INTERNATIONAL ISO

STANDARD 12677

Second edition
2011-10-01

Chemical analysis of refractory products

by X-ray fluorescence (XRF) — Fused
cast-bead method
Analyse chimique des matériaux réfractaires par fluorescence de
rayons X — Méthode de la perle fondue

iTeh STANDARD PREVIEW

(standards.iteh.ai)
ISO 12677:2011
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011

Reference number
ISO 12677:2011(E)

© ISO 2011
ISO 12677:2011(E)

iTeh STANDARD PREVIEW

(standards.iteh.ai)
ISO 12677:2011
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011

COPYRIGHT PROTECTED DOCUMENT

© ISO 2011
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or
mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO's member body in
the country of the requester.
ISO copyright office
Case postale 56  CH-1211 Geneva 20 Tel.
+ 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org Web
www.iso.org
Published in Switzerland

i © ISO 2011 – All rights reserved

 ISO

Contents Page

Foreword........................................................................................................................................................... v
1 Scope.................................................................................................................................................... 1
2 Normative references.......................................................................................................................... 1
3 Types of material................................................................................................................................. 1
4 Principle................................................................................................................................................ 2
5 Apparatus............................................................................................................................................. 2
6 Sample grinding................................................................................................................................... 3
7 Loss on ignition (and/or drying)......................................................................................................... 4
8 Flux........................................................................................................................................................ 4
8.1 Choice of flux and ratio of flux to sample..........................................................................................4
8.2 Compensations for moisture in flux................................................................................................... 5
9 Fusion casting procedures................................................................................................................. 5
9.1 Fusion of samples and casting of beads........................................................................................... 5
9.2
9.3 iTeh STANDARD
Automatic bead preparation............................................................................................................... 7
Storage.................................................................................................................................................. 7
9.4 Special problems ............(..s...t..a....n....d....a...r...d....s.....i..t...e...h......a....i..) .....8
10 Calibration............................................................................................................................................ 8
10.1 Calibration standards.....................I.S..O...1..2..6.7..7..:.2.0..1..1 ....................................................... 8
10.2 Reagents
anhdttpss:e//srtiaensdarredfse.itreehn.aci/ecamtalaogte/srtaiandlsar(dSs/
esiRst/Mf7s0)c.8.9..9..6..-.6..9.c..b..-.4..e.4..c.-..8.9..7..1 .................................................................................. 8
10.3 Calibration using reagents ..2..7.5..7..4..5.6..f.4..c.7..0../i.s.o..-.1..2..6..7.7..-.2..0..1..1 ..................... 10
10.4 Calibration using SeRMs................................................................................................................... 15
11 Corrections......................................................................................................................................... 17
11.1 Line-overlap correction..................................................................................................................... 17
11.2 Background correction...................................................................................................................... 17
11.3 Drift correction................................................................................................................................... 18
11.4 Calculation of results......................................................................................................................... 18
11.5 Software requirements...................................................................................................................... 19
12 Reproducibility and repeatability..................................................................................................... 20
12.1 Fusion tests........................................................................................................................................ 20
12.2 Frequency of instrument tests.......................................................................................................... 20
12.3 Maximum allowance differences of sample holders.......................................................................20
12.4 Sample measuring positions............................................................................................................ 21
12.5 Instrument repeatability.................................................................................................................... 21
12.6 Sequential systems............................................................................................................................ 21
12.7 Dead time............................................................................................................................................ 22
12.8 Other tests.......................................................................................................................................... 22
12.9 Flow gas.............................................................................................................................................. 22
13 Accuracy determined by certified reference materials...................................................................22
13.1 Validation of synthetic calibrations.................................................................................................. 22
13.2 Validation of SeRM calibrations....................................................................................................... 22
13.3 Fresh beads of the CRMs or synthetic standards used to check SeRM calibrations..................22
14 Definitions of limits of detection...................................................................................................... 23
15 Test report.......................................................................................................................................... 23

© ISO 2011 – All rights reserved i

ISO 12677:2011(E)

Annex A (normative) Calibration range and required detection limits........................................................24

