking industry5 and generally follows the trends
indicated in the classical paper of Adams and Williamson.6

0049-8246/90/040203-04 $05.00
0 1990 by John Wiley 8z Sons, Ltd.

When glass is cooled there are three possibilities: (1)

cooling from a relatively high temperature with the production of permanent stress; (2) cooling from a relatively medium temperature, in which case stress is
Received 1I September 1989
Accepted (revised) 6 February 1990

M. ALVAREZ

204

introduced, but less than in (1); and (3) cooling from a

relatively low temperature, in which case no permanent
stress is introduced, only temporary stress due to the
temperature gradient.

Detection of stresses in glass disks and

their interpretation
The device for detecting stresses in a glass disk is the
polariscope. The simplest polariscope can be made by
crossing two Polaroid filters in such a way that the
background remains dark. Introducing a glass disk in
the middle of the filters and looking through them,
using white light, is a very useful way of testing if the
disk is or is not well annealed, and of establishing the
degree of annealing. This information can be used for
choosing and/or optimizing the conditions established
for annealing, such as annealing temperature and time.
A well annealed disk should look completely black
through the polariscope. Sometimes annealed disks
show a black cross pattern, whose line width is an indication of the amount of stress present. Narrower lines
indicate higher stress.'
Highly stressed glass disks show coloured patterns
and these colours are directly related to the stress (see
Table 1). Other more sophisticated means for accurately
detecting and measuring stresses can be found in the
glass-making literature.'
Adams and Williamson6 found empirically that the
release of stress at constant temperature proceeds
according to the equation

1/F - 1/Fo = At

(1)

where F is the stress at time t, F, is the initial stress and

A is a constant for the particular glass at a particular
temperature and is a measure of the rate at which
stresses are relieved. The variation of A with temperature follows the equation
log A

= MIT - M ,

(2)

where T is the temperature in "C and M , and M , are

constants for a particular glass.
For the sake of convenience, the quantity experimentally measured is the birefringence, 6n, i.e. the optical

path difference per unit length (in nm cm-'), which is

directly related to the stress F.
Rearranging Eqn (1)yields
1/6n - 1/6n,

= Aft

where 6n, is the initial birefringence and A' is the variation of stress with time (in optical units).
The birefringence can be obtained using a polariscope, by measuring the optical path difference (in nm)
and dividing this value by the length (in cm) of the glass
in the line of sight.
A method for measuring the optical path difference is
to observe the colours produced when the sample is
placed in a polariscope and then using Table 1.

Annealing
Adams and Williamson6 pointed out that at any temperature, a glass requires a certain 'annealing time', and
this is arbitrarily defined as the time required to reduce
the stress, in optical unit, from 50 to 2.5 nm m-'.
The 'annealing temperature' is that temperature for
which the annealing time is 2 min. The 150C interval
of temperature lying immediately below is called the
'annealing range.' At temperatures below the annealing
range, very little permanent stress can be introduced.
Adams and Williamson6 showed that the best
method for annealing requires that the glass be held at
constant temperature, below its customary annealing
point, for the appropriate time, and then cooled at an
increased rate, as shown in Fig. 1. This seems to be in
contradiction with some authors' claims.
At this point, a word of caution is advisable. It is well
known that the strength of glass under tension is much
less than that under compression; the tensile strength of
glass is almost an order of magnitude less than its compressive strength. This means that although the cooling
rate can be increased when one surpasses the lower part
of the annealing range, one must be careful in doing
this, and bear in mind that the glass could crack, even if
it is well annealed, owing to the temporary stress
induced by cooling. At no time during cooling should

Table 1. Relationship between phase difference and colour with

white light
Phase difference
(nm)

Colour"

50
200
300
425
530
565
640
740
840

Iron grey
Greyish white
Yellow
Orange
Red
Violet
Blue
Green
Yellowish green

Phase difference
(nm)

Colour"

880
945
1030
1100
1200
1300
1425
1500

Yellow
Orange
Red
Violet
Bluish green
Green
Yellow
Orange

"The colours become paler as the phase difference increases.

._

T I M E (HOURS)

Figure 1. Recommended annealing procedure: the top dashed

line is the annealing temperature and the temperature range
between the dashed lines is the annealing range.

205

GLASS DISK FUSION METHOD FOR XRF ANALYSIS

the hot glass disk be touched by an object cooler than

itself.
Annealing temperature and time

The problem that arises is how to measure, experimentally, for a particular glass sample the annealing temperature and the annealing time. The annealing
temperature has been determined by three method^,^.'^
involving either the disappearance of the stresses using
a 'special' oven, differential thermal analysis (DTA) or
the rate of thermal expansion.
In the XRF field, only Bertin' has mentioned DTA
for determining the annealing temperature of glass
disks, but without going deeper into the subject.
Wilburn and Dawson," in the glass field, reported the
use of DTA use for this purpose and stated that DTA is
a rapid and convenient method for determining the
annealing temperature of glasses.
]in general, when powdered glass is subjected to DTA,
two peak temperatures are observed, one endothermic,
at fairly low temperature, and the other exothermic at a
higher temperature. These peaks depend on the glass
composition. The first endothermic peak is the so-called
'annealing dip' and the temperature where this occurs is
the annealing temperature. The exothermic peak is due
to devitrification of the glassy material and this temperature must be avoided when annealing glass disks or
crystallization may occur (see Fig. 2). Working below
this temperature greatly reduces the risk of crystallization, although this seems to be in contradiction
with some authors' claims.
Once the annealing temperature has been obtained,

