EN IEC 62321-3-4:2023
(Main)Determination of certain substances in electrotechnical products - Part 3-4: Screening - Phthalates in polymers of electrotechnical products by high performance liquid chromatography with ultraviolet detector (HPLC-UV), thin layer chromatography (TLC) and thermal desorption mass spectrometry (TD-MS)
Determination of certain substances in electrotechnical products - Part 3-4: Screening - Phthalates in polymers of electrotechnical products by high performance liquid chromatography with ultraviolet detector (HPLC-UV), thin layer chromatography (TLC) and thermal desorption mass spectrometry (TD-MS)
IEC 62321-3-4:2023 specifies procedures for the screening of di-isobutyl phthalate (DIBP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP) in polymers of electrotechnical products by using high performance liquid chromatography with ultraviolet detector (HPLC-UV), thin layer chromatography (TLC) and thermal desorption mass spectrometry (TD-MS). High performance liquid chromatography with ultraviolet detector (HPLC-UV), thin layer chromatography (TLC) and thermal desorption mass spectrometry (TD-MS) techniques are described in the normative part of this document. Fourier transform infrared spectroscopy (FT-IR) is described in the informative annexes of this document.
Verfahren zur Bestimmung von bestimmten Substanzen in Produkten der Elektrotechnik - Teil 3-4: Screening von Phthalaten in Polymeren von Produkten der Elektrotechnik durch Hochleistungs-Flüssigkeitschromatographie mit Ultraviolettdetektor (HPLC-UV), Dünnschichtchromatographie (TLC) und Thermodesorptions-Massenspektroskopie (TD-MS)
Détermination de certaines substances dans les produits électrotechniques - Partie 3-4: Détection - Phtalates dans les polymères des produits électrotechniques par chromatographie en phase liquide à haute performance avec détecteur d'ultraviolets (HPLC-UV), par chromatographie sur couche mince (CCM) et par spectrométrie de masse par désorption thermique (TD-MS)
IEC 62321-3-4:2023 spécifie des modes opératoires pour le criblage du phtalate de di-isobutyle (DIBP), du phtalate de di-n-butyle (DBP), du phtalate de benzyle et de butyle (BBP), du phtalate de bis (2-éthylhexyle) (DEHP) dans les polymères de produits électrotechniques en utilisant la chromatographie liquide à haute performance avec détecteur ultraviolet (HPLC-UV), la chromatographie sur couche mince (TLC) et la spectrométrie de masse par désorption thermique (TD-MS). Les techniques de chromatographie liquide à haute performance avec détecteur ultraviolet (CLHP-UV), chromatographie sur couche mince (CCM) et spectrométrie de masse par désorption thermique (TD-MS) sont décrites dans la partie normative du présent document. La spectroscopie infrarouge à transformée de Fourier (FT-IR) est décrite dans les annexes informatives du présent document.
Določevanje posameznih snovi v elektrotehničnih izdelkih-3-4: del: Presejanje ftalatov v polimerih elektronskih izdelkov s tekočinsko kromatografijo visoke ločljivosti z UV-detekcijo (HPLC-UV), tankoplastno kromatografijo (TCL) in masno spektrometrijo (TD-MS) s toplotno desorpcijo
Standard IEC 62321-3-4:2023 določa postopke za presejanje di-izobutil ftalata (DIBP), di-n-butil ftalata (DBP), benzil butil ftalata (BBP), di-(2-etilheksil) ftalata (DEHP) v polimerih elektronskih izdelkov s tekočinsko kromatografijo visoke ločljivosti z UV-detekcijo (HPLC-UV), tankoplastno kromatografijo (TLC) in masno spektrometrijo (TD-MS) s toplotno desorpcijo.
Tehnike tekočinske kromatografije visoke ločljivosti z UV-detekcijo, tankoplastne kromatografije in masne spektrometrije s toplotno desorpcijo so opisane v normativnem delu tega dokumenta. V informativnih dodatkih tega dokumenta je opisana infrardeča spektroskopija s Fourierjevo transformacijo (FT-IR).