Annex B (normative) Corrections for tungsten carbide grinding media.....................................................28
Annex C (informative) Examples of fluxes/flux ratios...................................................................................30
Annex D (normative) Examples of CRM to be used to check synthetic calibrations.................................32
Annex E (normative) Examples of SeRM........................................................................................................ 38
Annex F (normative) Equation for theoretical calculations..........................................................................43
Annex G (normative) Certified reference materials (CRMs)..........................................................................44
Annex H (normative) Method of inter-element correction used to compensate for the effects of
co-existing components when using SeRM for calibration...........................................................47
Annex I (normative) Standard deviations achieved with certified reference materials..............................68
Bibliography.................................................................................................................................................... 75

iTeh STANDARD PREVIEW

(standards.iteh.ai)
ISO 12677:2011
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011

i © ISO 2011 – All rights reserved

 ISO

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO
member bodies). The work of preparing International Standards is normally carried out through ISO technical
committees. Each member body interested in a subject for which a technical committee has been established has the right
to be represented on that committee. International organizations, governmental and non-governmental, in liaison with
ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on
all matters of electrotechnical standardization.

International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.

The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the
technical committees are circulated to the member bodies for voting. Publication as an International Standard requires
approval by at least 75 % of the member bodies casting a vote.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO
shall not be held responsible for identifying any or all such patent rights.

ISO 12677 was prepared by Technical Committee ISO/TC 33, Refractories.

iTeh STANDARD
This second edition cancels and replaces the first edition (ISO 12677:2003), which has been technically revised.
Although the method in this International Standard has been considerably modified editorially and in layout, the technical

(standards.iteh.a
changes are limited. Some minor corrections have been made to certain equations. The only significant changes are a
reference to a further International Standard method (being prepared) for the
preparation of reduced materials for analysis by this standard, and instructions on how to add other constituents to
calibrations at the end of 10.2IS.1O, P12u6r7it7y:2a0n1d1 preparation of reagents.
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011

© ISO 2011 – All rights reserved v

 iTeh STANDARD PREVIEW
(standards.iteh.ai)
ISO 12677:2011
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011
 INTERNATIONAL ISO

Chemical analysis of refractory products by X-ray fluorescence

(XRF) — Fused cast-bead method

1 Scope
This International Standard specifies a method for the chemical analysis of refractory and technical ceramic raw
materials, intermediates and products, by means of the X-ray fluorescence (XRF) fused cast-bead method. Typical
materials that can be analysed by this standard are given in Clause 3. This International Standard is not applicable to non-
oxide materials, such as silicon carbides or nitrides, etc. The method is applicable to a wide range of materials containing
a wide range of elements.

NOTE 1 The presence of significant amounts of certain elements, such as tin, copper, zinc and chromium, can present difficulties in
the fusion process. In this case, the Bibliography can be referred to.

NOTE 2 Constituents at concentrations greater than 99 % (on a dried basis) are reported by difference, provided that all likely
minor constituents and any loss on ignition have been determined. These figures can also be checked by direct

iTeh STANDARD PREVIEW

determination.

2 Normative
references
(standards.iteh.ai)
The following referenced documents are IiSnOdis1p26e7n7s:a20b1le1 for the application of this document. For
dated
references, only thehttepsd:/i/tsiotanndacridtes.diteha.apip/claietaslo. g/Fstoarnduarndds/asitset/df70rce8f9e9re6-
n6c9ecsb,-4teh4ec-8l9a7te1s- t edition of the referenced document (including any
amendments2)7a5p7p45li6efs4.c70/iso-12677-2011

ISO Guide 35:2006, Reference materials — General and statistical principles for certification

ISO 565, Test sieves — Metal wire cloth, perforated metal plate and electroformed sheet — Nominal sizes of
openings

ISO 26845, Chemical analysis of refractories — General requirements for wet chemical analysis, atomic
absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES)
methods

3 Types of material
Listed below are various types of ceramic material that have been successfully analysed by this method and for which
statistical data is available (see Annex I). The list is not exhaustive but serves as a guide to those using this International
Standard for the first time.

a) High alumina  45 % Al2O3

b) Alumino-silicate 7 % to 45 % Al2O3

c) Silica  93 % SiO2

d) Zircon

e) Zirconia and zirconates

© ISO 2011 – All rights reserved 1

ISO
f) Magnesia

2 © ISO 2011 – All rights reserved

 INTERNATIONAL ISO

g) Magnesia/alumina spinel (70/30)

h) Dolomite

i) Limestone

j) Magnesia/chromic oxide

k) Chrome ore

l) Chrome-alumina

m) Alumina/magnesia spinel (70/30)

n) Zirconia-alumina-silica cast material (AZS)

o) Calcium silicates

p) Calcium aluminates

q) Magnesium silicates

A list of elemental ranges and required detection limits are given in Annex A.

