ISO 13933:2014

Steel and iron — Determination of calcium and magnesium — Inductively coupled plasma atomic emission spectrometric method

ISO 13933:2014 specifies a method for determination of calcium and magnesium contents in iron, cast iron, steel, and alloyed steel by inductively coupled plasma (ICP) atomic emission spectrometry. The method is applicable to the determination of calcium and magnesium contents (mass fraction) in the range of 0,000 5 % to 0,006 % and 0,000 5 % to 0,20 %, respectively.

Aciers et fontes - Détermination du calcium et du magnésium - Méthode par spectrométrie d'émission atomique avec plasma induit

General Information

• Status: Published
• Publication Date: 10-Jul-2014
• ICS: 77.080.01 - Ferrous metals in general
• Technical Committee: ISO/TC 17/SC 1 - Methods of determination of chemical composition
• Drafting Committee: ISO/TC 17/SC 1 - Methods of determination of chemical composition
• Current Stage: 9020 - International Standard under periodical review
• Start Date: 15-Oct-2024
• Completion Date: 15-Oct-2024

Standards Content (Sample)

INTERNATIONAL ISO
STANDARD 13933
First edition
2014-07-15
Steel and iron — Determination of
calcium and magnesium — Inductively
coupled plasma atomic emission
spectrometric method
Aciers et fontes - Détermination du calcium et du magnésium -
Méthode par spectrométrie d’émission atomique avec plasma induit
Reference number
©
ISO 2014
© ISO 2014
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
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Published in Switzerland
ii © ISO 2014 – All rights reserved

Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents . 1
5 Apparatus . 3
5.1 Inductively coupled plasma atomic emission spectrometer . 3
5.2 Polytetrafluoroethylene (PTFE) beakers with PTFE cover . 4
6 Sampling . 5
7 Procedure. 5
7.1 Test portion . 5
7.2 Blank test . 5
7.3 Determination . 5
7.4 Adjustment of the apparatus . 7
7.5 Measurement of the calibration solutions . 7
7.6 Plotting a calibration curve . 8
7.7 Measurements of the test solution . 8
8 Expression of results . 8
8.1 Method of calculation . 8
8.2 Precision . 8
9 Test report . 9
Annex A (normative) Procedure for the determination of instrumental criteria .10
Annex B (informative) Additional information on international cooperative test .12
Annex C (informative) Graphical representation of precision data .14
Bibliography .16
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.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
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. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 17, Steel, Subcommittee SC 1, Methods of
determination of chemical composition.
iv © ISO 2014 – All rights reserved