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
01-januar-2024
Določevanje posameznih snovi v elektrotehničnih izdelkih-3-4: del: Presejanje
ftalatov v polimerih elektronskih izdelkov s tekočinsko kromatografijo visoke
ločljivosti z UV-detekcijo (HPLC-UV), tankoplastno kromatografijo (TCL) in masno
spektrometrijo (TD-MS) s toplotno desorpcijo
Determination of certain substances in electrotechnical products - Part 3-4: Screening of
Phthalates in polymers of electrotechnical products by high performance liquid
chromatography with ultraviolet detector (HPLC-UV), thin layer chromatography (TLC)
and thermal desorption mass spectrometry (TD-MS)
Verfahren zur Bestimmung von bestimmten Substanzen in Produkten der Elektrotechnik
- Teil 3-4: Screening von Phthalaten in Polymeren von Produkten der Elektrotechnik
durch Hochleistungs-Flüssigkeitschromatographie mit Ultraviolettdetektor (HPLC-UV),
Dünnschichtchromatographie (TLC) und Thermodesorptions-Massenspektroskopie (TD-
MS)
Détermination de certaines substances dans les produits électrotechniques - Partie 3-4:
Détection des phtalates dans les polymères des produits électrotechniques par
chromatographie en phase liquide à haute performance avec détecteur d'ultraviolets
(HPLC-UV), par chromatographie sur couche mince (CCM) et par spectrométrie de
masse par désorption thermique (TD-MS)
Ta slovenski standard je istoveten z: EN IEC 62321-3-4:2023
ICS:
29.020 Elektrotehnika na splošno Electrical engineering in
general
31.020 Elektronske komponente na Electronic components in
splošno general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
EUROPEAN STANDARD EN IEC 62321-3-4
NORME EUROPÉENNE
EUROPÄISCHE NORM June 2023
ICS 13.020.01; 29.100.01; 01.110
English Version
Determination of certain substances in electrotechnical products
- Part 3-4: Screening - Phthalates in polymers of electrotechnical
products by high performance liquid chromatography with
ultraviolet detector (HPLC-UV), thin layer chromatography (TLC)
and thermal desorption mass spectrometry (TD-MS)
(IEC 62321-3-4:2023)
Détermination de certaines substances dans les produits Verfahren zur Bestimmung von bestimmten Substanzen in
électrotechniques - Partie 3-4: Détection - Phtalates dans Produkten der Elektrotechnik - Teil 3-4: Screening von
les polymères des produits électrotechniques par Phthalaten in Polymeren von Produkten der Elektrotechnik
chromatographie en phase liquide à haute performance durch Hochleistungs-Flüssigkeitschromatographie mit
avec détecteur d'ultraviolets (HPLC-UV), par Ultraviolettdetektor (HPLC-UV),
chromatographie sur couche mince (CCM) et par Dünnschichtchromatographie (TLC) und
spectrométrie de masse par désorption thermique (TD-MS) Thermodesorptions-Massenspektroskopie (TD-MS)
(IEC 62321-3-4:2023) (IEC 62321-3-4:2023)
This European Standard was approved by CENELEC on 2023-06-07. CENELEC 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.
Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC
Management Centre or to any CENELEC member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CENELEC member into its own language and notified to the CEN-CENELEC Management Centre has the
same status as the official versions.
CENELEC members are the national electrotechnical committees of Austria, Belgium, Bulgaria, Croatia, Cyprus, the Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, the
Netherlands, Norway, Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Türkiye and the United Kingdom.
European Committee for Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2023 CENELEC All rights of exploitation in any form and by any means reserved worldwide for CENELEC Members.
Ref. No. EN IEC 62321-3-4:2023 E
European foreword
The text of document 111/695/FDIS, future edition 1 of IEC 62321-3-4, prepared by IEC/TC 111
"Environmental standardization for electrical and electronic products and systems" was submitted to
the IEC-CENELEC parallel vote and approved by CENELEC as EN IEC 62321-3-4:2023.
The following dates are fixed:
• latest date by which the document has to be implemented at national (dop) 2024-03-07
level by publication of an identical national standard or by endorsement
• latest date by which the national standards conflicting with the (dow) 2026-06-07
document have to be withdrawn
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CENELEC shall not be held responsible for identifying any or all such patent rights.
Any feedback and questions on this document should be directed to the users’ national committee. A
complete listing of these bodies can be found on the CENELEC website.
Endorsement notice
The text of the International Standard IEC 62321-3-4:2023 was approved by CENELEC as a
European Standard without any modification.