NOTE 1 Some of the above material types can be accommodated for common calibrations (see 10.3.4).

NOTE 2 Reduced materials, such as silicon carbide, cannot be determined directly by this International Standard and so are not
listed above. Such materials require special methods both for loss on ignition and fusion into a bead prior to XRF analysis. Suitable
iTeh STANDARD
procedures are described in ISO 21068-1, ISO 21068-2 and ISO 21068-3 and further methods are under development by the refractory
standards system. Once reduced materials are suitably ignited and subsequently prepared as fused beads, this standard can be applied
to the rest of the procedure.
(standards.iteh.a
WARNING — Failure to pretreat reduced materiaISlsO, s12u6c7h7:2a0s11silicon carbide, properly not
only leads to erroneous results but will
ahtltspos://csataundsaerdds.aitmeha.agi/ceattaolovg/astlaunadbarldes/psilsat/tf7in0uc8m99a6l-l6o9ycbc-
r4uec4cib-8le97s1a- nd dishes.
2757456f4c70/iso-12677-2011
4 Principle
The powdered sample is fused with a suitable flux to destroy its mineralogical and particulate composition. The
resultant melt is cast into the shape of a glass bead which is then introduced into an XRF spectrometer. The intensities of
the fluorescent X-rays of the required elements in the bead are measured and the chemical composition of the sample is
analysed by reference to previously determined calibration graphs or equations and applying corrections for inter-element
effects. The calibration equations and inter-element corrections are established from beads produced using pure reagents
and/or series reference materials (SeRMs), prepared in the same way as the samples. Certified reference materials
(CRMs) may be used providing they meet all the requirements of 10.2.2 and 10.4.1.

Because of the universality of the fused cast-bead technique, various fluxes and modes of calibration are permitted,
providing they have been demonstrated as being able to meet certain criteria of repeatability, sensitivity and accuracy.
Provided that a laboratory's own methods conform to all the various criteria set down, they will be accepted as
conforming to this International Standard.

5 Apparatus

5.1 Fusion vessels, of a non-wetted platinum alloy (Pt/Au 95 %/5 % is suitable). Lids, if used, shall be of a
platinum alloy (not necessarily non-wetted).

NOTE A useful guide to the care of platinum is given in Reference [5] of the Bibliography.

5.2 Casting moulds, of a non-wetted platinum alloy (Pt/Au 95 %/5 % is suitable).

NOTE Vessels that serve both as fusion vessels and casting moulds can be used.

© ISO 2011 – All rights reserved 3

 ISO

5.3 Heat reservoir for casting mould (optional), required in special circumstances when using moulds of small
sizes, so that the mould does not cool too rapidly when removed from the furnace. A small piece of flat refractory
material is suitable, e.g. a piece of sillimanite batt with dimensions 10 mm  50 mm  50 mm.

5.4 Air jet (optional), required to cool the mould rapidly. This may be any device whereon a narrow jet of air can be
directed to the centre of the base of the casting dish. A convenient way of doing this is to use the base of a Bunsen burner
without a barrel to serve as an air jet.

NOTE In most cases, it is very important to cool the melt rapidly. This is necessary to obtain a homogeneous bead and to free
the melt from the dish.

A water-cooled metal plate may also be used.

5.5 Fusion apparatus, electric resistance furnaces or high-frequency induction furnaces that may be heated up to a
fixed temperature of between 1 050 °C and 1 250 °C may be used.

5.6 Automatic fusion apparatus, for use in automatic bead preparation (see 9.2) where required.

5.7 Balance, capable of weighing to 0,1 mg.

5.8 Mechanical mixer, that moves in a linear or rotary way.

NOTE Vibratory mixers cannot be used as they induce segregation.

