SIST EN 13603:2021
(Main)Copper and copper alloys - Test methods for assessing protective tin coatings on drawn round copper wire for electrical purposes
Copper and copper alloys - Test methods for assessing protective tin coatings on drawn round copper wire for electrical purposes
This European Standard specifies methods for assessing the tin coating on drawn round copper wire for the manufacture of electrical conductors, e.g. according to EN 13602.
This European Standard includes test methods for the determination of the following characteristics:
a) thickness of the unalloyed tin coating;
b) continuity of the tin coating;
c) adherence of the tin coating.
WARNING - This European Standard can involve the use of hazardous materials, operations, and equipment. This standard does not purport to address all of the safety problems associated with their use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
Kupfer und Kupferlegierungen - Prüfverfahren zur Beurteilung von Schutzüberzügen aus Zinn auf gezogenen Runddrähten aus Kupfer für die Anwendung in der Elektrotechnik
Dieses Dokument legt Verfahren zur Beurteilung eines Zinnüberzuges auf gezogenem Runddraht aus Kupfer zur Herstellung von elektrischen Leitern fest, z. B. nach EN 13602.
Dieses Dokument enthält Prüfverfahren zur Bestimmung der folgenden Eigenschaften:
a) Dicke des unlegierten Zinnüberzuges;
b) Gleichmäßigkeit des Zinnüberzuges;
c) Haftung des Zinnüberzuges.
WARNUNG — Dieses Dokument kann die Benutzung von Stoffen, Verfahren und Geräten beinhalten, von denen Gefährdungen ausgehen können. Dieses Dokument beabsichtigt nicht, auf alle Sicherheits-probleme einzugehen, die mit deren Gebrauch zusammenhängen. Es liegt in der Verantwortung des Anwenders dieses Dokuments, entsprechende Sicherheits- und Gesundheitsvorkehrungen zu treffen und vorschriftsmäßige Einschränkungen vor dem Gebrauch zu bestimmen. Darüber hinaus behandelt dieses Dokument nicht die Aspekte in Bezug auf den Schutz von Personen gegen Röntgenstrahlung. Um Informationen zu erhalten, die auf diesen Aspekt zutreffen, ist es zweckmäßig, sich auf nationale und internationale Normen zu beziehen, sowie auf die lokalen Bestimmungen, falls diese vorhanden sind.
Cuivre et alliages de cuivre - Méthodes d’évaluation des revêtements en étain sur les fils ronds étirés en cuivre pour usages électriques
Le présent document spécifie les méthodes permettant d’évaluer le revêtement en étain sur les fils ronds
étirés en cuivre destinés à la fabrication des conducteurs électriques, par exemple conformément à
l’EN 13602.
Le présent document inclut les méthodes d’essais pour la détermination des caractéristiques suivantes :
a) l’épaisseur du revêtement en étain non allié ;
b) la continuité du revêtement en étain ;
c) l’adhérence du revêtement en étain.
AVERTISSEMENT — Le présent document peut impliquer l’utilisation de matières, opérations et
équipements dangereux. Le présent document n’a pas pour objet d’aborder tous les problèmes de
sécurité associés à leur utilisation. Il incombe à l’utilisateur du présent document d’établir, avant de
l’utiliser, des pratiques d’hygiène et de sécurité appropriées et de déterminer l’applicabilité des
restrictions réglementaires. De plus, le présent document ne traite pas les aspects liés à la protection des
personnes contre les rayons X. Pour obtenir des informations applicables à cet aspect, il convient de se
référer aux Normes nationales et internationales, ainsi qu’aux réglementations locales si elles existent.