In the official version, for Bibliography, the following notes have to be added for the standard indicated:
IEC 62321-8:2017 NOTE Approved as EN 62321-8:2017 (not modified)
IEC 62321-6:2015 NOTE Approved as EN 62321-6:2015 (not modified)
ISO 3696 NOTE Approved as EN ISO 3696
ISO/IEC 17025 NOTE Approved as EN ISO/IEC 17025
Annex A
(normative)
Normative references to international publications
with their corresponding European publications
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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.
NOTE 1 Where an International Publication has been modified by common modifications, indicated by (mod), the
relevant EN/HD applies.
NOTE 2 Up-to-date information on the latest versions of the European Standards listed in this annex is available
here: www.cencenelec.eu.
Publication Year Title EN/HD Year
IEC 62321-1 2013 Determination of certain substances in EN 62321-1 2013
electrotechnical products - Part 1:
Introduction and overview
IEC 62321-2 2021 Determination of certain substances in EN IEC 62321-2 2021
electrotechnical products - Part 2:
Disassembly, disjointment and mechanical
sample preparation
IEC 62321-3-4 ®
Edition 1.0 2023-05
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
Determination of certain substances In electrotechnical products –
Part 3-4: Screening – Phthalates in polymers of electrotechnical products by
high performance liquid chromatography with ultraviolet detector (HPLC-UV),
thin layer chromatography (TLC) and thermal desorption mass spectrometry
(TD-MS)
Détermination de certaines substances dans les produits électrotechniques –
Partie 3-4: Détection – Phtalates dans les polymères des produits
électrotechniques par chromatographie en phase liquide à haute performance
avec détecteur d'ultraviolets (HPLC-UV), par chromatographie sur couche mince
(CCM) et par spectrométrie de masse par désorption thermique (TD-MS)
INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 01.110; 13.020.01; 29.100.01 ISBN 978-2-8322-6853-7
– 2 – IEC 62321-3-4:2023 © IEC 2023
CONTENTS
FOREWORD . 5
INTRODUCTION . 7
1 Scope . 8
2 Normative references . 9
3 Terms, definitions and abbreviated terms . 9
3.1 Terms and definitions . 9
3.2 Abbreviated terms . 10
4 Principle . 10
5 HPLC-UV and TLC method . 11
5.1 Reagents and materials . 11
5.1.1 Reagents and materials of HPLC-UV method . 11
5.1.2 Reagents and materials of TLC method . 11
5.2 Equipment, apparatus and tools . 12
5.2.1 Equipment, apparatus and tools for HPLC-UV method . 12
5.2.2 Equipment, apparatus and tools for TLC method . 12
5.3 Sampling. 12
5.4 Procedure . 13
5.4.1 Procedure of HPLC-UV method . 13
5.4.2 Procedure of TLC method . 15
5.5 Calculation of phthalates concentration . 17
5.6 Precision . 17
5.6.1 Precision of HPLC-UV method . 17
5.6.2 Precision of TLC method . 18
5.7 Quality assurance and control . 19
5.7.1 Quality assurance and control of HPLC-UV method . 19
5.7.2 Quality assurance and control of TLC method . 21
5.8 Test report . 22
6 TD-MS method . 22
6.1 Reagents and materials . 22
6.2 Equipment, apparatus and tools . 22
6.2.1 Equipment . 22
6.2.2 Apparatus and tools . 22
6.3 Sampling. 22
6.4 Procedure . 23
6.4.1 Procedure of APCI-MS method . 23
6.4.2 Procedure of IA-MS method . 25
6.5 Calculation of phthalates concentration . 27
6.6 Precision . 27
6.7 Quality assurance and control . 28
6.7.1 Sensitivity . 28
6.7.2 Stability test . 28
6.7.3 Blank test . 29
6.7.4 Limit of detection (LOD) or method detection limit (MDL) and limit of
quantification (LOQ) . 29
6.8 Test report . 29
Annex A (informative) FT-IR method . 30
IEC 62321-3-4:2023 © IEC 2023 – 3 –
A.1 Principle . 30
A.2 Reagents and materials . 32
A.3 Apparatus . 32
A.4 Sampling. 33
A.5 Procedure . 33
A.5.1 Sample preparation . 33
A.5.2 Instrumental parameters . 33
A.5.3 Calibration . 33
A.6 Calculation of phthalates concentration . 34
A.7 Precision . 34
A.8 Quality assurance and control . 35
A.9 Test report . 35