Sample grindin g
6 i Teh STANDARD PREVIEW
This International Standard shall s(tasrttwaithnadlaaborradtosry.istamephle..ai)
NOTE 1 Bulk sampling is not within the scope of this method but can be found in ISO 26845.
ISO 12677:2011
The sample shall be hgttrposu://nstdanudsarindgs.itteuhn.agi/sctaetanlocg/asrtabniddaer.dsT/shiset/fa7p0pc8ro99p6ri-
a6t9ecbc-o4rer4ecc-t8io97n1s- for tungsten carbide (and its binder if necessary) shall be applied
to27lo5s7s45o6nf4icg7n0i/tisioon-1a26n7d7a-2n0a1l1ysis figures in accordance with Annex B.

NOTE 2 It is permissible to apply the sample grinding methods cited in conventional chemical methods for the classes of materials
covered. However, the tungsten carbide method is the preferred method.

The maximum particle size shall be 100 µm.

NOTE 3 The purpose of grinding is to obtain a sample sufficiently fine to be fused easily but below a set limit of introduced
contamination. But for certain samples that are difficult to fuse (e.g. chrome ores), finer grinding to less than 60 µm might be
necessary.

One of the following two methods shall be used to obtain the required particle size.

a) For mechanical grinding devices, establish what grinding times are sufficient to grind the various samples to be
analysed to the correct fineness and thereafter apply these minimum times for grinding. In order to establish
grinding times, use the mechanical grinder to prepare typical materials analysed for progressively increasing lengths
of time of 2 min. Sieve each ground sample through a 100 µm sieve until a grinding time is reached where the
entire sample passes through the sieve. Then use this time for that material or the longest time of any material
analysed, if applied to all materials. When grinding hard materials, such as chromite, sieving shall be used, but this
might induce segregation. Therefore, after sieving, the sample shall be mixed thoroughly by stirring or tumbling
prior to transferring to a sample tube. Because heavier minerals can segregate on standing, it is advisable to stir the
sample once more, prior to weighing out.

b) After hand-grinding for 20 s, sieve the ground powder through a sieve of 100 µm aperture, in accordance with ISO
565. Regrind any material remaining on the sieve for a further 20 s, sieve and repeat this procedure until the whole
of the sample passes through the sieve. Transfer the sample to a suitable container and mix for 1 min, using a
mechanical mixer such as a vertical linear mixer.

© ISO 2011 – All rights reserved 3

 ISO

NOTE 4 As the object of the exercise is to obtain a sample suitable for fusion, and not to test the fineness of the sample
itself, method a) is generally preferred.

7 Loss on ignition (and/or drying)

Loss on ignition shall be carried out in accordance with ISO 26845.

8 Flux

8.1 Choice of flux and ratio of flux to sample

8.1.1 One of the advantages of the XRF fused cast-bead method is that a wide variety of fluxes may be chosen. For a
given calibration, the same flux shall be used throughout. The conditions given in 8.1.2 to 8.1.9 shall be met for any flux
and flux/sample ratio used.

NOTE Fluxes used with success in the analysis of refractory materials are given in Annex C. Prefused fluxes have the
advantage of lower moisture contents.

8.1.2 Under the conditions of preparation used, the sample shall be totally dissolved by the flux and shall not come
out of solution during the casting procedure.

8.1.3 The resulting bead shall be transparent and show no signs of devitrification.

8.1.4 At a reasonably high

i Tunetinhg tiSmeT(A20N0 sD), tAhe RreqDuirePd
c o

d
ReteEctiVonIliEmitWs shall be achieved for the elements determined. Detection limits are
(dseftinaednads ian Crldausse.i1t4eahnd.laistie)d in Annex A.
8.1.5 At a reasonable counting time (200 s), the counts recorded for each element determined shall give
the required standard of repeatability for the determISiOna1t2io6n77o:2f0t1h1at element (as measured according to 12.1
and defined as in G.1). https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
2757456f4c70/iso-12677-2011
8.1.6 A heavy element absorber may be incorporated into the flux provided that:

a) it does not reduce sensitivities so that conditions 8.1.4 and 8.1.5 are not met;

b) the heavy element does not have a line overlap with any of the elements to be determined.

8.1.7 If volatile components are to be determined, then a flux of sufficiently low melting point, which permits a
fusion temperature low enough to retain that element during fusion, shall be used.

8.1.8 For the determination of elements that alloy with platinum (e.g. lead, zinc, cobalt), the melting point shall be
such as to allow fusion below the temperature at which this reaction occurs (1 050 °C).

