prEN 15991

SLOVENSKI STANDARD
01-september-2024
Preskušanje keramičnih surovin in keramičnih materialov - Neposredno
določevanje masnih frakcij nečistoč v prahu in zrnih silicijevega karbida z optično
emisijsko spektroskopijo in induktivno sklopljeno plazmo z elektrotermičnim
uparevanjem (ETV-ICP-OES)
Testing of ceramic raw materials and ceramic materials - Direct determination of mass
fractions of impurities in powders and granules of silicon carbide by inductively coupled
plasma optical emission spectrometry with electrothermal vaporisation (ETV-ICP-OES)
Prüfung keramischer Roh- und Werkstoffe - Direkte Bestimmung der Massenanteile von
Spurenverunreinigungen in pulver- und kornförmigem Siliciumcarbid mittels optischer
Emissionsspektroskopie mit induktiv gekoppeltem Plasma und elektrothermischer
Verdampfung (ETV-ICP-OES)
Essai des matières premières céramiques et des matériaux céramiques - Détermination
directe des fractions massiques d'impuretés dans les poudres et les granulés de carbure
de silicium par spectroscopie d'émission optique avec plasma induit par haute fréquence
avec vaporisation électrothermique (ETV-ICP-OES)
Ta slovenski standard je istoveten z: prEN 15991
ICS:
81.060.10 Surovine Raw materials
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

DRAFT
EUROPEAN STANDARD
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2024
ICS 81.060.10 Will supersede EN 15991:2015
English Version
Testing of ceramic raw materials and ceramic materials -
Direct determination of mass fractions of impurities in
powders and granules of silicon carbide by inductively
coupled plasma optical emission spectrometry with
electrothermal vaporisation (ETV-ICP-OES)
Essai des matières premières céramiques et des Prüfung keramischer Roh- und Werkstoffe - Direkte
matériaux céramiques - Détermination directe des Bestimmung der Massenanteile von
fractions massiques d'impuretés dans les poudres et Spurenverunreinigungen in pulver- und kornförmigem
les granulés de cabure de silicium par spectroscopie Siliciumcarbid mittels optischer
d'émission optique avec plasma induit par haute Emissionsspektroskopie mit induktiv gekoppeltem
fréquence avec vaporisation électrothermique (ETV- Plasma und elektrothermischer Verdampfung (ETV-
ICP-OES) ICP-OES)
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 187.
If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations
which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.

This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC
Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
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United Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2024 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 15991:2024 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Principle . 4
5 Spectrometry . 5
6 Apparatus . 6
7 Reagents and auxiliary material . 7
8 Sampling and sample preparation . 8
9 Calibration . 8
10 Procedure. 9
11 Emission lines and working range .10
12 Calculation of the results and evaluation .10
13 Reporting of results .10
14 Precision .11
14.1 Repeatability .11
14.2 Reproducibility .11
15 Test report .11
Annex A (informative) Results of interlaboratory study .12
Annex B (informative) Emission lines and working range .17
Annex C (informative) Possible interferences and their elimination .19
Annex D (informative) Information regarding the evaluation of the uncertainty of the mean
value .22
Annex E (informative) Commercial certified reference materials .23
Annex F (informative) Calibration using aqueous solutions and powdered calibration
samples .24
Bibliography .27