Annex B (informative) Details of analysis by TLC method . 36
B.1 Separation by TLC . 36
B.2 Detection by image analysis. 36
B.3 Re-measurement . 38
Annex C (informative) Examples of spectrums and chromatograms at suggested
conditions . 41
C.1 FT-IR spectrum . 41
C.2 HPLC-UV chromatogram . 41
C.3 TLC chromatogram . 42
C.4 APCI-MS mass spectrum . 42
C.5 IA-MS mass spectrum . 43
Annex D (informative) Commercially available reference materials and solutions
considered suitable for the suggested methods . 44
Annex E (informative) Flowchart of test methods . 45
Annex F (informative) Commonly used phthalates. 46
Annex G (informative) Results of international inter-laboratory study 3-4 (IIS 3-4). 47
Bibliography . 51
Figure 1 – Polymer samples in glass vials with acetonitrile (tightened with sealing tape) . 15
Figure A.1 – Phthalate analysis in polymers (check) . 31
Figure A.2 – Phthalate analysis in polymers with pre-treatment . 31
Figure B.1 – Usage of TLC plate (20 cm × 10 cm) . 36
Figure B.2 – Set-up of camera-equipment for TLC (inside of darkroom) . 37
Figure B.3 – TLC chromatogram . 38
Figure B.4 – Separation by re-measurement conditions (in case of pattern a)) . 39
Figure B.5 – Peak shift affected by large amount of DEHA . 39
Figure B.6 – TLC re-measurement by standard addition method (in case of pattern b)) . 40
Figure C.1 – Spectrum of FT-IR . 41
Figure C.2 – Chromatogram of HPLC-UV . 41
Figure C.3 – Developed TLC plate exposed to UV light of 254 nm . 42
Figure C.4 – Image processed TLC chromatogram of Figure C.3 . 42
Figure C.5 – Mass spectrums of APCI-MS . 43
Figure C.6 – Mass spectrums of IA-MS . 43
Figure E.1 – Flowchart for screening step and verification test step . 45
– 4 – IEC 62321-3-4:2023 © IEC 2023
Table 1 – Standard mixture solution concentrations . 13
Table 2 – Measurement conditions of HPLC-UV . 14
Table 3 – Standard mixture solution concentrations . 15
Table 4 – Measurement conditions of TLC . 16
Table 5 – IIS 3-4 Repeatability and reproducibility of HPLC-UV . 18
Table 6 – IIS 3-4 Repeatability and reproducibility of TLC . 19
Table 7 – Measurement conditions of APCI-MS . 24
Table 8 – Measurement conditions of IA-MS . 26
Table 9 – IIS 3-4 Repeatability and reproducibility of TD-MS . 28
Table A.1 – IIS 3-4 Repeatability and reproducibility of FT-IR . 34
Table B.1 – Conditions of photography . 37
Table B.2 – Range of Rf values of target phthalates . 38
Table D.1 – Example list of commercially available reference materials . 44
Table F.1 – Example list of commonly used phthalates in products . 46
Table G.1 – Formulation of samples. 47
Table G.2 – Statistical data for HPLC-UV . 48
Table G.3 – Statistical data for TLC . 49
Table G.4 – Statistical data for TD-MS . 50
Table G.5 – Statistical data for FT-IR . 50
IEC 62321-3-4:2023 © IEC 2023 – 5 –
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –
Part 3-4: Screening – Phthalates in polymers of electrotechnical
products by high performance liquid chromatography with ultraviolet
detector (HPLC-UV), thin layer chromatography (TLC) and thermal
desorption mass spectrometry (TD-MS)
FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote international
co-operation on all questions concerning standardization in the electrical and electronic fields. To this end and
in addition to other activities, IEC publishes International Standards, Technical Specifications, Technical Reports,
Publicly Available Specifications (PAS) and Guides (hereafter referred to as "IEC Publication(s)"). Their
preparation is entrusted to technical committees; any IEC National Committee interested in the subject dealt with
may participate in this preparatory work. International, governmental and non-governmental organizations liaising
with the IEC also participate in this preparation. IEC collaborates closely with the International Organization for
Standardization (ISO) in accordance with conditions determined by agreement between the two organizations.