Baker in bakrove zlitine - Preskusne metode za ocenjevanje kakovosti zaščitnih kositrovih prevlek na okroglih bakrovih vlečenih žicah za elektrotehniko
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 13603:2021
01-september-2021
Nadomešča:
SIST EN 13603:2013
Baker in bakrove zlitine - Preskusne metode za ocenjevanje kakovosti zaščitnih
kositrovih prevlek na okroglih bakrovih vlečenih žicah za elektrotehniko
Copper and copper alloys - Test methods for assessing protective tin coatings on drawn
round copper wire for electrical purposes
Kupfer und Kupferlegierungen - Prüfverfahren zur Beurteilung von Schutzüberzügen aus
Zinn auf gezogenen Runddrähten aus Kupfer für die Anwendung in der Elektrotechnik
Cuivre et alliages de cuivre - Méthodes d’évaluation des revêtements en étain sur les fils
ronds étirés en cuivre pour usages électriques
Ta slovenski standard je istoveten z: EN 13603:2021
ICS:
25.220.40 Kovinske prevleke Metallic coatings
77.150.30 Bakreni izdelki Copper products
SIST EN 13603:2021 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN 13603:2021
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SIST EN 13603:2021
EN 13603
EUROPEAN STANDARD
NORME EUROPÉENNE
May 2021
EUROPÄISCHE NORM
ICS 25.220.40; 77.150.30 Supersedes EN 13603:2013
English Version
Copper and copper alloys - Test methods for assessing
protective tin coatings on drawn round copper wire for
electrical purposes
Cuivre et alliages de cuivre - Méthodes d'évaluation des Kupfer und Kupferlegierungen - Prüfverfahren zur
revêtements en étain sur les fils ronds étirés en cuivre Beurteilung von Schutzüberzügen aus Zinn auf
pour usages électriques gezogenen Runddrähten aus Kupfer für die
Anwendung in der Elektrotechnik
This European Standard was approved by CEN on 12 April 2021.
CEN 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 CEN
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 CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 13603:2021 E
worldwide for CEN national Members.
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EN 13603:2021 (E)
Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Thickness of the unalloyed tin coating . 5
4.1 General. 5
4.2 Principle of the method based on the electrolytic dissolution of the tin coating . 5
4.2.1 General. 5
4.2.2 Reagents and materials . 5
4.2.3 Apparatus . 5
4.2.4 Preparation of the test piece . 7
4.2.5 Procedure for determining the thickness of unalloyed tin coatings . 7
4.2.6 Expression of results . 10
4.3 Principle of the method based on XRF . 11
4.3.1 General. 11
4.3.2 Devices with measuring spots larger than the wire dia7meter — Overlap technique. 11
4.3.3 Devices with measuring spots smaller than the wire diameter – Full-spot technique . 12
4.3.4 Preparation of the test piece . 12
4.3.5 Factors affecting the measuring accuracy . 13
5 Continuity of the tin coating . 17
5.1 Principle . 17
5.2 Test solution . 17
5.3 Reference solution . 18
5.4 Preparation of the test piece . 18
5.5 Cleaning of the test piece . 18
5.6 Immersion for testing . 18
5.7 Determination . 19
5.7.1 General. 19
5.7.2 Comparison by Nessler cylinders . 19
5.7.3 Colorimetric method . 19
6 Adherence of the tin coating . 19
6.1 Principle . 19
6.2 Stock solution . 19
6.3 Test solution . 19
6.4 Preparation of the test piece . 19
6.5 Cleaning of the test piece . 20
6.6 Immersion for testing . 20
6.7 Examination . 20
7 Test report . 21
Bibliography . 22
2
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EN 13603:2021 (E)
European foreword
This document (EN 13603:2021) has been prepared by Technical Committee CEN/TC 133 “Copper and
copper alloys”, the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by November 2021, and conflicting national standards
shall be withdrawn at the latest by November 2021.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN 13603:2013.
In comparison with the previous edition, the following technical modifications have been made:
— included the X-ray fluorescence analysis (XRF) to measure the thickness of the tin layer.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,
Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of
North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the
United Kingdom.
3
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SIST EN 13603:2021
EN 13603:2021 (E)
1 Scope
This document specifies methods for assessing the tin coating on drawn round copper wire for the
manufacture of electrical conductors, e.g. according to EN 13602.
This document includes test methods for the determination of the following characteristics:
a) thickness of the unalloyed tin coating;
b) continuity of the tin coating;
c) adherence of the tin coating.
WARNING — This document can involve the use of hazardous materials, operations, and equipment.
This document does not purport to address all of the safety problems associated with their use. It is the
responsibility of the user of this document to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use. Moreover this document does not
cover the aspects related to the people protection against the X-ray. To obtain information applicable to
this aspect, it is convenient to refer to national and international standards, and also to the local
regulations if they exist.