European foreword
This document (prEN 15991:2024) has been prepared by Technical Committee CEN/TC 187 “Refractory
products and materials”, the secretariat of which is held by BSI.
This document is currently submitted to the CEN Enquiry.
This document will supersede EN 15991:2015.
1 Scope
This document defines a method for the determination of the mass fractions of the elements Al, Ca, Cr,
Cu, Fe, Mg, Ni, Ti, V and Zr in powdered and granular silicon carbide.
Dependent on element, emission lines, plasma conditions and sample mass, this test method is applicable
for mass fractions of the above trace contaminations from about 0,1 mg/kg to about 1 000 mg/kg, after
evaluation also from 0,001 mg/kg to about 5 000 mg/kg.
NOTE 1 Generally for optical emission spectrometry using inductively coupled plasma and electrothermal
vaporization (ETV-ICP-OES) there is a linear working range of up to four orders of magnitude. This range can be
expanded for the respective elements by variation of the sample mass or by choosing emission lines with different
sensitivity.
After adequate verification, this document is also applicable to further metallic elements (excepting Rb
and Cs) and some non-metallic contaminations (like P and S) and other allied non-metallic powdered or
granular materials like carbides, nitrides, graphite, soot, coke, coal, and some other oxidic materials (see
[1], [4], [5], [6], [7], [8], [9] and [10]).
NOTE 2 There is positive experience with materials like, for example, graphite, boron carbide (B C), silicon
nitride (Si N ), boron nitride (BN) and several metal oxides as well as with the determination of P and S in some of
3 4
these materials.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
No terms and definitions are listed in this document.
4 Principle
For the determination of impurities in silicon carbide, ICP-OES is a suited method. The classic application
of ICP-OES is based on the nebulization of sample solutions. For silicon carbide, sample digestion by wet-
chemical methods is required to obtain these sample solutions, for example by melt-fusion or
acid/pressure-decomposition. These sample digestion procedures are time-consuming, require the use
of hazardous chemicals, deteriorate the detection limits due to the dilution of the sample and the
possibility of introduction of impurities as well as analyte losses represents a source of systematic errors.
With ETV-ICP-OES, the impurities are measured directly from the powdered silicon carbide sample, thus
avoiding sample digestion and the associated disadvantages. Compared to wet-chemical ICP-OES
methods, ETV-ICP-OES requires more effort for method development and is therefore particularly
suitable when many samples of one matrix are to be measured with high sample throughput and with
high detection sensitivity.
In ETV-ICP-OES, sample introduction by nebulization of liquids is replaced by the electrothermal
vaporization of solid samples at high temperatures in the graphite tube furnace of the ETV-system.
The sample material, crushed if necessary, is evaporated in an argon carrier-gas stream in a graphite boat
in the graphite tube furnace of the ETV-system. A suitable design of the furnace (see Figures 1 and 2) and
an optimized gas flow in the transition area between graphite tube and transport tube (see Figure 3)
ensure that the sample vapour is transferred into a form that is transported to the ICP-OES with almost
no losses (see [5], [6], [7], [8], [10]). Elements, for example titanium or zirconium, forming refractory
carbides that are incompletely or not evaporating need to be converted in the graphite tube furnace into
a chemical form which easily evaporates. For this purpose, a suitable reaction gas (halogenating agent)
is mixed to the argon carrier-gas stream (see Figures 1 and 2) which converts the carbides into volatile
halides (see [1], [3], [5] and [10].)
The evaporation products containing the element traces are transported by the transport tube as dry
aerosol to the ICP-torch, injected into the plasma and there excited for the emission of optical radiation
(see Figure 2).
5 Spectrometry
Optical emission spectrometry is based on the generation of line spectra of excited atoms or ions, where
each emission line is associated with an element and the line intensities are proportional to the mass
fractions of the elements in the analysed sample.
In a simultaneous emission spectrometer in, for example Paschen-Runge- or Echelle-configuration, the
optical radiation is dispersed. The intensities of suited emission lines or background positions are
registered with applicable detectors like photomultipliers (PMT), charge coupled devices (CCD),
complementary metal-oxide semiconductor (CMOS), charge injection devices (CID), and serial coupled
devices (SCD). By comparison of the intensities of the element-specific emission lines of the sample with
calibration samples of known composition, the mass fractions of the trace elements in the sample are
determined.
Key
1 graphite tube with graphite boat and sample 5 bypass gas (Ar)
2 carrier gas (Ar) 6 dry aerosol
3 reaction gas (CCl2F2) 7 to the ICP-torch
4 shield gas (Ar)
Figure 1 — Schematic representation of the ETV gas flows
Key
1 graphite tube furnace 6 bypass-gas (Ar)
2 pyrometer 7 dry aerosol to ICP-OES
3 carrier gas (Ar) + reaction gas (CCl2F2) 8 transport tube
4 solid sample in graphite boat 9 inductively coupled plasma of the OES
5 evaporation products 10 power supply for graphite tube furnace
Figure 2 — Schematic design of the ETV-system/ICP-OES coupling (example)

Key
1 alumina transport tube 5 carrier gas (Ar + CCl F ) and evaporation products of the sample
2 2
2 alumina transition ring 6 bypass gas (Ar)
3 nozzle of graphite tube 7 dry aerosol in laminar flow to ICP-OES
4 graphite tube
Figure 3 — Schematic design of the transition area between graphite-tube and transport-tube
(example)
NOTE Figure 1, Figure 2 and Figure 3 show a commercially available ETV-system.
6 Apparatus
6.1 Common laboratory instruments and la
...