EN 62321-3-1:2014

Determination of certain substances in electrotechnical products - Part 3-1: Screening - Lead, mercury, cadmium, total chromium and total bromine by X-ray fluorescence spectrometry

IEC 62321-3-1:2013 describes the screening analysis of five substances, specifically lead (Pb), mercury (Hg), cadmium (Cd), total chromium (Cr) and total bromine (Br) in uniform materials found in electrotechnical products, using the analytical technique of X-ray fluorescence (XRF) spectrometry.

Verfahren zur Bestimmung von bestimmten Substanzen in Produkten der Elektrotechnik - Teil 3-1: Screening - Blei, Quecksilber, Cadmium, Gesamtchrom und Gesamtbrom durch Röntgenfluoreszenz-Spektrometrie

Détermination de certaines substances dans les produits électrotechniques - Partie 3-1: Méthodes d'essai - Plomb, du mercure, du cadmium, du chrome total et du brome total par la spectrométrie par fluorescence X

La CEI 62321-3-1:2013 décrit des procédures d'analyse de détection de cinq substances, spécifiquement le plomb (Pb), le mercure (Hg), le cadmium (Cd), le chrome total (Cr) et le brome total (Br) dans des matériaux uniformes utilisés dans les produits électrotechniques en utilisant la technique d'analyse de spectrométrie par fluorescence X (XRF).

Določevanje posameznih snovi v elektrotehničnih izdelkih - 3-1. del: Presejanje elektrotehničnih izdelkov glede svinca, živega srebra, kadmija, celotnega kroma in celotnega broma z rentgensko fluorescenčno spektrometrijo (IEC 62321-3-1:2013)

Standard EN-IEC 62321-3-1opisuje presejalno analizo petih snovi, zlasti svinca (Pb), živega srebra (Hg), kadmija (Cd), skupnega kroma (Cr) in skupnega broma (Br) v homogenih materialih, ki se nahajajo v elektrotehničnih izdelkih, z rentgensko fluorescenčno spektrometrijo (XRF). Velja za polimere, kovine in keramične materiale. Preskusna metoda se lahko uporabi za surovine, posamezne materiale, pridobljene iz proizvodov, in »homogenizirane« mešanice več kot enega materiala. Presejanje vzorca se izvede z uporabo katere koli vrste spektrometra za rentgensko fluorescenčno spektrometrijo, če ima zmogljivostne lastnosti, navedene v tej preskusni metodi. Vse vrste spektrometrov za rentgensko fluorescenčno spektrometrijo niso primerne za vzorce vseh velikosti in oblik. Treba je paziti, da za izbrano nalogo izberete ustrezno zasnovan spektrometer.

General Information

• Status: Published
• Publication Date: 24-Apr-2014
• Withdrawal Date: 14-Nov-2016
• ICS: 13.020 - Environmental protection
• ICS: 43.040.10 - Electrical and electronic equipment
• Technical Committee: CLC/TC 111X - Environment
• Drafting Committee: IEC/TC 111 - Environmental standardization for electrical and electronic products and systems
• Current Stage: 6060 - Document made available - Publishing
• Start Date: 25-Apr-2014
• Completion Date: 25-Apr-2014
• Directive: 2002/95/EC - Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment
• Directive: 2011/65/EU - DIRECTIVE 2011/65/EU OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 8 June 2011 on the restriction of the use of certain hazardous substances in electrical and electronic equipment
• Ref Project: SIST EN 62321-3-1:2014 - Determination of certain substances in electrotechnical products - Part 3-1: Screening test methods - Screening of electrotechnical products for lead, mercury, cadmium, total chromium and total bromine using X-ray fluorescence spectrometry

Relations

• Replaces: EN 62321:2009 - Electrotechnical products - Determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers)
• Effective Date: 29-Jan-2023
• Revised: prEN IEC 62321-3-1:2025 - Determination of certain substances in electrotechnical products - Part 3-1: Screening - Lead, mercury, cadmium, total chromium total bromine, total phosphorus, total chlorine, total tin and total antimony content by x-ray fluorescence spectrometry
• Effective Date: 26-Jan-2023