2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international
consensus of opinion on the relevant subjects since each technical committee has representation from all
interested IEC National Committees.
3) IEC Publications have the form of recommendations for international use and are accepted by IEC National
Committees in that sense. While all reasonable efforts are made to ensure that the technical content of IEC
Publications is accurate, IEC cannot be held responsible for the way in which they are used or for any
misinterpretation by any end user.
4) In order to promote international uniformity, IEC National Committees undertake to apply IEC Publications
transparently to the maximum extent possible in their national and regional publications. Any divergence between
any IEC Publication and the corresponding national or regional publication shall be clearly indicated in the latter.
5) IEC itself does not provide any attestation of conformity. Independent certification bodies provide conformity
assessment services and, in some areas, access to IEC marks of conformity. IEC is not responsible for any
services carried out by independent certification bodies.
6) All users should ensure that they have the latest edition of this publication.
7) No liability shall attach to IEC or its directors, employees, servants or agents including individual experts and
members of its technical committees and IEC National Committees for any personal injury, property damage or
other damage of any nature whatsoever, whether direct or indirect, or for costs (including legal fees) and
expenses arising out of the publication, use of, or reliance upon, this IEC Publication or any other IEC
Publications.
8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of patent
rights. IEC shall not be held responsible for identifying any or all such patent rights.
IEC 62321-3-4 has been prepared IEC technical committee 111: Environmental standardization
for electrical and electronic products and systems. It is an International Standard.
The text of this International Standard is based on the following documents:
Draft Report on voting
111/695/FDIS 111/701/RVD
Full information on the voting for its approval can be found in the report on voting indicated in
the above table.
The language used for the development of this International Standard is English.
– 6 – IEC 62321-3-4:2023 © IEC 2023
This document was drafted in accordance with ISO/IEC Directives, Part 2, and developed in
accordance with ISO/IEC Directives, Part 1 and ISO/IEC Directives, IEC Supplement, available
at www.iec.ch/members_experts/refdocs. The main document types developed by IEC are
described in greater detail at www.iec.ch/publications.
A list of all parts in the IEC 62321 series, published under the general title Determination of
certain substances in electrotechnical products, can be found on the IEC website.
The committee has decided that the contents of this document will remain unchanged until the
stability date indicated on the IEC website under webstore.iec.ch in the data related to the
specific document. At this date, the document will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.
IEC 62321-3-4:2023 © IEC 2023 – 7 –
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries all over the world, this has resulted in the adaptation of
regulations affecting wastes, substances and energy use of electrotechnical products.
The use of certain substances (e.g. lead (Pb), cadmium (Cd), polybrominated diphenyl ethers
(PBDEs) and specific phthalates) in electrotechnical products is a source of concern in current
and proposed regional legislation.
The purpose of the IEC 62321 series is therefore to provide test methods that will allow the
electrotechnical industry to determine the levels of certain substances of concern in
electrotechnical products on a consistent global basis.
This first edition of IEC 62321-3-4 introduces a new part in the IEC 62321 series.
Appropriate test methods are required in order to facilitate the monitoring of the contents of
certain substances in affected materials. Faced with the enormous task of testing a diversity of
electronic and electric equipment, the industry adopted the concept of 'screening' in order to
reduce the amount of testing. As defined in IEC 62321-1:2013, 3.1.10, "…screening is an
analytical procedure to determine the presence or absence of substances in the representative
part or section of a product, relative to the value or values chosen as the criterion for presence,
absence or further testing". Executed as a predecessor to any other test analysis of the product,
the main objective of screening is to quickly, expediently, inexpensively and preferably in a non-
destructive manner, determine whether the screened product:
– contains a certain substance at a concentration significantly higher than its value accepted
as criterion, and therefore can be rejected as being above the threshold;
– contains a certain substance at a concentration significantly lower than its value accepted
as criterion, and therefore can be considered below the threshold;
– contains a certain substance at a concentration so close to the value accepted as criterion
that when all possible errors of measurement and safety factors and measurement
uncertainty are considered, no conclusive decision can be made about the absence or
presence of substance and, therefore, a follow-up action can be required, such as another,
more specific or more precise and accurate analysis.
WARNING – Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address all of the safety problems, if any, associated with
its use. It is the responsibility of the user to establish appropriate safety and health practices
and to ensure compliance with any national regulatory conditions.