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.
EN 610, Tin and tin alloys - Ingot tin
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at https://www.electropedia.org/
3.1
unalloyed tin coating
layer of pure tin on the surface of tinned wire
3.2
alloyed tin coating
diffusion layer of copper and tin formed at the copper wire and tin coating interface during tinning and
subsequent drawing and annealing processes
3.3
total tin coating
sum of the thicknesses of the unalloyed tin coating and the alloyed tin coating
3.4
measuring area
area of the surface over which a single measurement is made
4
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EN 13603:2021 (E)
3.5
X-ray fluorescence
XRF
secondary radiation occurring when a high intensity incident X-ray beam impinges upon a material
placed in the path of the incident beam
Note 1 to entry: The secondary emission has wavelengths and energies characteristic of that material.
[SOURCE: EN ISO 3497:2000-12, 2.1]
4 Thickness of the unalloyed tin coating
4.1 General
This document refers to two different methods to measure the thickness of the tin coating layers on
copper wires, the first one is based on the electrolytic dissolution of the tin layer. The second one is
based on the direct measure of the tin layer on the wires by means of the reflection of an X-ray beam on
its surface.
4.2 Principle of the method based on the electrolytic dissolution of the tin coating
4.2.1 General
Anodic dissolution of a well-defined area of the unalloyed coating using a suitable electrolyte, followed
by detection of the virtually complete dissolution of the unalloyed coating by a rapid change in cell
voltage. Calculation of the unalloyed coating thickness from the quantity of electricity (in coulombs)
used, which can in turn be calculated from:
a) the time interval between the start of the test and the first rapid change of cell voltage, if it is
conducted at constant current density; or
b) the integrated quantity of electricity used in dissolving the unalloyed coating.
4.2.2 Reagents and materials
4.2.2.1 Electrolyte, either a hydrochloric acid electrolyte or an electrolyte recommended by the
instrument manufacturer.
For the hydrochloric acid electrolyte, dilute 170 ml of hydrochloric acid (HCl), ρ = 1,18 g/ml, to 1 000 ml
with deionised water.
NOTE The unalloyed tin coating dissolves anodically at an efficiency of nearly 100 %; for determination of the
electrolyte efficiency, see 4.2.5.6.
WARNING — Hydrochloric acid causes burns and is irritating to the respiratory system. Avoid
breathing the vapour and prevent contact with eyes and skin.
This electrolyte dissolves tin coatings at very low cell voltages at which there is no anodic attack on the
substrates when they are exposed at the end of the test.
4.2.2.2 Tin, tin grade in accordance with EN 610.
4.2.3 Apparatus
Suitable instruments may be constructed from readily available components. Alternatively, a
proprietary instrument may be used.
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EN 13603:2021 (E)
4.2.3.1 Direct reading instruments
Proprietary direct reading instruments are available for use with electrolytes recommended by the
manufacturer.
The calculation of thickness of tin coating from current density is made electronically. The instrument
shall have some means of indicating when the unalloyed tin coating has been fully removed.
4.2.3.2 Other instruments
Instruments other than proprietary direct reading instruments record the quantity of electricity, in
coulombs, used in dissolving the unalloyed coating from the measuring area, usually in arbitrary units,
from which the thickness can be calculated using factors or tables.
4.2.3.3 Electrolytic cell
The electrolytic cell consists of a container for the electrolyte, a cathode and an anode, which is the test
piece. If the container is made of metal, such as stainless steel, the container can serve as the cathode. If
the container is made of insulating material, a separate cathode is required.
Also required are a device for supporting the appropriate length of the test piece and an agitation
mechanism. Depending on the wire diameter, the test piece may be a straight length of wire or, if
necessary to obtain sufficient surface area for smaller diameter wires, a holding device such as that
shown schematically in Figure 1 is required. A magnetic stirrer or similar system shall be used to
provide agitation.
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EN 13603:2021 (E)
Key
1 tee-frame to support test piece of non-conducting material, manufactured from nylon or other plastics
2 test piece
3 test piece connection (anode)
4 cathode connection
5 electrolyte level
6 test piece length L
7 electrolyte
8 non-metallic pin
9 cathode (stainless steel or lead), container (beaker)
Figure 1 — Alternative method for supporting fine wire or wire which cannot be straightened
4.2.4 Preparation of the test piece
Select a suitable length of test piece in order to provide the appropriate test piece area for exposure to
the electrolyte. If necessary, clean the test surface with a suitable organic solvent (see 5.5).