Standards Content (Sample)

SLOVENSKI STANDARD
01-junij-2014
1DGRPHãþD
SIST EN 62321:2009
'RORþHYDQMHSRVDPH]QLKVQRYLYHOHNWURWHKQLþQLKL]GHONLKGHO3UHVHMDQMH
HOHNWURWHKQLþQLKL]GHONRYJOHGHVYLQFDåLYHJDVUHEUDNDGPLMDFHORWQHJDNURPDLQ
FHORWQHJDEURPD]UHQWJHQVNRIOXRUHVFHQþQRVSHNWURPHWULMR,(&
Determination of certain substances in electrotechnical products - Part 3-1: Screening
test methods - Screening of electrotechnical products for lead, mercury, cadmium, total
chromium and total bromine using X-ray fluorescence spectrometry
Verfahren zur Bestimmung von bestimmten Substanzen in Produkten der Elektrotechnik
- Teil 3-1: Ermittlung von Blei (Pb), Quecksilber (Hg), Cadmium (Cd), Gesamtchrom (Cr)
und Brom (Br) durch Röntgenfluoreszenz-Spektrometrie in elektrotechnischen Produkten
Détermination de certaines substances dans les produits électrotechniques -- Partie 3-1:
Détection du plomb, du mercure, du cadmium, du chrome total et du brome total dans
les produits électrotechniques par spectrométrie par fluorescence X
Ta slovenski standard je istoveten z: EN 62321-3-1:2014
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 62321-3-1
NORME EUROPÉENNE
April 2014
EUROPÄISCHE NORM
ICS 13.020; 43.040.10 Supersedes EN 62321:2009 (partially)

English version
Determination of certain substances in electrotechnical products -
Part 3-1: Screening -
Lead, mercury, cadmium, total chromium and total bromine by X-ray
fluorescence spectrometry
(IEC 62321-3-1:2013)
Détermination de certaines substances Verfahren zur Bestimmung von
dans les produits électrotechniques - bestimmten Substanzen in Produkten der
Partie 3-1: Méthodes d'essai - Elektrotechnik -
Plomb, du mercure, du cadmium, du Teil 3-1: Screening -
chrome total et du brome total par la Blei, Quecksilber, Cadmium,
spectrométrie par fluorescence X Gesamtchrom und Gesamtbrom durch
(CEI 62321-3-1:2013) Röntgenfluoreszenz-Spektrometrie
(IEC 62321-3-1:2013)
This European Standard was approved by CENELEC on 2013-11-15. 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, Former Yugoslav Republic of Macedonia, France, Germany,
Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, the Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.

CENELEC
European Committee for Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung

CEN-CENELEC Management Centre: Avenue Marnix 17, B - 1000 Brussels

© 2014 CENELEC - All rights of exploitation in any form and by any means reserved worldwide for CENELEC members.
Ref. No. EN 62321-3-1:2014 E
Foreword
The text of document 111/298/FDIS, future edition 1 of IEC 62321-3-1, 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 62321-3-1:2014.
The following dates are fixed:
(dop) 2014-10-25
• latest date by which the document has
to be implemented at national level by
publication of an identical national
standard or by endorsement
• latest date by which the national (dow) 2016-11-15
standards conflicting with the

document have to be withdrawn
generally replacing Clauses 6 and Annex D.
Future parts in the EN 62321 series will gradually replace the corresponding clauses in EN 62321:2009.
Until such time as all parts are published, however, EN 62321:2009 remains valid for those clauses not
yet re-published as a separate part.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CENELEC [and/or CEN] shall not be held responsible for identifying any or all such patent
rights.
Endorsement notice
The text of the International Standard IEC 62321-3-1:2013 was approved by CENELEC as a European
Standard without any modification.