– 8 – IEC 62321-3-4:2023 © IEC 2023
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –
Part 3-4: Screening – Phthalates in polymers of electrotechnical
products by high performance liquid chromatography with ultraviolet
detector (HPLC-UV), thin layer chromatography (TLC) and thermal
desorption mass spectrometry (TD-MS)
1 Scope
This part of IEC 62321 specifies procedures for the screening of di-isobutyl phthalate (DIBP),
di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP) in
polymers of electrotechnical products by using high performance liquid chromatography with
ultraviolet detector (HPLC-UV), thin layer chromatography (TLC) and thermal desorption mass
spectrometry (TD-MS).
High performance liquid chromatography with ultraviolet detector (HPLC-UV), thin layer
chromatography (TLC) and thermal desorption mass spectrometry (TD-MS) techniques are
described in the normative part of this document. Fourier transform infrared spectroscopy
(FT-IR) is described in the informative annexes of this document.
The HPLC-UV and TLC techniques are suitable for screening and semi-quantitative analysis of
DIBP, DBP, BBP and DEHP in polymers that are used as parts in electrotechnical products
above 300 mg/kg.
Theu TD-MS technique is suitable for screening and semi-quantitative analysis of DIBP, DBP,
BBP and DEHP in polymers that are used as parts in electrotechnical products above 300 mg/kg.
The FT-IR technique is suitable for preliminary screening of total phthalates (DIBP, DBP, BBP,
DEHP and so forth) in polymers that are used as parts in electrotechnical products above
50 000 mg/kg.
These test methods have been evaluated by testing polyethylene (PE), polyvinyl chloride (PVC)
materials containing individual phthalates between 500 mg/kg to 3 000 mg/kg as depicted in
this document. The use of the methods described in this document for other polymer types,
phthalate compounds or concentration ranges other than those specified above has not been
specifically evaluated.
A flow chart is given as an example of how each method included in this document can be used
for screening. The test methods in this document differ from those given in IEC 62321-8 [1] in
that not all phthalates in this scope are separated from each other. Detectable combinations
are DIBP + DBP + BBP and DEHP for the HPLC-UV technique, DIBP + DBP, BBP and DEHP
for the TLC technique and TD-MS technique, total phthalates for the FT-IR technique. FT-IR is
a suitable analytical technique for preliminary screening in the first step of phthalates screening.
These test methods are characterized by a shorter measuring time compared with IEC 62321-8
because all phthalates in this scope are not separated from each other.
NOTE See Annex F for commonly used phthalates in products.
This document has the status of a horizontal publication in accordance with IEC Guide 108 [2].
___________
Numbers in square brackets refer to the Bibliography.
IEC 62321-3-4:2023 © IEC 2023 – 9 –
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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.
IEC 62321-1:2013, Determination of certain substances in electrotechnical products – Part 1:
Introduction and overview
IEC 62321-2:2021, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjointment and mechanical sample preparation
3 Terms, definitions and abbreviated terms
3.1 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following
addresses:
• IEC Electropedia: available at https://www.electropedia.org/
• ISO Online browsing platform: available at https://www.iso.org/obp
3.1.1
screening
analytical procedure to determine the presence or absence of substances in the representative
part or section of a product, relative to the value or values chosen as the criterion for presence,
absence or further testing
Note 1 to entry: If the screening method produces values that are not conclusive, then additional analysis or other
follow-up actions may be necessary to make a final presence/absence decision.