8.1.9 The flux shall be pure with respect to the analytes determined. As the flux to sample ratio is greater than 1 (see
Annex C), impurities to the flux can influence the measured result negatively. The greater the ratio of the flux to sample,
the greater the influence. Therefore, the permitted levels of impurity of analyte levels in the flux shall be no more than:

D/(3R)

where

R is the ratio of flux to sample;

D is the detection limit claimed for the determination of the analyte element.

Most reagents sold by reputable manufacturers as “flux” grade quality meet this requirement but an analysis shall be
obtained for each batch of flux supplied. Recheck calibrations when batches of flux are changed.

4 © ISO 2011 – All rights reserved

 ISO

8.2 Compensations for moisture in flux

The flux contains a certain amount of moisture, which shall be compensated for in one of two ways.

a) Calcine the entire quantity of flux required overnight at 700 °C immediately before it is used for analysis, and store
it in a desiccator.

b) Carry out duplicate losses on ignition on 1 g portions of well-mixed flux for each kilogram of flux used. Carry out
the calcining at the normal fusion temperature for 10 min, or the normal fusion time, whichever is the greater [see
9.1.2 f)]. Store the flux in a tightly sealed container except when in use. The loss on
ignition, expressed as a percentage by mass, wL, is then used to calculate a flux factor, F [see Equation (1)],
which is in turn used to calculate the mass of the unignited flux needed to produce the required mass of flux on the
ignited basis (F times the required mass of ignited flux  required mass of
unignited flux). Carry out this loss on ignition at weekly intervals or for each kilogram of flux used, whichever is the
more frequent.

100
F (1)
100  wL

NOTE The compensation might be unnecessary if the loss on ignition is 0,50 % or lower (prefused fluxes).

9 Fusion casting procedures

9.1 Fusion of samp l i TeseahndScaTstAingNoDf beAadRs D PREVIEW

9.1.1 Choice of
procedure (standards.iteh.ai)
At several of the stages, a choice of procedIuSrOes12is67g7iv:2e0n1.1Once a choice has been made, the procedure shall
be adhered to throughhttopus:t/,/sutannldeasrsdsa.itetoh.taai/lcraetacloagli/bstraantdioarndsis/sicsta/fr7r0iec8d9o9u6-
t.69cb-4e4c-8971-
2757456f4c70/iso-12677-2011
9.1.2 Requirements

Before fusing the samples and casting the beads, the following requirements shall be satisfied.

a) Duplicate or single beads may be prepared; the number used shall be stated in the test report.

b) The total mass of sample and flux shall be chosen for the particular casting-mould type used, and this mass shall
always be the same.

c) The ratio, R, by mass of the flux to that of the sample, shall be the same for the material type analysed.

d) The melts produced shall be visually homogeneous.

e) There shall be no measurable loss of any component from the sample during fusion, e.g. loss by reduction or
evaporation (excessive temperature).

f) The variations of any loss of flux shall be minimized by using consistent times and temperature during fusion in the
preparation of both calibration standards and samples.

g) The sample shall not be contaminated in any way by the sample preparation by any constituent being measured on
that sub-sample. This can either be established by knowing the composition of the grinding media or by measuring
the amount of contamination added in grinding pure materials or materials of known composition.

h) The beads produced shall be free from blemishes on the chosen measuring surface.

i) If the top surface of the bead is to be used for analysis, it shall be either convex or flat and be symmetrical across
any diameter.

© ISO 2011 – All rights reserved 5

 ISO

j) Standard glass beads of known composition shall be prepared in the same way as sample beads.

k) If moulds become distorted in use, they shall be reshaped by pressing in a suitable former. If the bottom (flat)
surface of the bead is used for analysis, the top surface of the mould shall also be kept flat and free from blemishes.

l) Beads shall be infinitely thick for the X-ray wavelengths measured. For line parameters used in refractory analysis,
infinite thickness is normally achieved.

NOTE 1 Duplicate beads are preferable to single beads. However, if all the oxides given in Annex A are determined for the
relevant class of material, an analytical total will be achieved, which acts as a check on the result of analysis.

NOTE 2 Fusions at 1 200 °C will volatilize certain elements, e.g. sulfur, even when an oxidizing agent is used.