- 3 - EN 62321-3-1:2014
Annex ZA
(normative)
Normative references to international publications
with their corresponding European publications

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.

NOTE  When an international publication has been modified by common modifications, indicated by (mod), the relevant EN/HD
applies.
Publication Year Title EN/HD Year

IEC 62321-1 - Determination of certain substances in EN 62321-1 -
electrotechnical products -
Part 1: Introduction and overview

IEC 62321-2 - Determination of certain substances in EN 62321-2 -
electrotechnical products -
Part 2: Disassembly, disjunction and
mechanical sample preparation
ISO/IEC Guide 98-1 - Uncertainty of measurement - - -
Part 1: Introduction to the expression of
uncertainty in measurement
IEC 62321-3-1 ®
Edition 1.0 2013-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
colour
inside
Determination of certain substances in electrotechnical products –

Part 3-1: Screening – Lead, mercury, cadmium, total chromium and total bromine

by X-ray fluorescence spectrometry

Détermination de certaines substances dans les produits électrotechniques –

Partie 3-1: Méthodes d'essai – Plomb, du mercure, du cadmium, du chrome total

et du brome total par la spectrométrie par fluorescence X

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
PRICE CODE
INTERNATIONALE
CODE PRIX X
ICS 13.020; 43.040.10 ISBN 978-2-83220-839-7

– 2 – 62321-3-1 © IEC:2013
CONTENTS
FOREWORD . 5
INTRODUCTION . 7
1 Scope . 8
2 Normative references . 10
3 Terms, definitions and abbreviations . 10
4 Principle . 10
4.1 Overview . 10
4.2 Principle of test . 11
4.3 Explanatory comments . 11
5 Apparatus, equipment and materials . 12
5.1 XRF spectrometer . 12
5.2 Materials and tools . 12
6 Reagents . 12
7 Sampling . 12
7.1 General . 12
7.2 Non-destructive approach . 12
7.3 Destructive approach. 12
8 Test procedure . 13
8.1 General . 13
8.2 Preparation of the spectrometer . 13
8.3 Test portion . 14
8.4 Verification of spectrometer performance . 14
8.5 Tests . 15
8.6 Calibration . 15
9 Calculations . 16
10 Precision . 17
10.1 General . 17
10.2 Lead . 17
10.3 Mercury . 17
10.4 Cadmium . 17
10.5 Chromium . 18
10.6 Bromine. 18
10.7 Repeatability statement for five tested substances sorted by type of tested
material . 18
10.7.1 General . 18
10.7.2 Material: ABS (acrylonitrile butadiene styrene), as granules and
plates . 18
10.7.3 Material: PE (low density polyethtylene), as granules . 19
10.7.4 Material: PC/ABS (polycarbonate and ABS blend), as granules . 19
10.7.5 Material: HIPS (high impact polystyrene) . 19
10.7.6 Material: PVC (polyvinyl chloride), as granules . 19
10.7.7 Material: Polyolefin, as granules . 19
10.7.8 Material: Crystal glass . 20
10.7.9 Material: Glass . 20
10.7.10 Material: Lead-free solder, chips . 20

