CEN/TR 10354:2011
(Main)Chemical analysis of ferrous materials - Analysis of ferro-silicon - Determination of Si and Al by X-ray fluorescence spectrometry
Chemical analysis of ferrous materials - Analysis of ferro-silicon - Determination of Si and Al by X-ray fluorescence spectrometry
This Technical Report describes a X-ray fluorescence (XRF) spectrometric method for the determination of Si and Al contents in Ferro Silicon materials.
The method is applicable to:
- Si content between 40 and 90 %;
- Al content between 0,5 and 6 %.
The Technical Report specifies the general requirements for analysis by X-ray fluorescence spectrometry and the preparation of the test sample.
The correction of the spectrometric measurement from spectral interferences on the analytical lines used is essential. This Technical Report is valid for the analytical lines:
- Si Kα 7.126 (for element contents between 45 and 90 %);
- Al Kα 8.339 (for element contents between 0,8 and 6 %);
- Fe Kα 1.937 (for element contents between 10 and 58 %).
NOTE For matrix matching purposes, iron is included in the analytical program to be prepared.
Within the conditions here above, spectral interferences don’t need to be calculated.
Chemische Analyse von Ferrolegierungen - Analyse von Ferrosilizium - Bestimmung von Si und Al in Ferrolegierungen durch Röntgenfluoreszenzanalyse
Analyse chimique des matériaux ferreux - Analyse du ferro-silicium - Détermination de Si et Al dans le ferro-silicium par spectrométrie de fluorescence de rayons X
Le présent Rapport Technique décrit une méthode par spectrométrie de fluorescence de rayons X pour la
détermination de la teneur en Si et Al des alliages ferro-silicium.
La méthode est applicable aux :
- teneurs en Si comprises entre 40 et 90 % ;
- teneurs en Al comprises entre 0,5 et 6,0 %.
La correction de la mesure spectrométrique pour les interférences spectrales affectant les raies analytiques
utilisées est essentielle. Le présent Rapport Technique n’est applicable que pour les raies analytiques :
- Si Ka 7.126 (pour des teneurs comprises entre 45 et 90 %) ;
- Al Ka 8.339 (pour des teneurs comprises entre 0,8 et 6,0 %) ;
- Fe Ka 1.937 (pour des teneurs comprises entre 10 et 58 %).
NOTE Le fer est inclus dans le programme analytique à mettre en oeuvre pour des raisons d’effets de matrice.
Dans les conditions définies ci-dessus, les interférences spectrales n’ont pas besoin d’être calculées.
Kemična analiza železovih zlitin - Analiza ferosilicija - Določevanje Si in Al v ferosiliciju s fluorescenčno spektrometrijo
To tehnično poročilo opisuje rentgensko fluorescenčno (XRF) spektrometrično metodo za določevanje Si in Al v ferosilikonskih materialih. Ta metoda se uporablja za: vsebnost Si med 40 % in 90 %; vsebnost Al med 0,5 % in 6 %. Korekcija spektrometričnih meritev zaradi spektralnih interferenc na uporabljenih analitičnih linijah je bistvenega pomena. To tehnično poročilo je potrjeno za analitične linije: Si Kα 7.126 (za vsebnost elementa med 45 % in 90 %); Al Kα 8.339 (za vsebnost elementa med 0,8 % in 6 %); Fe Kα 1.937 (za vsebnost elementa med 10 % in 58 %).
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
01-januar-2012
.HPLþQDDQDOL]DåHOH]RYLK]OLWLQ$QDOL]DIHURVLOLFLMD'RORþHYDQMH6LLQ$OY
IHURVLOLFLMXVIOXRUHVFHQþQRVSHNWURPHWULMR
Chemical analysis of ferrous materials - Analysis of ferro-silicon - Determination of Si and
Al by X-ray fluorescence spectrometry
Chemische Analyse von Ferrolegierungen - Analyse von Ferrosilicium - Bestimmung von
Si und Al in Ferrolegierungen durch Röntgenfluoreszenzanalyse
Analyse chimique des matériaux ferreux - Analyse du ferro-silicium - Détermination de Si
et Al dans le ferro-silicium par spectrométrie de fluorescence de rayons X
Ta slovenski standard je istoveten z: CEN/TR 10354:2011
ICS:
77.040.30 Kemijska analiza kovin Chemical analysis of metals
77.080.10 Železo Irons
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
TECHNICAL REPORT
CEN/TR 10354
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
November 2011
ICS 77.080.10
English Version
Chemical analysis of ferrous materials - Analysis of ferro-silicon
- Determination of Si and Al by X-ray fluorescence spectrometry
Analyse chimique des matériaux ferreux - Analyse du ferro- Chemische Analyse von Ferrolegierungen - Analyse von
silicium - Détermination de Si et Al dans le ferro-silicium Ferrosilizium - Bestimmung von Si und Al in
par spectrométrie de fluorescence de rayons X Ferrolegierungen durch Röntgenfluoreszenzanalyse
This Technical Report was approved by CEN on 24 April 2011. It has been drawn up by the Technical Committee ECISS/TC 102.