9.1.3 Conversion of the sample to bead form

The sample to be analysed may be converted into bead form in a number of ways.

a) Calcine the sample to constant mass at (1 025  25) °C, desiccate and allow to cool to room temperature. Weigh it in
the fusion dish and record the mass, m, to the nearest 0,000 1 g. Weigh the flux samples as described in 8.2.

b) Take a sample of uncalcined flux of mass R · m· F and mix thoroughly with the sample, where F is the flux factor
determined in 8.2 b). Dry the sample to constant mass at (110  10) °C. Weigh in the fusion dish and record, to the
nearest 0,000 1 g, the sample mass
iTeh STANDARD PREVIEW
m 1


wL
100
%
 (standards.iteh.ai)

 

where wL is the percentage by mass of sample IlSoOst 1d2u6r7in7g:20ig1n1ition at (1 025  25) °C.
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
As in item a), the sample may be mixed with e2i7th5e7r45c6afl4ccin70e/disoo-r12u6n7c7a-l2c0in1e1d flux.

NOTE 1 For problems affecting the fusion of materials containing chromium oxide or zirconia, see 9.4.

Fuse the sample and flux together, with occasional swirling, until the sample is seen to be dissolved and the melt
homogeneous.

During the initial part of the fusion process, fuse carbonate samples slowly to avoid “spurting” (ejection of sample or
flux).

NOTE 2 In the case of limestone, dolomite and magnesium carbonate, it is preferable to weigh out an amount of the dried
sample, corrected for loss on ignition, for fusion.

NOTE 3 The fusion temperature can be specified according to material type.

9.1.4 Manual casting of beads

9.1.4.1 General

The final part of the fusion process consists of heating the fusion vessel, the mould and the heat reservoir (if used) in a
muffle furnace (1 200  50) °C for 5 min. Then cast the beads using one of the following methods.

a) Outside the furnace: after 5 min at (1 200  50) °C, remove the heat reservoir (5.3) from the furnace (5.5) and
place it on a horizontal surface. Immediately place the mould onto the heat reservoir. Then remove the lid from the
fusion vessel and immediately pour the melt into the casting mould (5.2).

6 © ISO 2011 – All rights reserved

 ISO

b) In the furnace: after 5 min at (1 200  50) °C, remove the lid from the fusion vessel (5.1) and pour the melt into
the mould (5.2) inside the furnace (5.5), ensuring that as much of the melt is transferred to the mould as possible.
Remove the mould from the furnace and place it on a horizontal surface.

c) Combined fusion mould: after 5 min at (1 200  50) °C, remove the fusion vessel from the furnace. If a
releasing agent is not used, the melt can rise up the sides of the vessel. Therefore, careful manipulation of the
vessel is required to work the melt into the mould part of the vessel. Then put the fusion vessel on a graphite brick
to cool.

d) Mould heated over a burner: after preparation of the melt at the fusion temperature and the time chosen for that
type of material, pour the melt into the preheated mould and turn the burner off. Allow the melt to solidify and use
an air jet (5.4), as described in 9.1.4.2., or a water-cooled metal plate to accelerate the cooling process.

When the top surface of the bead is used [not c)] for subsequent analysis, a rippled surface produced in the casting
process can lead to erroneous results. In order to avoid this rippled effect, the melt should be poured into the mould at a
point nearer to the edge of the mould than the centre. When using top surfaces, in order to maintain a uniform curvature
on the top surface, it is necessary to get as much of the melt into the casting mould as possible, so as to achieve consistent
bead masses.

NOTE Most refractory materials contain small amounts (as low as 0,1 %) of Cr 2O3, ZrO2, and -Al2O3 which, if the fusion is not
completed at (1 200  50) °C, will cause the melt to devitrify. However, if experience shows that de- vetrification is not a problem,
samples can be cast in furnaces at as low as (1 050  25) °C, providing calibration standards are prepared the same way.