62321-3-1 © IEC:2013 – 3 –
10.7.11 Material: Si/Al Alloy, chips . 20
10.7.12 Material: Aluminum casting alloy, chips . 20
10.7.13 Material: PCB – Printed circuit board ground to less than 250 µm . 20
10.8 Reproducibility statement for five tested substances sorted by type of tested
material . 20
10.8.1 General . 20
10.8.2 Material: ABS (Acrylonitrile butadiene styrene), as granules and
plates . 21
10.8.3 Material: PE (low density polyethtylene), as granules . 21
10.8.4 Material: PC/ABS (Polycarbonate and ABS blend), as granules . 21
10.8.5 Material: HIPS (high impact polystyrene) . 21
10.8.6 Material: PVC (polyvinyl chloride), as granules . 22
10.8.7 Material: Polyolefin, as granules . 22
10.8.8 Material: Crystal glass . 22
10.8.9 Material: Glass . 22
10.8.10 Material: Lead-free solder, chips . 22
10.8.11 Material: Si/Al alloy, chips . 22
10.8.12 Material: Aluminum casting alloy, chips . 22
10.8.13 Material: PCB – Printed circuit board ground to less than 250 µm . 22
11 Quality control . 23
11.1 Accuracy of calibration . 23
11.2 Control samples . 23
12 Special cases . 23
13 Test report . 23
Annex A (informative) Practical aspects of screening by X-ray fluorescence
spectrometry (XRF) and interpretation of the results . 25
Annex B (informative) Practical examples of screening with XRF . 31
Bibliography . 40

Figure B.1 – AC power cord, X-ray spectra of sampled sections . 32
Figure B.2 – RS232 cable and its X-ray spectra . 33
Figure B.3 – Cell phone charger shown partially disassembled . 34
Figure B.4 – PWB and cable of cell phone charger . 35
Figure B.5 – Analysis of a single solder joint on a PWB . 36
Figure B.6 – Spectra and results obtained on printed circuit board with two collimators . 36
Figure B.7 – Examples of substance mapping on PWBs . 38
Figure B.8 – SEM-EDX image of Pb free solder with small intrusions of Pb (size = 30 µm) . 39

Table 1 – Tested concentration ranges for lead in materials . 8
Table 2 – Tested concentration ranges for mercury in materials . 9
Table 3 – Tested concentration ranges for cadmium in materials . 9
Table 4 – Tested concentration ranges for total chromium in materials . 9
Table 5 – Tested concentration ranges for total bromine in materials . 9
Table 6 – Recommended X-ray lines for individual analytes . 14
Table A.1 – Effect of matrix composition on limits of detection of some controlled
elements . 26

– 4 – 62321-3-1 © IEC:2013
Table A.2 – Screening limits in mg/kg for regulated elements in various matrices . 27
Table A.3 – Statistical data from IIS2 . 29
Table A.4 – Statistical data from IIS4 . 30
Table B.1 – Selection of samples for analysis of AC power cord . 32
Table B.2 – Selection of samples (testing locations) for analysis after visual inspection
– Cell phone charger. 34
Table B.3 – Results of XRF analysis at spots (1) and (2) as shown in Figure B.6 . 37

62321-3-1 © IEC:2013 – 5 –
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-1: Screening – Lead, mercury, cadmium, total chromium
and total bromine by X-ray fluorescence spectrometry

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.
International Standard IEC 62321-3-1 has been prepared by IEC technical committee 111:
Environmental standardization for electrical and electronic products and systems.
The first edition of IEC 62321:2008 was a 'stand alone' standard that included an introduction,
an overview of test methods, a mechanical sample preparation as well as various test method
clauses.
This first edition of IEC 62321-3-1 is a partial replacement of IEC 62321:2008, forming a
structural revision and generally replacing Clauses 6 and Annex D.
Future parts in the IEC 62321 series will gradually replace the corresponding clauses in
IEC 62321:2008. Until such time as all parts are published, however, IEC 62321:2008 remains
valid for those clauses not yet re-published as a separate part.