Care should be taken to avoid removal of metal during the cleaning operation.
4.2.5 Procedure for determining the thickness of unalloyed tin coatings
4.2.5.1 General
If commercial equipment is used, follow the manufacturer’s instructions with respect to the operating
procedure for measurement, the electrolyte and, if necessary, calibration. Appropriate attention shall be
given to the factors listed in 4.2.5.4. The performance of the instrument shall be checked using a
reference specimen of pure tin wire. A tin grade in accordance with EN 610 shall be used. The test shall
be carried out in accordance with 4.2.5.6.
If the instrument readings or the calculation of K give an electrolytic efficiency of equal to or greater
than 98 %, the instrument may be used without further adjustment. Otherwise, the cause of
discrepancy shall be remedied. Proprietary instruments shall be calibrated in accordance with the
manufacturer's instructions.
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4.2.5.2 Determination of measuring area
The measuring area A in square centimetres is given by the Formula (1):
d ××L π
A= (1)
100
where
A is the measuring area in square centimetres;
d is the diameter of the test piece in millimetres;
L is the length of the test piece in millimetres.
For the determination of the measuring area, the length L of the test piece in millimetres shall be
determined with an accuracy of 1 % and the diameter d of the test piece for wires with a nominal
diameter of < 0,6 mm shall be determined with an accuracy of 1 % and for wires with a nominal
diameter of ≥ 0,6 mm with an accuracy of 0,5 %.
An exact area of stripping is necessary for accuracy and the main source of error is due to the meniscus
and current field at the electrolyte surface.
4.2.5.3 Electrolysis (Dissolution of the unalloyed tin coating)
The electrolyte (4.2.2.1) and test piece shall be introduced into the cell so that a known area is exposed
to the electrolyte. Efforts shall be made to ensure that no gas bubbles occur on the measuring area by
use of the agitation mechanism. The electrical connections shall be made and the agitator operated.
Electrolysis shall be continued until dissolution of the unalloyed tin coating is complete, as indicated by
a sharp change in the anode potential or cell voltage, or by the operation of the automatic cut-out.
After completion of the test, the test piece shall be removed from the cell, rinsed with water and
examined to ensure that complete removal of the unalloyed tin coating has occurred over the
measuring area (see 4.2.5.4.9).
4.2.5.4 Factors affecting the measuring accuracy
4.2.5.4.1 Coating thickness
The optimum accuracy is achieved with coating thicknesses in the range 0,2 μm up to 50 μm.
4.2.5.4.2 Current variation
For instruments using the constant current and time measuring technique, current variation will cause
errors. For instruments using a current-time integrator, too large a change in current can change the
anode current efficiency or interfere with the end-point, causing an error.
4.2.5.4.3 Area variation
The accuracy of the thickness measurement will be no better than the accuracy to which the measuring
area is known. Area variations due to electrolyte level (excessive agitation), can lead to measurement
errors. In some cases it can be advantageous to measure the length after electrolysis is complete and re-
calculate the area.
4.2.5.4.4 Agitation
Agitation (i.e. the rate of stirring) shall be sufficient to remove any gas bubbles formed during the test,
which can adhere to the test piece or cathode. Excessive agitation shall be avoided to prevent
interference with the length of test piece submerged.
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4.2.5.4.5 Condition of the test piece surface
Oil, grease, paint, corrosion products, staining or other surface chemical treatments can interfere with
the test.
4.2.5.4.6 Cleanliness of the cell
Deposition of tin can take place on the cathode in some electrolytes. This deposit can alter the cell
voltages. It is, therefore, essential to keep the cathode clean.
4.2.5.4.7 Cleanliness of the electrical connections
In the case of instruments other than the constant current type, if the electrical connections are not
clean, the current/potential relationship will be disturbed and false end-points obtained.
4.2.5.4.8 Calibration standards
Measurements made using calibration standards are subject to the additional error of the calibration
standards.