Small amounts of lithium iodide or iodate, or ammonium iodate, may be added to the melt to assist in preventing
iTeh STANDARD
cracking of fused beads on cooling and to aid release from the mould. Iodine does have a small line overlap with
TiK, so if low levels of TiO2 are to be determined, corrections may be needed. If small amounts of releasing agents are
(standards.iteh.a
to be used, then all samples and any calibration standards prepared should include the same releasing agent added in the
same quantity and at the same stage of bead preparation. Maintaining a good polish on the casting
moIuSldOs1s2h6o77u:l2d01o1bviate the need for such agents, but there are further
problems
o s s i b l with
e to sample
u s e htsNtpcHs:oBr
//nor
sttaLiBr
anidbut
nairitndshould
gs.ihtebe
igh.hai/lceavtaellosg/ostfaCndra2rOds3/.siIstt/ifs70acl8s9o96p-
6 9 c b - 4 e4 c- 8 9 71 - 4
noted that there is a Br L line nea2r75th7e45A6fl4Kc70/ilsino-e1.26H7i7g-h20a1m1 ounts of Br may cause
serious line-overlap problems when measuring low alumina concentrations and corrections may need to be applied. For
low levels
of Al2O3, iodide or iodate is recommended. The amount of NH 4Br or LiBr added should not exceed 1 mg per gram of
sample. If a chromium tube is used, the effect of bromine will be greater; therefore, the effect of bromine on aluminium
should be checked before using a bromine-based releasing agent.

9.1.4.2 Cooling of beads

If no air jet is used, allow the mould to cool on a horizontal surface. If the air jet is used, transfer the mould to it when the
melt has cooled from red heat. The melt may be molten or solid at this stage; if it is molten and top surfaces are to be
measured, ensure that the support over the air jet is horizontal.

Hold the dish in a horizontal position above the air jet so that the air is directed onto the centre of the base of the mould.
When the bead has solidified and released itself, turn off the air jet.

NOTE It might be necessary to encourage the release of the beads at this stage by gently tapping the casting mould on a solid
surface.

9.2 Automatic bead preparation

Automatic bead equipment may be used as an alternative to 9.1.4, and shall be in accordance with 9.1.2 and 12.1.

9.3 Storage

Beads can deteriorate because of adverse temperature and humidity conditions. Therefore they should be stored in such a
manner as to avoid hydration and contamination.

© ISO 2011 – All rights reserved 7

 ISO

The measuring surfaces of beads shall be thoroughly cleaned before use, or possibly polished after long-term storage.

NOTE Reported sources of contamination are as follows:

a) sulfur from vacuum oil in the spectrometer or from the laboratory atmosphere;
b) sodium and chlorine from the atmosphere if the laboratory is near the sea;
c) potassium from cigarette smoke;
d) contamination from the surface of plastic bags that may be used for storing the beads.

9.4 Special problems

Samples with high chromium oxide or zirconia content can create problems during fusion. Chromium oxide is difficult to
dissolve in the molten flux and zirconia also suffers from this problem to a lesser degree but can also cause
devitrification on cooling, even after complete dissolution. Before establishing methods of fusion for these materials,
fusion trials are required to establish a method for preparing the samples of the highest content of these oxides, likely to
be encountered by the laboratory. In these trials, optimum flux, sample/flux ratio, temperatures and fusion times need to
be established. Normally, different procedures will be required for chrome-bearing material, zircon and zirconia.

NOTE Even if the storage conditions in 9.3 are observed, beads containing high levels of ZrO 2 tend to absorb moisture onto the
surface more than other beads. This causes increased backgrounds on light elements. The problem can be cured by drying the bead
overnight at 220 °C.

10 Calibration
iTeh STANDARD PREVIEW
(standards.iteh.ai)
10.1 Calibration standards
ISO 12677:2011
The calibration equations ahnttdps:i/n/stteanr-
dealredms.ietenht.aic/coartraelocgt/isotannsdaardrse/siests/ft7a0bcl8is9h9e6-d69ucsbi-n4ge4cb-e8a9d71s- produced
with pure reagents or series reference materials (SeRM27s5).74T5h6ef4cS7e0R/isMo-s12a6r7e7-d2i0ff1e1rent from
certified reference materials (CRMs) which validate the calibrations using pure reagents. CRMs and SeRMs are shown in
Annexes D and E,
respectively. The series of CRMs meeting the requirements of 10.2.2 and 10.4.1 may be regarded as SeRMs.

10.2 Reagents and series reference materials (SeRMs)

10.2.1 Purity and preparation of reagents

The reagents used to prepare the standard beads for cations shall be pure oxides or carbonates of at least 99,95 % purity
(excluding moisture or CO2) for minor constituents and of at least 99,99 % purity for silica and alumina. For the
calibration of elements such as sulfur or phosphorus which do not form stable oxides or carbonates, some guarantee of
stoichiometry is required.