– 6 – 62321-3-1 © IEC:2013
The text of this standard is based on the following documents:
FDIS Report on voting
111/298/FDIS 111/308/RVD
Full information on the voting for the approval of this standard can be found in the report on
voting indicated in the above table.
This publication has been drafted in accordance with the ISO/IEC Directives, Part 2.
A list of all parts in the IEC 62321 series can be found on the IEC website under the general
title: Determination of certain substances in electrotechnical products
The committee has decided that the contents of this publication will remain unchanged until
the stability date indicated on the IEC web site under "http://webstore.iec.ch" in the data
related to the specific publication. At this date, the publication will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.
IMPORTANT – The 'colour inside' logo on the cover page of this publication indicates
that it contains colours which are considered to be useful for the correct
understanding of its contents. Users should therefore print this document using a
colour printer.
62321-3-1 © IEC:2013 – 7 –
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries 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) and polybrominated diphenyl
ethers (PBDEs)) 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.
WARNING – Persons using this International Standard should be familiar with normal
laboratory practice. This standard 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 – 62321-3-1 © IEC:2013
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-1: Screening – Lead, mercury, cadmium, total chromium
and total bromine by X-ray fluorescence spectrometry

1 Scope
Part 3-1 of IEC 62321 describes the screening analysis of five substances, specifically lead
(Pb), mercury (Hg), cadmium (Cd), total chromium (Cr) and total bromine (Br) in uniform
materials found in electrotechnical products, using the analytical technique of X-ray
fluorescence (XRF) spectrometry.
It is applicable to polymers, metals and ceramic materials. The test method may be applied to
raw materials, individual materials taken from products and “homogenized” mixtures of more
than one material. Screening of a sample is performed using any type of XRF spectrometer,
provided it has the performance characteristics specified in this test method. Not all types of
XRF spectrometers are suitable for all sizes and shapes of sample. Care should be taken to
select the appropriate spectrometer design for the task concerned.
The performance of this test method has been tested for the following substances in various
media and within the concentration ranges as specified in Tables 1 to 5.
Table 1 – Tested concentration ranges for lead in materials
Substance/
Lead
element
Medium/material tested
Unit of
a b d
ABS PE Low- Al, Lead- Ground Crystal PVC Poly-
Parameter
measure
c
alloy Al-Si free PWB glass olefine
steel alloy solder
Concentration
15,7 14 190 22 000 390
or 380 to
e
mg/kg to to 30 to 174 to 240 000 to
concentration 640
954 108 930 23 000 665
range tested
a
Acrylonitrile butadiene styrene.
b
Polyethylene.
c
Printed wiring board.
d
Polyvinyl chloride.
e
This lead concentration was not detectable by instruments participating in tests.

62321-3-1 © IEC:2013 – 9 –
Table 2 – Tested concentration ranges for mercury in materials
Substance/element Mercury
Medium/material tested
Parameter Unit of measure
a b
ABS PE
Concentration or concentration range
mg/kg 100 to 942 4 to 25
tested
a
Acrylonitrile butadiene styrene.
b
Polyethylene.
Table 3 – Tested concentration ranges for cadmium in materials
Substance/element Cadmium
Medium/material tested
Parameter Unit of measure
a b
Lead-free solder ABS PE
Concentration or concentration
c
mg/kg 3 10 to 183 19,6 to 141
range tested
a
Acrylonitrile butadiene styrene.
b
Polyethylene.
c
This cadmium concentration was not detectable by instruments participating in tests.