INTERNATIONAL STANDARD ISO 13933:2014(E)
Steel and iron — Determination of calcium and
magnesium — Inductively coupled plasma atomic emission
spectrometric method
1 Scope
This International Standard specifies a method for determination of calcium and magnesium contents in
iron, cast iron, steel, and alloyed steel by inductively coupled plasma (ICP) atomic emission spectrometry.
The method is applicable to the determination of calcium and magnesium contents (mass fraction) in
the range of 0,000 5 % to 0,006 % and 0,000 5 % to 0,20 %, respectively.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
ISO 385, Laboratory glassware — Burettes
ISO 648, Laboratory glassware — Single-volume pipettes
ISO 1042, Laboratory glassware — One-mark volumetric flasks
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 14284, Steel and iron — Sampling and preparation of samples for the determination of chemical
composition
3 Principle
A test portion is dissolved in a hydrochloric, nitric and hydrofluoric acid mixture and fumed with
perchloric acid. Hydrochloric acid, nitric acid, and an internal standard element (if used) are added and
the solution is diluted to a known volume. The solution is filtered if necessary, nebulized into an ICP
spectrometer and the intensity of the emitted light from each element measured simultaneously with
the intensity of the light emitted by the internal standard element.
4 Reagents
During the analysis, unless otherwise stated, use only reagents of recognized analytical grade with very
low calcium and magnesium contents and only grade 2 water as specified in ISO 3696.
4.1 Pure iron, containing less than 0,5 μg/g of calcium and magnesium.
4.2 Hydrochloric acid, ρ about 1,19 g/ml.
4.3 Hydrochloric acid, ρ about 1,19 g/ml, diluted 1 + 1.
4.4 Hydrochloric acid, ρ about 1,19 g/ml, diluted 1 + 4.
4.5 Hydrochloric acid, ρ about 1,19 g/ml, diluted 1 + 100.
4.6 Nitric acid, ρ about 1,42 g/ml.
4.7 Hydrofluoric acid, ρ about 1,14 g/ml.
4.8 Perchloric acid, ρ about 1,67 g/ml.
4.9 Acid mixture.
Mix two volumes of hydrochloric acid (4.2), one volume of nitric acid (4.6), and three volumes of water.
4.10 Calcium standard solutions.
4.10.1 Calcium stock solution, corresponding to 1 000 mg of calcium per litre.
Dry several grams of calcium carbonate [purity ≥99,9 % (mass fraction)] in an oven at 100 °C ± 5 °C
for at least 1 h and cool to room temperature in a desiccator. Weigh, to the nearest 0,000 1 g, 2,497 g of
the dried product into a 400 ml beaker, add 20 ml of hydrochloric acid (4.3), cover with a watch-glass
and heat gently until the product is completely dissolved. Cool to room temperature and transfer the
solution into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.
1 ml of this stock solution contains 1,000 mg of calcium.
4.10.2 Calcium standard solution A, corresponding to 100 mg of calcium per litre.
Transfer 10,00 ml of calcium stock solution (4.10.1) into a 100 ml one-mark volumetric flask. Add 10 ml
of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,100 mg of calcium.
4.10.3 Calcium standard solution B, corresponding to 10 mg of calcium per litre.
Transfer 10,00 ml of calcium standard solution A (4.10.2) into a 100 ml one-mark volumetric flask. Add
10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,010 mg of calcium.
4.10.4 Calcium standard solution C, corresponding to 1,0 mg of calcium per litre.
Transfer 10,00 ml of calcium standard solution B (4.10.3) into a 100 ml one-mark volumetric flask. Add
10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,001 mg of calcium.
4.11 Magnesium standard solutions
4.11.1 Magnesium stock solution, corresponding to 1 000 mg of magnesium per litre.
Weigh, to the nearest 0,000 1 g, 1,000 g of pure magnesium [purity ≥99,9 % (mass fraction)] and transfer
into a 250 ml beaker. Add 20 ml of water, then add hydrochloric acid (4.3) drop by drop while swirling
until the acid action ceases and continue adding hydrochloric acid (4.3) to a total volume of 20 ml. Cover
with a watch-glass and heat to boil for 10 min. After cooling, transfer the solution quantitatively into a
1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.
1 ml of this stock solution contains 1,000 mg of magnesium.
2 © ISO 2014 – All rights reserved

4.11.2 Magnesium standard solution A, corresponding to 100 mg of magnesium per litre.
Transfer 10,00 ml of magnesium stock solution (4.11.1) into a 100 ml one-mark volumetric flask. Add
10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,100 mg of magnesium.
4.11.3 Magnesium standard solution B, corresponding to 10 mg of magnesium per litre.
Transfer 10,00 ml of magnesium standard solution A (4.11.2) into a 100 ml one-mark volumetric flask.
Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,010 mg of magnesium.
4.11.4 Magnesium standard solution C, corresponding to 1,0 mg of magnesium per litre.
Transfer 10,00 ml of magnesium standard solution B (4.11.3) into a 100 ml one-mark volumetric flask.
Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,001 mg of magnesium.
4.12 Yttrium internal standard solution, corresponding to 100 mg of yttrium per litre.
Calcine several grams of yttrium oxide [purity ≥99,9 % (mass fraction)] in a muffle furnace at
850 °C ± 10 °C for at least 40 min and then cool to room temperature in a desiccator. Weigh 0,127 0 g of
the calcined product into a 400 ml beaker, add 10 ml of hydrochloric acid (4.3), cover with a watch-glass,
and heat gently until the product is completely dissolved. Cool to room temperature and transfer the
solution to a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,100 mg of yttrium.
5 Apparatus
All volumetric glassware shall be class A and calibrated in accordance with ISO 385
...

DRAFT INTERNATIONAL STANDARD ISO/DIS 13933
ISO/TC 17/SC 1 Secretariat: JISC
Voting begins on Voting terminates on

2012-08-28 2013-01-28
INTERNATIONAL ORGANIZATION FOR STANDARDIZATION    МЕЖДУНАРОДНАЯ ОРГАНИЗАЦИЯ ПО СТАНДАРТИЗАЦИИ    ORGANISATION INTERNATIONALE DE NORMALISATION

Steel and iron — Determination of calcium and magnesium —
Inductively coupled plasma atomic emisson spectrometric
method
Aciers et fontes — Détermination du calcium et du magnésium — Méthode spcectrométrique d'émission
atomique avec plasma induit
ICS 77.080.01
To expedite distribution, this document is circulated as received from the committee
secretariat. ISO Central Secretariat work of editing and text composition will be undertaken at
publication stage.
Pour accélérer la distribution, le présent document est distribué tel qu'il est parvenu du
secrétariat du comité. Le travail de rédaction et de composition de texte sera effectué au
Secrétariat central de l'ISO au stade de publication.