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, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 10354:2011: E
worldwide for CEN national Members.
Contents Page
Foreword .3
1 Scope .4
2 Principle .4
3 Reagents .5
4 Apparatus .5
5 Safety precautions .5
6 Sampling .5
7 Procedure .6
8 Expression of results .7
9 Precision .7
10 Test report .8
Annex A (informative) Test samples used for the precision test .9
Annex B (informative) Detailed results obtained from the precision test . 10
Annex C (informative) Calibration curve - Preparation of oxide beads with pure metals and/or
oxides . 17
Bibliography . 19
Foreword
This document (CEN/TR 10354:2011) has been prepared by Technical Committee ECISS/TC 102 “Methods
of chemical analysis for iron and steel”, the secretariat of which is held by SIS.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
1 Scope
This Technical Report describes a X-ray fluorescence (XRF) spectrometric method for the determination of Si
and Al contents in ferro-silicon materials.
The method is applicable to:
Si contents between 40 % and 90 %;
Al contents between 0,5 % and 6 %.
The correction of the spectrometric measurement from spectral interferences on the analytical lines used is
essential. This Technical Report is valid for the analytical lines:
Si Kα 7.126 (for element contents between 45 % and 90 %);
Al Kα 8.339 (for element contents between 0,8 % and 6 %);
Fe Kα 1.937 (for element contents between 10 % and 58 %).
NOTE For matrix matching purposes, iron is included in the analytical program to be prepared.
Within the conditions here above, spectral interferences don’t need to be calculated.
2 Principle
Preparation of oxide beads, comprising the oxidation of the sample with strontium nitrate and its melting with
lithium tetraborate, in a platinum crucible.
The beads are irradiated by an X-ray beam of suitable energy. The secondary X-rays produced are dispersed
by means of crystals and the corresponding intensities are measured by detectors at the selected
wavelengths.
The contents of the relevant elements are determined by relating the measured intensities of unknown
samples to calibration curves recorded with beads prepared with certified reference materials.
Fixed channel or sequential systems may be used to provide simultaneous or sequential determinations of
element concentrations.
3 Reagents
During the analysis, use only reagents of recognised analytical grade.
3.1 Strontium Nitrate [Sr(NO ) ]
3 2
3.2 Sodium Carbonate [Na CO ]
2 3
3.3 Lithium Tetraborate [Li B O ]
2 4 7
3.4 Sodium Iodide [NaI]
4 Apparatus
4.1 X-ray fluorescence spectrometer
The spectrometer can be either a simultaneous or a sequential wavelength dispersive model and shall be
optimised according to the manufacturer instructions.
4.2 Melting devices
4.3 Platinum crucibles
4.4 Nickel crucibles
4.5 Platinum dishes
5 Safety precautions
They shall be in accordance with national regulations for X-ray equipment.
X-ray equipment shall be used only under the guidance and supervision of a responsible, qualified person.
6 Sampling
Sampling shall be carried out in accordance with appropriate international or national standards for ferro
alloys.
7 Procedure
7.1 Test sample preparation
In a platinum crucible (4.3), weigh 6,00 g of Li B O (3.3) to the nearest 0,001 g.
2 4 7
In a nickel crucible (4.4), weigh, to the nearest 0,001 g:
0,750 g of Sr(NO ) (3.1);
3 2
2,500 g of Na CO (3.2);
2 3
1,000 g of Li B O (3.3).
2 4 7
Then, weigh 0,250 0 g of the sample, to the nearest 0,000 1 g and add it into the same nickel crucible (4.4).
Finally transfer into the nickel crucible (4.4) 0,020 g of NaI (3.4), weighted to the nearest 0,001 g.
Carefully mix all the components added into the nickel crucible (4.4) and then completely pour the mixture
contained in the nickel crucible (4.4) into the platinum crucible (4.3), onto the 6,00 g of Li B O (3.3), whilst
2 4 7
avoiding the contact of the mixture with the wall of the platinum crucible (4.3).
Introduce the platinum crucible (4.3) in a furnace set up at the temperature of 650 °C for 6 min, in order to
oxidise the sample.
Melt the sample at the temperature of 1 200 °C, whilst mixing continuously and then pour the melted sample
in a platinum dish (4.5) preheated with a Bunsen flame.
Allow the so prepared bead to cool.