4.2.5.4.9 Non-uniform dissolution
If the rate of dissolution is not uniform over the measuring area, a premature end-point can be obtained
and yield low results. Examination of the surface shall be made after the test (see 4.2.5.3) to verify that
most of the coating has dissolved.
The presence of other matter in the coating, the roughness of the coating surface and the presence of
porosity in the coating can cause fluctuation of the cell voltage. Such fluctuation can affect the end-point.
4.2.5.4.10 Electrolyte efficiency
The determination of tin thickness by this method depends upon the efficiency of the electrolyte K
being at least 98 %. The value of K should be determined periodically (see 4.2.5.6).
4.2.5.5 Measurement uncertainty
The test equipment and the procedure shall be such that the coating thickness can be measured to
within a 5,0 % uncertainty under the following conditions:
— the electrical current shall be controlled within 10 mA;
— the time shall be controlled within 1 s;
— the area shall be controlled within the accuracy given in 4.2.5.2;
— the efficiency of the electrolyte K shall be greater than 98 % (see 4.2.5.6).
4.2.5.6 Determination of electrolyte efficiency
Where a manufacturer of apparatus recommends the use of a particular electrolyte for determining tin
thickness on copper wire, the control of electrolyte efficiency shall be in accordance with the
manufacturer's instructions. In other cases, the value of K shall be determined periodically using the
following procedure:
a) a suitable test anode shall be manufactured comprising wire in the range of diameter 0,5 mm up to
and including 2,00 mm, of suitable length, coated with pure, unalloyed tin (4.2.2.2) to a thickness of
at least 4 μm;
b) the test anode shall be accurately weighed and its mass recorded;
9
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EN 13603:2021 (E)
c) the test anode shall be immersed in the cell containing the electrolyte using either the same length
as that recommended by the instrument manufacturer or used in the routine determination of tin
thickness;
d) the current shall be either that recommended by the instrument manufacturer or used in the
routine determination of tin thickness;
e) the duration of the test shall be sufficient to ensure a significant removal of tin but not so long that
the tin coating is completely removed;
f) the duration of the test in seconds and the current in amperes shall be noted;
g) the anode shall be removed, washed, rinsed and dried without wiping;
h) the anode shall be re-weighed to the same accuracy as before;
i) the electrolytic efficiency K shall be calculated by the Formula (2):
m
K= (2)
E ××I t
where
m is the loss in mass of anode, in milligram (mg);
E is the electrochemical equivalent = 0,615 2 mg Sn/coulomb;
I is the current, in amperes (A);
t is the duration, in seconds (s).
In order to maintain precision in weighing, the ratio of the mass of the anode to the mass of tin removed
should be 1 000 : 1.
NOTE The value of 0,615 2 for electrochemical equivalent is based on the fact that 96 485 coulomb will
2+
remove 59,35 g of Sn at 100 % efficiency.
If the value of K determined is less than 98 %, the electrolyte shall be discarded.
4.2.6 Expression of results
The unalloyed tin coating thickness tk, in micrometres, is given by Formula (3):
Q × E I × t × E
tk 100 ××K or 100 ×K × (3)
A ××ρρA
where
K is the electrolytic efficiency of the dissolution process and shall be assumed
to be 100 in the case of 100 % efficiency (see 4.2.5.6);
E is the electrochemical equivalent = 0,615 2 mg Sn/coulomb;
2
A
is the area, in square centimetres (cm ), from which the coating is dissolved,
i.e. the measuring area;
3
ń
is the density, in grams per cubic centimetre (g/cm ), of the unalloyed tin
3
coating which for tin shall be 7,29 g/cm ;
Q is the quantity of electricity, in coulomb, passed in dissolving the unalloyed
tin coating; if an integrating meter is not used, calculate Q from Formula (4):
10
=
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EN 13603:2021 (E)
Q It× (4)
where
I is the current, in amperes (A);
t is the test duration, in seconds (s).