THIS DOCUMENT IS A DRAFT CIRCULATED FOR COMMENT AND APPROVAL. IT IS THEREFORE SUBJECT TO CHANGE AND MAY NOT BE
REFERRED TO AS AN INTERNATIONAL STANDARD UNTIL PUBLISHED AS SUCH.
IN ADDITION TO THEIR EVALUATION AS BEING ACCEPTABLE FOR INDUSTRIAL, TECHNOLOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON OCCASION HAVE TO BE CONSIDERED IN THE LIGHT OF THEIR POTENTIAL TO BECOME
STANDARDS TO WHICH REFERENCE MAY BE MADE IN NATIONAL REGULATIONS.
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.
©  International Organization for Standardization, 2012

ISO/DIS 13933
Copyright notice
This ISO document is a Draft International Standard and is copyright-protected by ISO. Except as permitted
under the applicable laws of the user’s country, neither this ISO draft nor any extract from it may be
reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic,
photocopying, recording or otherwise, without prior written permission being secured.
Requests for permission to reproduce should be addressed to 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 [e-mail]
Web www.iso.org
Reproduction may be subject to royalty payments or a licensing agreement.
Violators may be prosecuted.
ii © ISO 2012 – All rights reserved

ISO/DIS 13933
Contents Page
Foreword . iv
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents . 1
5 Apparatus . 3
6 Sampling . 5
7 Procedure . 5
7.1 Test portion . 5
7.2 Blank test . 6
7.3 Determination . 6
7.4 Preparation for spectrometric measurements . 8
7.5 Measurement of the calibration solutions . 8
7.6 Plotting of calibration curve . 8
7.7 Measurements of the test solution . 8
8 Expression of results . 9
8.1 Method of calculation . 9
8.2 Precision . 9
9 Test report . 10
Annex A (normative) Procedure for the determination of instrumental criteria . 11
Annex B (informative) Additional information on international cooperative tests . 13
Annex C (informative) Graphical representation of precision data . 15
Bibliography . 17

ISO/DIS 13933
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 13933 was prepared by Technical Committee ISO/TC 17, Steel, Subcommittee SC 1, Methods of
determination of chemical composition.
iv © ISO 2012 – All rights reserved