It is essential that the reagents be free of (or corrected for) the presence of water (and, in the case of oxides, carbon
dioxide) when weighed out for fusion. Also, the reagents shall be in a known oxidation state.

The procedures listed ensure that the correct oxidation state is obtained. The reagents used for calibration shall be of high
purity and, when fresh batches of reagents are purchased, they shall be compared with previous batches. Therefore, a
fresh bead shall be made at the highest level of content calibrated and measured against a similar bead prepared from the
previous batch of the same reagent. The intensities achieved for elements other than those in the reagent shall not differ
by more than the detection limit for that element.

In order to obtain the reagents of a known stoichiometry in terms of content, they shall be treated before use as follows.

a) Silica, alumina and magnesia: determine the loss on ignition as follows. Calcine 5 g of the material, as received,
at (1 200  50) °C and keep them at this temperature for a minimum of 30 min. Cool in a

8 © ISO 2011 – All rights reserved

 ISO

desiccator to room temperature and reweigh. After allowing for this loss, weigh the appropriate amount of the
uncalcined material to prepare the standard bead.

b) Manganese oxide (Mn3O4), titanium(IV) oxide and nickel(II) oxide, chromium(III) oxide, zirconia, hafnia, ceria,
yttria, lanthia and other rare earths. Calcine 5 g of the material at (1 000  25) °C and keep them at this temperature
for a minimum of 30 min. Cool in a desiccator to room temperature before use.

NOTE 1 Rare earths absorb water and carbon dioxide from the atmosphere.

c) Iron(III) oxide, tin(IV) oxide, cobalt oxide (Co3O4) and lithium orthophosphate. Calcine 5 g of the material at (700
 25) °C and keep them at this temperature for a minimum of 30 min. Cool in a desiccator to room temperature
before use.

d) Calcium carbonate, barium and strontium carbonates, potassium and sodium carbonates, tungstic oxide, gallium
oxide, lithium sulfate. Dry the material at (230  20) °C before use. Cool in a desiccator to room temperature before
use.

Other oxides may be added to calibrations, as long as the oxides or their compounds used for the calibration are of a
sufficient purity and of guaranteed stoichiometry by heat treatment, etc. In addition, problems regarding volatility of that
element/oxide in fusion are taken into account, as well as any tendency for the element to alloy with the fusion vessel
during the fusion process. A list of useful references to deal with these points is given in References [5] to [9]. This list is
not exhaustive and other references may also be of use. In addition, the calibrations should meet the other requirements
of this International Standard.

NOTE 2 A 2 h treatment is usually sufficient for drying.

iTwillebhe inStrToduAceNd aDs aAcoRntaDminPanRt
Tungsten carbide (WC) if
EthiVs
I E Wis used for grinding. Laboratories
m e dia (standards.iteh.a
using tungsten carbide for sample grinding should calibrate for WO 3 in order to monitor its presence in samples, and
hence correct the analysis and the loss on ignition for WC contamination (see Annex B). Unlike the wet chemical
analysis procedure, X-ray fluorescence determinations are not subject to any significant
cross interference due to tungsten and furtheISrmOo1r2e67th7e:20c1o1ntaminating tungsten may be easily monitored.
https://standards.iteh.ai/catalog/standards/sist/f70c8996-69cb-4e4c-8971-
If tungsten contamination exceeds 0,52%75,7c4o56rrfe4cc7ti0o/nisso-s1h26a7ll7b-2e0a1p1 plied. See Annex B.

10.2.2 Preparation of series reference materials (SeRMs)

SeRMs may be used for calibration instead of synthetic standards. The SeRMs shall cover the following points.

a) SeRMs shall satisfy the requirements of ISO Guide 35:2006.

b) SeRMs shall be formulated to provide regular intervals of concentration.

c) The variation in concentrations of the oxides of the SeRMs shall be independent of each other.

d) There shall be a minimum of ten SeRMs in a series.

e) The SeRMs shall be homogeneous.

f) Full statistics of between- and within-laboratory variation shall be provided in their certification.

g) The chemical analyses shall be checked by a second technique [e.g. inductively coupled plasma (ICP)].

© ISO 2011 – All rights reserved 9