Formula (3) above may be simplified, by substitution, to Formula (5):
QQ
tk 0,,008 44× K× i. e. tk 0 844× (5)
AA
4.3 Principle of the method based on XRF
4.3.1 General
The proposed measurement techniques applying the energy-dispersive XRF method relies on the
availability of certified reference material (CRM). Its structure and its composition should be equal or
close to those of the measuring sample. Only the use of CRM ensures true (traceable) and reproducible
measuring results. The proposed techniques require to difference types of CRM:
— Overlap technique: CRM as one or several wires with the same diameter and appropriate coating
thickness;
— Full-spot technique: CRM as one or several wires with the same diameter and appropriate coating
thickness;
or CRM as flat coated metal sheets or Sn foils on top of Cu base material.
4.3.2 Devices with measuring spots larger than the wire diameter — Overlap technique
Provided that reference standards for calibration in the form of wires with the same diameter are
available – an elegant and time-saving technique can be applied. In this method, referred to as overlap
technique, the measuring spot has to be larger than the wire’s diameter. Data thus obtained comprise
information from all areas of the wire including the rim and are not sensitive to the particular geometry
of the surface (see below).
Key
1 detector
Figure 2 — Placement of wire sample, detector and measuring spot in case of circular shaped
11
= =
=
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EN 13603:2021 (E)
Key
1 detector
Figure 3 — Placement of wire sample, detector and measuring spot in case of asymmetric spots
For the application of the overlap technique precise and dedicated reference standards are required.
In case of spots with radial symmetric shapes the measurement spot has to be placed such that the wire
is irradiated symmetrically to its axis (Figure 2). In case of asymmetric measuring spots, e.g. with
rectangular geometry like slits, the sample is placed perpendicular to the measuring spot (Figure 3).
The wire has to be placed such that it will be entirely covered by the measuring area. It is recommended
to place the sample such that the detector is oriented in the same direction as the long axis of the wire
and not perpendicular to it in order to minimize the nonlinear absorption effects, i.e. the wire should be
placed on the symmetry axis of the set-up.
The XRF spectrometer has to be calibrated with a dedicated reference standard with adequate
properties. Since the measuring spot is larger than the sample the intensity for a given thickness or
concentration will be lower than expected from the size of the measuring spot. Since the common
analysis approaches in commercial XRF spectrometers rely on models with flat and infinite surface
geometry the used analysis software should be able to account for this intensity mismatch.
4.3.3 Devices with measuring spots smaller t
...
SLOVENSKI STANDARD
oSIST prEN 13603:2020
01-april-2020
Baker in bakrove zlitine - Preskusne metode za ocenjevanje kakovosti zaščitnih
kositrovih prevlek na okroglih bakrovih vlečenih žicah za elektrotehniko
Copper and copper alloys - Test methods for assessing protective tin coatings on drawn
round copper wire for electrical purposes
Kupfer und Kupferlegierungen - Prüfverfahren zur Beurteilung von Schutzüberzügen aus
Zinn auf gezogenen Runddrähten aus Kupfer für die Anwendung in der Elektrotechnik
Cuivre et alliages de cuivre - Méthodes d'évaluation des revêtements en étain sur les fils
ronds étirés en cuivre pour usages électriques
Ta slovenski standard je istoveten z: prEN 13603 rev
ICS:
25.220.40 Kovinske prevleke Metallic coatings
77.150.30 Bakreni izdelki Copper products
oSIST prEN 13603:2020 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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oSIST prEN 13603:2020
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oSIST prEN 13603:2020
DRAFT
EUROPEAN STANDARD
prEN 13603
NORME EUROPÉENNE
EUROPÄISCHE NORM
February 2020
ICS 25.220.40; 77.150.30 Will supersede EN 13603:2013
English Version
Copper and copper alloys - Test methods for assessing
protective tin coatings on drawn round copper wire for
electrical purposes
Cuivre et alliages de cuivre - Méthodes d'évaluation des Kupfer und Kupferlegierungen - Prüfverfahren zur
revêtements en étain sur les fils ronds étirés en cuivre Beurteilung von Schutzüberzügen aus Zinn auf
pour usages électriques gezogenen Runddrähten aus Kupfer für die
Anwendung in der Elektrotechnik
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 133.
If this draft becomes a European Standard, CEN 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.
This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC
Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
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.
Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 13603:2020 E
worldwide for CEN national Members.