the annealing time can be determined from Eqns (1) and

(2) developed by Adams and Williamson.6 For this, one
needs to know the constants M I and M , in Eqn (2),
which are particular to each glass and are not known a
priori.
A practical way of solving the problem is to create a
series of highly stressed glass disks. This can easily be
done by quickly cooling them from a temperature
higher than the annealing temperature (i.e. > 600 "C).
Subsequently each can be kept at different times (i.e. 0.5,
1, 2 h and so on) in a fixed temperature environment
slightly below the annealing temperature (1.e. 500 "C in
an oven). When this time has elapsed, the oven is turned
off and allowed to cool slowly, keeping the disk inside
the oven, without opening the door, until the lower part
of the annealing range is reached (1 h is normally sufficient but one can experiment). Below this temperature,
the disk may be removed and cooled to room temperature. If the annealing was properly done it can be
established by viewing the disk through the polariscope.
The time should be adjusted until one obtains a well
annealed disk.
After optimization, the disks are quite sturdy and can
be ground and/or polished with confidence. Disks prepared according to the steps described above have a
zero breakage rate and can even be dropped without
breakage.
It should be mentioned that the rate of annealing
doubles approximately for each 10C rise in temperature. This means that if 30 min are needed for
annealing a particular glass disk at 500 "C, at 440 "C it
requires more than 1 day! Therefore, it is very important to know as accurately as possible the annealing
temperature of a particular glass

0.2

10

Temperature

("'2)

Figure 2. DTA curve for a glass disk formed from a rock sample-lithium tetraborate (1 : 9) mixture (<120 mesh). The endothermic peak A
at ca. 500C is the 'annealing dip' and this is the annealing temperature (heating rate 10C min-'). The exothermic peak B above 600C is
due to devitrification or crystallization.

206

M. ALVAREZ

Lastly, it is also important to note that another

means used for toughening glass in the glass-making
industry is tempering, that is all glass surfaces are
cooled so that they end up with compression balancing
the tension forces, which must be completely buried
under the surface." Tempering is normally done by
fast, uniform cooling of the glass from a temperature
close to its annealing temperature. The technique
resembles some of the methods used for producing glass
disks in XRF.13

PROCEDURE FOR PREPARATION OF GLASS

DISK SAMPLE
This sample preparation method involves the use of
lithium tetraborate in a flux-to-sample ratio of 9 : 1. If a
different fluxing reactant or flux-to-sample ratio is used,
the appropriate annealing temperature and time must
be determined as indicated above.
1. Weigh 9.000 0.001 g of lithium tetraborate in a
small plastic cup, previously weighed and tared.
2. Weigh 1.000 f 0.001 g of rock sample powder on a
piece of weighing paper, previously weighed and tared.
3. Weigh 0.2 g of ammonium nitrate [to oxidize
iron(I1) to iron(III)] on a piece of weighing paper, previously weighed and tared.
4. Transfer the weighed rock sample powder from 2
and the ammonium nitrate from 3 to the small plastic
cup with the flux from 1.
5. Manually mix the powders for 1-2 min.
6. Transfer the homogenized mixture to a graphite
crucible and heat at 1150C in an electric muffle
furnace for 15 min. Every 5 min swirl the crucibles for
ca 10 s to eliminate bubbles and to ensure homogeneity.
7. Pour the melt into a graphite mould (with sloping
walls) previously heated to ca. 500 "C.
8. Introduce the glass disk (on the graphite mould)
into a second oven previously heated to ca. 500C (the
annealing temperature was ca. 525 "C, see Fig. 2). Keep
it there for ca. 1 h, which is the annealing time, without
opening the oven door.
9. Turn off the oven and wait until the temperature
falls below 350C (ca. 1 h with the oven door closed)

before removing the glass disk to cool to room temperature.

10. Steps 8 and 9 are essential to prevent shattering
during grinding and polishing. Moreover, if grinding or
polishing are not done, these steps prevent unpredictable cracking of the glass disks. The rate of breakage is
reduced almost to zero.
11. To establish whether the glass disk is properly
annealed it can be viewed through crossed Polaroid
filters, and should look black. Sometimes the glass disk
looks completely white when examined through a
polariscope, but appears completely black after being
ground. This may be caused by graphite contamination
in the lower surface.
12. Grinding and polishing are important and almost
essential to avoid graphite contamination in the lower
surface of the glass disks.

CONCLUSION
A detailed study of the physical and practical aspects
that need to be considered in order to produce a successful glass disk for the XRF analysis of rocks and silicates has been made in light of the theory and practice
developed in the glass-making industry. According to
these there are only two methods for dealing with the
stresses in a glass disk : annealing and tempering.
In this work the measurement and optimization of
the annealing method have been stressed. It is proposed
as an inexpensive method that gives well annealed disks
and can be applied under a variety of conditions, e.g.
with different fluxes, with only minor changes.

Acknowledgements
The author is indebted to the International Atomic Energy Agency
for financial support in the form of a fellowship (C6/DOM/8803). For
their kind cooperation in the supervision of this work the author
thanks Dr W. Rose and Dr T. Bornhorst of the Geology Department
of Michigan Technological University, where this project was carried
out, and Mrs E. Ducy de Perez and Mrs V. Mazo of the Universidad
Nacional Pedro Henriquez Uretia and Dr E. Greaves of the Universidad Simon Bolivar for their many helpful suggestions concerning
the text.

REFERENCES
1. E. P. Bertin, Principles and Practice of X-Ray Spectrometric
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(1981 ).
3. R. Tertian and F. Claisse, Principles of Quantitative X-Ray
Fluorescence Analysis, pp. 323-333. Wiley- Heyden, New
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4. M. Alvarez and M. Dowaji, Part of the final report presented at
the ANL/IAEA Inter-Regional Training Course on X-Ray
Analysis and Fluorescence, Argonne National Lab, Argonne,
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5. A. G. Pincus and T. R. Holmes (Eds), Annealing and
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