[SOURCE: IEC 62321-1:2013, 3.1.10]
3.1.2
semi-quantitative
level of accuracy in a measurement amount where the relative uncertainty of the result is
typically 30 % or better at a defined level of confidence of 68 %
[SOURCE: IEC 62321-6:2015, 3.1.1 [3]]
3.1.3
calibrant
calibration standard
substance in solid or liquid form with known and stable concentration(s) of the analyte(s) of
interest used to establish instrument response (calibration curve) with respect to analyte(s)
concentration(s)
– 10 – IEC 62321-3-4:2023 © IEC 2023
3.2 Abbreviated terms
ACN acetonitrile
APCI atmospheric pressure chemical ionization
APCI-MS atmospheric pressure chemical ionization mass spectrometry
BBP benzyl butyl phthalate
CRM certified reference material
DBP di-n-butyl phthalate
DEHP di-(2-ethylhexyl) phthalate
DIBP di-isobutyl phthalate
DIP direct injection probe
DNOP di-n-octyl phthalate
FT-IR Fourier Transform infrared spectroscopy
HPLC-UV high performance liquid chromatography with ultraviolet detector
IA-MS ion attachment mass spectrometry
TLC thin layer chromatography
IS internal standard
LOD limit of detection
LOQ limit of quantification
MDL method detection limit
MS mass spectrometry
PVC polyvinyl chloride
QC quality control
SIM selected ion monitoring
TD-MS thermal desorption mass spectrometry
THF tetrahydrofuran
4 Principle
In the HPLC-UV method, DIBP, DBP, BBP and DEHP are determined using ultrasonic extraction
followed by high-pressure, liquid chromatography separation and ultraviolet detection. Owing
to the peak overlapping of DIBP, DBP and BBP, occurrence of the peak indicates only
qualitative information of possible presence of DIBP, DBP and BBP or a combination of one or
two of either of these phthalates.
The TLC method, as well as the HPLC method, is one of the liquid chromatography methods
and can be performed with simple instruments. In the TLC method, DIBP, DBP, BBP and DEHP
in the polymer are separated by TLC after ultrasonic extraction and detected by image analysis
after photography under UV light. DIBP and DBP are detected as sum peaks because it is
difficult to separate them by TLC.
IEC 62321-3-4:2023 © IEC 2023 – 11 –
TD-MS techniques use a thermal desorption system directly connected to mass spectrometry
with ionization systems such as an atmospheric pressure chemical ionization or ion attachment
to screen for the presence of DIBP, DBP, BBP and DEHP in polymers. This method allows for
the direct analysis of a polymer sample without pre-treatment process. For example:
+
– The APCI-MS method has an ion source that attaches H to target molecules by a corona
discharge under atmospheric pressure and is coupled with a furnace stabilized at 330 °C
and a sample heater. The sample heater is programmed to heat up to 230 °C to thermally
desorb sample molecules. The thermally desorbed sample molecules (M) form adducts
+ +
(M + H ) with H in the reaction and are analysed by a mass spectrometer via select ion
monitoring.
+ +
– The IA-MS method includes a Li attachment reaction chamber with a Li emitter and is
coupled with a direct injection probe (DIP). The DIP is programmed to heat up to 350 °C to
thermally desorb sample molecules. The thermally desorbed sample molecules (M) form
+ +
adducts (M + Li ) with Li in the reaction chamber and those adducts are analysed by a
mass spectrometer via select ion monitoring.
Therefore, target molecules with the same molecular weight such as DBP and DIBP, DEHP and
Di-n-octyl phthalate (DNOP) are detected as sum peaks by TD-MS techniques.
The principle of phthalate detection by FT-IR can be referenced in Annex A.
These test methods are based on the concept of performance. Apparatus, sampling and
calibration are specified in this document in relatively general terms. It is the responsibility of
the user to document all procedures developed in the laboratory that uses the test methods
described in this document. The user shall establish a written procedure for all cases denoted
in the test methods described in this document by the term "work instructions". A flowchart is
provided in Annex E as an example of how these methods can be used for screening.
5 HPLC-UV and TLC method
5.1 Reagents and materials
5.1.1 Reagents and materials of HPLC-UV method
All chemicals shall be tested for contamination and blank values prior to application, as follows:
a) methanol (HPLC grade, purity greater than a volume fraction of 99,7 %);
b) THF (HPLC grade, purity greater than a volume fraction of 99,7 %);
c) ethanol (HPLC grade, purity greater than a volume fraction of 99,7 %);
d) ultrapure water (HPLC grade);
e) standard mixture solution or reference polymer materials as calibrants:
one contains approximately 1 000 mg/kg of phthalates.
NOTE Commercially available reference materials are listed in Annex D.
5.1.2 Reagents and materials of TLC method
All chemicals shall be tested for contamination and blank values prior to application, as follows:
a) acetonitrile;
b) methanol;
c) standard mixture solution or reference polymer materials as calibrants:
one contains approximately 1 000 mg/kg of phthalates;
NOTE Commercially available reference materials are listed in Annex D.