Table 4 – Tested concentration ranges for total chromium in materials
Substance/element Chromium
Medium/material tested
Unit of
Low-
Parameter
Al, Al-Si
measure a b
ABS PE alloy Glass
alloy
steel
Concentration or
concentration range mg/kg 16 to 944 16 to 115 240 130 to 1 100 94
tested
a
Acrylonitrile butadiene styrene.
b
Polyethylene.
Table 5 – Tested concentration ranges for total bromine in materials
Substance/element Bromine
Medium/material tested
Unit of
Parameter
measure c a d b
HIPS , ABS PC/ABS PE
Concentration or concentration
mg/kg 25 to 118 400 800 to 2 400 96 to 808
range tested
a
Acrylonitrile butadiene styrene.
b
Polyethylene.
c
High impact polystyrene.
d
Polycarbonate and ABS blend.
These substances in similar media outside of the specified concentration ranges may be
analysed according to this test method; however, the performance has not been established
for this standard.
– 10 – 62321-3-1 © IEC:2013
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.
IEC 62321-1, Determination of certain substances in electrotechnical products – Part 1:
Introduction and overview
IEC 62321-2, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjointment and mechanical sample preparation
IEC/ISO Guide 98-1, Uncertainty of measurement – Part 1: Introduction to the expression of
uncertainty in measurement
3 Terms, definitions and abbreviations
For the purposes of this document, the terms, definitions and abbreviations given in
IEC 62321-1 and IEC 62321-2 apply.
4 Principle
4.1 Overview
The concept of 'screening' has been developed to reduce the amount of testing. Executed as
a predecessor to any other test analysis, the main objective of screening is to quickly
determine whether the screened part or section of a product:
– contains a certain substance at a concentration significantly higher than its value or values
chosen as criterion, and therefore may be deemed unacceptable;
– contains a certain substance at a concentration significantly lower than its value or values
chosen as criterion, and therefore may be deemed acceptable;
– contains a certain substance at a concentration so close to the value or values chosen as
criterion that when all possible errors of measurement and safety factors are considered,
no conclusive decision can be made about the acceptable absence or presence of a
certain substance and, therefore, a follow-up action may be required, including further
analysis using verification testing procedures.
This test method is designed specifically to screen for lead, mercury, cadmium, chromium and
bromine (Pb, Hg, Cd, Cr, Br) in uniform materials, which occur in most electrotechnical
products. Under typical circumstances, XRF spectrometry provides information on the total
quantity of each element present in the sample, but does not identify compounds or valence
states of the elements. Therefore, special attention shall be paid when screening for
chromium and bromine, where the result will reflect only the total chromium and total bromine
present. The presence of Cr(VI) or the brominated flame retardants PBB or PBDE shall be
confirmed by a verification test procedure. When applying this method to electronics “as
received”, which, by the nature of their design, are not uniform, care shall be taken in
interpreting the results. Similarly, the analysis of Cr in conversion coatings may be difficult
due to the presence of Cr in substrate material and/or because of insufficient sensitivity for Cr
in typically very thin (several hundred nm) conversion coating layers.
Screening analysis can be carried out by one of two means:
___________
To be published.
62321-3-1 © IEC:2013 – 11 –
• non-destructively – by directly analysing the sample “as received”;
• destructively – by applying one or more sample preparation steps prior to analysis.
In the latter case, the user shall apply the procedure for sample preparation as described in
IEC 62321-2. This test method will guide the user in choosing the proper approach to sample
presentation.
4.2 Principle of test
The representative specimen of the object tested is placed in the measuring chamber or over
the measuring aperture of the X-ray fluorescence spectrometer. Alternatively, a measuring
window/aperture of a handheld, portable XRF analyser is placed flush against the surface of
the object tested. The analyser illuminates the specimen for a preselected measurement time
with a beam of X rays which in turn excite characteristic X rays of elements in the specimen.
The intensities of these characteristic X rays are measured and converted to mass fractions
or concentrations of the elements in the tested sample using a calibration implemented in the
analyser.
The fundamentals of XRF spectrometry, as well as practical aspects of sampling for XRF, are
covered in detail in [1, 2 and 3].
4.3 Explanatory comments
To achieve its purpose, this test method shall provide rapid, unambiguous identification of the
elements of interest. The test method shall provide at least a level of accuracy that is
sometimes described as semi-quantitative, i.e. the relative uncertainty of a result is typically
30 % or better at a defined level of confidence of 68 %. Some users may tolerate higher
relative uncertainty, depending on their needs. This level of performance allows the user to
sort materials for additional testing. The overall goal is to obtain information for risk
management purposes.
This test method is designed to allow XRF spectrometers of all designs, complexity and
capability to contribute screening analyses. However, the capabilities of different XRF
spectrometers cover such a wide range that some will be relatively inadequate in their
selectivity and sensitivity while others will be more than adequate. Some spectrometers will
allow easy measurement of a wide range of sample shapes and sizes, while others, especially
research-grade WDXRF units, will be very inflexible in terms of test portions.
Given the above level of required performance and the wide variety of XRF spectrometers
capable of contributing useful measurements, the requirements for the specification of
procedures are considerably lower than for a high-performance test method for quantitative
determinations with low estimates of uncertainty.
This test method is based on the concept of a performance based measurement system.
Apparatus, sample preparation and calibration are specified in this standard in relatively
general terms. It is the responsibility of the user to document all procedures developed in the
laboratory that uses the test method. The user shall establish a written procedure for all cases
denoted in this method by the term “work instructions”.
The user of this test method shall document all relevant spectrometer and method
performance parameters.
WARNING 1 Persons using the XRF test method shall be trained in the use of XRF
spectrometers and the related sampling requirements.
WARNING 2 Xrays are hazardous to humans. Care shall be taken to operate the equipment
in accordance with both the safety instructions provided by the manufacturer and the
applicable local health and occupational safety regulations.