7.2 Preparation of the calibration curves
Prepare the calibration of the X-ray fluorescence spectrometer by using oxide beads of ferro-silicon Certified
Reference Materials (CRMs).
For each element, prepare a minimum of six oxide beads with different contents of Si, Al and Fe, in the same
way as for the test samples (see 7.1), only using Certified Reference Materials. These Certified Reference
Materials shall cover the entire calibration range.
Use the analytical line Kα 7.126 for Si, Kα 8.339 for Al and Kα 1.937 for Fe and plot the absolute intensities
versus the related certified contents.
NOTE The calibration curves can also be obtained by using oxide beads prepared with pure metals and/or oxides.
Annex C describes the related preparation.
7.3 Spectrometric measurements
7.3.1 Spectrometric measurements of the calibration and the re-calibration samples
For each element (each analytical line) measure the related absolute intensity of the calibration samples
together with the re-calibration samples according to the instrument manufacturer instructions, at least four
times each.
NOTE 1 To compensate the instrumental day to day drift, re-calibration samples and procedures are required.
NOTE 2 It's advisable to prepare the re-calibration samples as described in 7.1. These samples can be internal
reference materials provided that their homogeneity has been carefully check, approved and recorded.
Prepare the related calibration graphs by plotting the mean intensity values of the Certified Reference
Materials beads against the corresponding Si and Al certified contents.
Record the regression calculations and store the relevant parameters, together with the corresponding
coefficients of correlation, the standard error of estimate, the error of the slope and the confidence limits.
Check the calibration trueness by measuring a set of Certified Reference Materials not used in the calibration
and prepared as described in 7.1. The silicon and aluminium certified values of these samples shall cover at
least the low, mid and top points of the corresponding calibration ranges.
7.3.2 Spectrometric measurements of the test samples
Following the manufacturer instructions, measure the intensity of each test sample bead at least twice and
calculate the mean value of the corresponding results.
8 Expression of results
On the calibration curves, read the contents, expressed in percent (mass fraction) of the elements (Si, Al and
Fe) determined in the test sample.
9 Precision
Four laboratories in two European countries participated in an inter laboratory test programme under the
auspices of ECISS/TC 102/WG 5, involving three determinations of Al and Si at several levels.
Each laboratory carried out two determinations under repeatability conditions as defined in ISO 5725-1, i.e.
one operator, same apparatus, identical operating conditions, same calibration and a minimum period of time.
The third determination was carried out on a different day using the same apparatus with a different
calibration.
Details on the samples used are given in Annex A and the results obtained are reported in Annex B.
The sets of data available were too few for a statistical evaluation based on ISO 5725-2 and ISO 5725-3. Only
Mandel’s h and k statistics were used (see Figures B.1 to B.4) rather for illustrative purposes.
A short comment on the suitability of the data presented is also given in Annex B.
10 Test report
The test report shall contain the following information:
a) identification of the test sample;
b) method used;
c) results;
d) any unusual characteristics noted during the determination;
e) any operation not included in this Technical Report or in the document to which reference is made or
regarded as optional;
f) date of the test and/or date of preparation or signature of the test report;
g) signature of the responsible person.
Annex A
(informative)
Test samples used for the precision test
The test samples used are listed in Table A.1, here below. Elements and/or contents reported in grey cells
were out of the scope of the precision test.
Table A.1 — Composition of the test samples used for the precision test
Sample label Al (%) Ti (%) P (%) Si (%) Fe (%) B (%)
NBS 59 A 0,35 0,016 48,1 50,0 0,058
DL 2307 6,01 0,073 0,020 55,9 12,6
NBS 58 A 0,95 0,051 0,009 73,2 25,2 0,001
IPT 56 0,31 0,020 0,022 75,0 24,1
ECRM 582-2 1,15 0,225 0,018 75,2 21,4 0,005
JSS 720-4 1,52 0,032 76,4
ECRM 529-1 0,86 0,090 0,032 91,1 6,2
Annex B
(informative)
Detailed results obtained from the precision test
B.1 Aluminium results
B.1.1 Results
Table B.1 — Aluminium
ECRM 529-1 NBS 58 A ECRM 582-2 JSS 720-4 DL 2307
Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2
LAB 1 0,739 0 0,752 7 0,858 1 0,871 3 1,034 4 1,021 6 1,362 3 1,321 5 5,958 9 6,010 8
Individual values
0,792 8 0,858 1 1,009 7 1,368 5 5,998 6
Laboratory mean
0,761 5 0,862 5 1,021 9 1,350 8 5,989 4
LAB 2 0,932 7 0,941 3 0,993 8 0,959 3 1,264 0 1,259 5 1,542 4 1,534 4 6,155 4 6,154 5
Individual values
0,971 5 1,017 6 1,263
...
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