– 12 – IEC 62321-3-4:2023 © IEC 2023
5.2 Equipment, apparatus and tools
5.2.1 Equipment, apparatus and tools for HPLC-UV method
The following equipment shall be used for the analysis:
a) high-performance liquid chromatography (HPLC) system equipped with a UV or PDA/UV
detector, auto sampler, pump and column oven;
b) analytical balance capable of measuring accurately to 0,000 1 g (0,1 mg);
c) ultrasonic bath (capable of heating above 50 °C);
The following equipment should be used for sample preparation as necessary:
d) cryogenic grinding or milling with liquid N cooling.
The following items shall be used for the analysis:
e) column;
f) glass vials for HPLC-UV;
g) glass vials for extraction (40 ml volume is recommended);
h) volumetric flask;
i) adjustable pipettes;
j) paper filters, medium-fast filtration, general laboratory use.
NOTE The size of the required glass vial for HPLC depends on the instrument.
5.2.2 Equipment, apparatus and tools for TLC method
The following equipment shall be used for the analysis:
a) ultrasonic bath (capable of heating above 60 °C);
b) analytical balance (capable of measuring accurately to 0,000 1 g (0,1 mg));
c) TLC plate (stationary phase C18, size 20 cm × 20 cm, cut in half to 20 cm × 10 cm);
d) TLC developing chamber;
e) UV lamp (λ = 254 nm, 2 units required);
f) digital camera (with UV lens filter for ultraviolet adsorption as optional);
g) clamp (for fixing UV lamps and a camera);
h) desktop darkroom.
The following items shall be used for the analysis:
a) glass vials for extraction (4 ml volume is recommended);
d) capillary (capacity 1 µl);
c) volumetric flask;
d) adjustable pipettes or micro syringes;
e) scissors or cutter knife.
5.3 Sampling
Unless otherwise specified in this document, the sampling procedure described in IEC 62321-2
shall be referred to.
IEC 62321-3-4:2023 © IEC 2023 – 13 –
All items used in the samples preparation for measurements shall be shown to be free of
contamination, specific for the analytes of this TLC method. This means that all grinding
materials, solvents, fluxes, etc. shall not contain detectable quantities of phthalates (DIBP, DBP,
BBP, and DEHP).
Tools used in the handling of samples shall be chosen to minimize contamination by the
analytes of this TLC test method as well as by any other elements or species. The procedures
which will be used for cleaning different tools shall not introduce any contaminants.
5.4 Procedure
5.4.1 Procedure of HPLC-UV method
5.4.1.1 Sample preparation
5.4.1.1.1 General
Sample preparation requires clean glassware (e.g. single use items) to avoid cross
contamination.
5.4.1.1.2 Polymer sample
a) Cryogenic grinding with liquid N cooling is recommended to achieve a particle size under
1 mm.
b) Weigh 150 mg ± 20 mg of the sample and transfer it into a glass vial for extraction. Record
the mass to the nearest 0,1 mg.
c) Transfer 5 ml of THF to the vial.
d) Tightly cap the sample vial. Place it in an ultrasonic bath (50 °C) and sonicate for 60 min
until the sample has dissolved. A small piece of adhesive tape may be used to prevent the
cap from loosening due to vibration.
e) After the sample is dissolved, allow the vial to cool to ambient temperature.
f) Accurately add 10 ml of ethanol dropwise into the vial to precipitate the sample matrix.
g) Allow the polymer to settle or filter the mixture through a paper filter made of hydrophilic
polytetrafluoroethylene.
5.4.1.1.3 Standard solution
Whenever possible, the solvent used for the HPLC sample and standard solutions shall be the
same to avoid any potential solvent effects.
The standard mixture solutions of phthalates given in Table 1 are used for calibration. A
reference polymer material which concentration is approximately 1 000 mg/kg can be used for
preparing the standard stock solution. When using reference polymer materials, the standard
mixture solution shall be prepared in accordance with 5.4.1.1.2.
Table 1 – Standard mixture solution concentrations
No. DIBP DBP BBP DEHP
10 µg/ml 10 µg/ml 10 µg/ml 10 µg/ml
(equivalent to (equivalent to (equivalent to (equivalent to
1 000 mg/kg) 1 000 mg/kg) 1 000 mg/kg) 1 000 mg/kg)
5.4.1.2 Instrumental parameters
Different conditions can be necessary to optimize a specifi
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