– 12 – 62321-3-1 © IEC:2013
5 Apparatus, equipment and materials
5.1 XRF spectrometer
An XRF spectrometer consists of an X-ray excitation source, a means of reproducible sample
presentation, an X-ray detector, a data processor and a control system [4, 5 and 6]:
a) source of X-ray excitation – X-ray tube or radio-isotope sources are commonly used;
b) X-ray detector (detection subsystem) – Device used to convert the energy of an X-ray
photon to a corresponding electric pulse of amplitude proportional to the photon energy.
5.2 Materials and tools
All materials used in the preparation of samples for XRF measurements shall be shown to be
free of contamination, specifically by the analytes of this test method. This means that all
grinding materials, solvents, fluxes, etc. shall not contain detectable quantities of Pb, Hg, Cd,
Cr and/or Br.
Tools used in the handling of samples shall be chosen to minimize contamination by the
analytes of this test method as well as by any other elements. Any procedures used to clean
the tools shall not introduce contaminants.
6 Reagents
Reagents, if any, shall be of recognized analytical grade and shall not contain detectable
quantities of Pb, Hg, Cd, Cr and/or Br.
7 Sampling
7.1 General
It is the responsibility of the user of this test method to define the test sample using
documented work instructions. The user may choose to define the test sample in a number of
ways, either via a non-destructive approach in which the portion to be measured is defined by
the viewing area of the spectrometer, or by a destructive approach in which the portion to be
measured is removed from the larger body of material and either measured as is, or
destroyed and prepared using a defined procedure.
7.2 Non-destructive approach
The user of this test method shall:
a) establish the area viewed by the spectrometer and place the test sample within that area,
taking care to ascertain that no fluorescent X-rays will be detected from materials other
than the defined test portion. Usually, the area viewed by the spectrometer is a section of
a plane delineated by the shape and boundary of the measuring window of the instrument.
The area of the test sample viewed by the spectrometer shall be flat. Any deviation from
the flat area requirement shall be documented;
b) make sure that a repeatable measurement geometry with a repeatable distance between
the spectrometer and the test portion is established;
c) document the steps taken to disassemble a larger object to obtain a test portion.
7.3 Destructive approach
The following points shall be taken into account in the destructive approach:

62321-3-1 © IEC:2013 – 13 –
a) the user shall create and follow a documented work instruction for the means of
destruction applied to obtain the test portion, as this information is critical for correct
interpretation of the measurement results;
b) a procedure that results in a powder shall produce a material with a known or controlled
particle size. In cases where the particles have different chemical, phase or mineralogical
compositions, it is critical to reduce their size sufficiently to minimize differential
absorption effects;
c) in a procedure that results in a material being dissolved in a liquid matrix, the quantity and
physical characteristics of the material to be dissolved shall be controlled and documented.
The resulting solution shall be completely homogeneous. Instructions shall be provided to
deal with undissolved portions to ensure proper interpretation of the measured results.
Instructions shall be provided for presentation of the test portion of the solution to the X-
ray spectrometer in a repeatable manner, i.e. in a liquid cell of specified construction and
dimensions;
d) in a procedure that results in a sample material being fused or pressed in a solid matrix,
the quantity and physical characteristics of the sample material shall be controlled and
documented. The resulting solid (fused or pressed pellet) shall be completely uniform.
Instructions shall be provided to deal with unmixed portions to ensure proper
interpretation of the measured results.
8 Test procedure
8.1 General
The test procedure covers preparation of the X-ray spectrometer, preparation and mounting of
test portions and calibration. Certain instructions are presented in general terms due to the
wide range of XRF equipment and the even greater variety of laboratory and test samples to
which this test method will be applied. However, a cardinal rule that applies without exception
to all spectrometers and analytical methods shall be followed; that is that the calibration and
sample measurements be performed under the same conditions and using the same sample
preparation procedures.
In view of the wide range of XRF spectrometer designs and the concomitant range of
detection capabilities, it is important to understand the limitation of the chosen instrument.
Certain designs may be incapable of detecting or accurately determining the composition of a
very small area or very thin samples. As a consequence, it is imperative that users carefully
establish and clearly document the performance of the test method as implemented in their
laboratories. One goal is to prevent false negative test results.
8.2 Preparation of the spectrometer
Prepare the spectrometer as follows:
a) switch on the instrument and prepare it for operation according to the manufacturer’s
manual. Allow the instrument to stabilize as per guidelines established by the
manufacturer or laboratory work instructions;
b) set the measurement conditions to the optimum conditions previously established by the
manufacturer or the laboratory.
Many instruments available on the market are already optimized and preset for a particular
application, and therefore this step might not be necessary. Otherwise, the laboratory should
establish optimum operating conditions for each calibration. Choices should be made to
optimize sensitivity and minimize spectral interferences. Excitation conditions may vary by
material, analyte and X-ray line energy. A list of recommended analytical X-ray lines is given
in Table 6. Detection system settings should optimize the compromise between sensitivity and
energy resolution. Guidance can usually be found in the instrument manual and in literature
on X-ray spectrometry [1, 2 and 3].

– 14 – 62321-3-1 © IEC:2013
a
Table 6 – Recommended X-ray lines for individual analytes
Analyte Preferred line Secondary line
Lead (Pb) L –M (Lβ ) L –M (Lα )
2 4 1 3 4,5 1,2
Mercury (Hg) L –M (Lα )
3 4,5 1,2
b
Cadmium (Cd) K–L (Kα )
2,3 1,2
Chromium (Cr) K–L (Kα )
2,3 1,2
Bromine (Br) K–L (Kα ) K–M (Kβ )
2,3 1,2 2,3 1,3
a
Other X-ray line choices may provide adequate performance. However, when deciding on alternative
analytical lines one should be aware of possible spectral interferences from other elements present in the
sample (e.g. BrKα on PbLα or AsKα on PbLα lines; see Clause A.2 b) for more typical examples).
b
K–L (Kα ) means that there are actually two transitions to the K shell, i.e. one from the L shell which
2,3 1,2 2
generates Kα X-rays and another from the L shell that generates Kα X- rays. However, since both energies
2 3 1
are very close, energy dispersive spectrometers cannot distinguish them and so they are analysed as one
combined K α energy.
1,2
8.3 Test portion
The creation of a test portion is described in Clause 7.
In the case of destructive sample preparation, measure the mass and dimensions of the test
portion as required by the calibration method and the work instruction established by the
laboratory to ensure repeatable sampling. The location of the test portion shall also be documented
in relation to its origin on the electrotechnical product.
8.4 Verification of spectrometer performance
Spectrometer performance shall be verified as follows:
a) Users shall provide objective evidence of the performance of the method as implement
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