SIST-TP CEN/TR 10354:2012

SLOVENSKI STANDARD
SIST-TP CEN/TR 10354:2012
01-januar-2012
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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
SIST-TP CEN/TR 10354:2012 en,fr
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 10354:2012

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SIST-TP CEN/TR 10354:2012


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.





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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.

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SIST-TP CEN/TR 10354:2012
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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

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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.
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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.
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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.
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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.
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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
...