DRAFT INTERNATIONAL STANDARD ISO/DIS 13933

Steel and iron — Determination of calcium and magnesium —
Inductively coupled plasma atomic emission spectrometric
method
1 Scope
This draft specifies a method for determination of calcium and magnesium contents in iron, cast iron, steel and
alloyed steel by inductively coupled plasma atomic emission spectrometry.
The method is applicable to the determination of calcium and magnesium in content range (mass fraction) from
0,000 5 % to 0.006 % and from 0,000 5 % to 0,20 %, respectively.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated references,
only the edition cited applies. For undated references, the latest edition of the referenced document (including any
amendments) applies.
ISO 385, Laboratory glassware – Burettes
ISO 648, Laboratory glassware -- Single-volume pipettes
ISO 1042, Laboratory glassware – One mark volumetric flasks
ISO 3696, Water for analytical laboratory use – Specification and test methods
ISO 14284, Steel and iron -- Sampling and preparation of samples for the determination of chemical composition
3 Principle
A test portion is dissolved in hydrochloric, nitric and hydrofluoric acid mixture and fumed with perchloric acid.
Hydrochloric acid and an internal standard element (if used) are added and the solution is diluted to a known
volume. The solution is filtered, if necessary, and nebulized into an ICP and the intensity of the emitted light from
each element is measured simultaneously with the intensity of the light emitted by the internal standard element.
Iron is used as matrix in the calibration solution, the quantities of iron being the same as that of the test portion.
4 Reagents
During the analysis, unless otherwise stated, use only reagents of recognized analytical grade having very low
calcium and magnesium contents and only grade 2 water as specified in ISO 3696.
ISO/DIS 13933
4.1 Pure iron, containing less than 0,000 1 % (mass fraction) of calcium and magnesium.
4.2 Hydrochloric acid, ρ about 1,19 g/ml.
4.3 Hydrochloric acid, ρ about 1,19 g/ml, diluted 1+1
4.4 Hydrochloric acid, ρ about 1,19 g/ml, diluted 1+4.
4.5 Nitric acid, ρ about 1,42 g/ml.
4.6 Hydrofluoric acid, ρ about 1,14 g/ml.
4.7 Perchloric acid, ρ about 1,67 g/ml.
4.8 Acid mixture
Mix two volumes of hydrochloric acid (4.2), one volume of nitric acid (4.5) and three volumes of water.
4.9 Calcium standard solution
4.9.1 Calcium stock solution, corresponding to 1 000 mg of calcium per litre.
Dry several grams of calcium carbonate [purity ≥ 99,9 % (mass fraction)] in an oven at 100 ˚C ± 5 ˚C for at least
1 h and cool to room temperature in a desiccator. Weigh, to the nearest 0,0001 g, 2,497 g of the dried product into
a 400 ml beaker, add 20 ml of hydrochloric acid (4.3), cover with a watch-glass and heat gently until the product is
completely dissolved. Cool to room temperature and transfer the solution into a 1 000 ml one-mark volumetric flask,
dilute to the mark with water and mix.
1 ml of this stock solution contains 1,000 mg of calcium.
4.9.2 Calcium standard solution A, corresponding to 100 mg of calcium per litre.
Transfer, with a calibrated pipette, 10,00 ml of calcium stock solution (4.9.1) into a calibrated 100 ml one-mark
volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,100 mg of calcium.
4.9.3 Calcium standard solution B, corresponding to 10 mg of calcium per litre.
Transfer, with a calibrated pipette, 10,00 ml of calcium standard solution A (4.9.2) into a calibrated 100 ml one-mark
volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,010 mg of calcium.
4.9.4 Calcium standard solution C, corresponding to 1,0 mg of calcium per litre.
Transfer, with a calibrated pipette, 10,00 ml of calcium standard solution A (4.9.3) into a calibrated 100 ml one-mark
volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,001 mg of calcium.
2 © ISO 2012 – All rights reserved

ISO/DIS 13933
4.10 Magnesium standard solution
4.10.1 Magnesium stock solution, corresponding to 1 000 mg of magnesium per litre.
Weigh, to the nearest 0,000 1 g, 1,000 g of pure magnesium [purity ≥ 99,9 % (mass fraction)] and transfer into a
250 ml beaker. Add 20 ml of water, and add hydrochloric acid (4.3) drop by drop whilst swirling until the acid action
ceases, and continue adding hydrochloric acid (4.3) to 20 ml. Cover with a watch glass and heat to boil for 10 min.
After cooling, transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with
water and mix.
1 ml of this stock solution contains 1,000 mg of magnesium.
4.10.2 Magnesium standard solution A, corresponding to 100 mg of magnesium per litre.
Transfer, with a calibrated pipette, 10,00 ml of magnesium stock solution (4.10.1) into a calibrated 100 ml one-mark
volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,100 mg of magnesium.
4.10.3 Magnesium standard solution B, corresponding to 10 mg of magnesium per litre.
Transfer, with a calibrated pipette, 10.00 ml of magnesium standard solution A (4.10.2) into a calibrated 100 ml one-
mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,010 mg of magnesium.
4.10.4 Magnesium standard solution C, corresponding to 1,0 mg of magnesium per litre.
Transfer, with a calibrated pipette, 10,00 ml of magnesium standard solution A (4.10.3) into a calibrated 100 ml one-
mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.
1 ml of this standard solution contains 0,001 mg of magnesium.
4.11 Yttrium internal standard solution, corresponding to 100 mg of yttrium per litre.
Calcine several grams of yttrium oxide [purity ≥ 99,9 % (mass fraction)] in a muffle furnace at 850 ˚C ± 10 ˚C for at
least 40 min and then cool to room temperature in a desiccator. Weigh 0,127 0 g of the calcined product into a 400
ml beaker, add 10 ml of hydrochloric acid (4.3), cover with a watch-glass, and heat gently until the product is
completely dissolved. Cool to room temperature and transfer the solution to a 1 000 ml one-mark volumetric flask,
dilute to the mark with water and mix.
1 ml of this stock solution contains 0,100 mg of yttrium.
5 Apparatus
All volumetric glassware shall be class A, in accordance with ISO 385, ISO 648 or ISO 1042 as appropriate.
Ordinary laboratory apparatus and
5.1 Inductively coupled plasma atomic emission spectrometer
The inductively coupled plasma atomic emission spectrometer used will be sat
...