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Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Thickness of the unalloyed tin coating . 5
4.1 Principle of the method based on the electrolytic dissolution of the tin coating . 5
4.1.1 General. 5
4.1.2 Reagents and materials . 5
4.1.3 Apparatus . 5
4.1.4 Preparation of the test piece . 7
4.1.5 Procedure for determining the thickness of unalloyed tin coatings . 7
4.1.6 Expression of results . 10
4.2 Principle of the method based on XRF . 10
4.2.1 General. 10
4.2.2 Devices with measuring spots larger than the wire diameter - Overlap technique . 11
4.2.3 Devices with measuring spots smaller than the wire diameter – Full-spot technique . 12
4.2.4 Preparation of the test piece . 12
4.2.5 Factors affecting the measuring accuracy . 12
5 Continuity of the tin coating . 17
5.1 Principle . 17
5.2 Test solution . 17
5.3 Reference solution . 17
5.4 Preparation of the test piece . 18
5.5 Cleaning of the test piece . 18
5.6 Immersion for testing . 18
5.7 Determination . 18
5.7.1 General. 18
5.7.2 Comparison by Nessler cylinders . 19
5.7.3 Colorimetric method . 19
6 Adherence of the tin coating . 19
6.1 Principle . 19
6.2 Stock solution . 19
6.3 Test solution . 19
6.4 Preparation of the test piece . 19
6.5 Cleaning of the test piece . 20
6.6 Immersion for testing . 20
6.7 Examination . 20
7 Test report . 21
Bibliography . 22
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European foreword
This document (prEN 13603:2020) has been prepared by Technical Committee CEN/TC 133 “Copper
and copper”, the secretariat of which is held by DIN.
This document is currently submitted to the CEN enquiry.
This document will supersede EN 13603:2013.
In comparison with the previous edition, the following technical modifications have been made:
— Include the X-Ray fluorescence analysis (XRF) to measure the thickness of the tin layer.
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1 Scope
This document specifies methods for assessing the tin coating on drawn round copper wire for the
manufacture of electrical conductors, e.g. according to EN 13602.
This document includes test methods for the determination of the following characteristics:
a) thickness of the unalloyed tin coating;
b) continuity of the tin coating;
c) adherence of the tin coating.
WARNING — This document can involve the use of hazardous materials, operations, and
equipment. This document does not purport to address all of the safety problems associated
with their use. It is the responsibility of the user of this document to establish appropriate safety
and health practices and determine the applicability of regulatory limitations prior to use.
Moreover this document does not cover the aspects related to the people protection against the
X-ray. To obtain information applicable to this aspect it is convenient to refer to national and
international standards, and also to the local regulations if they exist.
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.
EN 610, Tin and tin alloys - Ingot tin
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.1
unalloyed tin coating
layer of pure tin on the surface of tinned wire
3.2
alloyed tin coating
diffusion layer of copper and tin formed at the copper wire and tin coating interface during tinning and
subsequent drawing and annealing processes
3.3
total tin coating
sum of the thicknesses of the unalloyed tin coating and the alloyed tin coating
3.4
measuring area
area of the surface over which a single measurement is made
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3.5
X-Ray Fluorescence
XRF
secondary radiation occurring when a high intensity incident X-ray beam impinges upon a material
placed in the path of the incident beam
Note 1 to entry: The secondary emission has wavelengths and energies characteristic of that material.
4 Thickness of the unalloyed tin coating
NOTE This document refers to two different methods to measure the thickness of the tin coating layers on
copper wires, the first one is based on the electrolytic dissolution of the tin layer. The second one is based on the
direct measure of the tin layer on the wires by means of the reflection of an X-ray beam on its surface.
4.1 Principle of the method based on the electrolytic dissolution of the tin coating
4.1.1 General
Anodic dissolution of a well-defined area of the unalloyed coating using a suitable electrolyte, followed
by detection of the virtually complete dissolution of the unalloyed coating by a rapid change in cell
voltage. Calculation of the unalloyed coating thickness from the quantity of electricity (in coulombs)
used, which can in turn be calculated from:
a) the time interval between the start of the test and the first rapid change of cell voltage, if it is
conducted at constant current density; or
b) the integrated quantity of electricity used in dissolving the unalloyed coating.
4.1.2 Reagents and materials
4.1.2.1 Electrolyte, either a hydrochloric acid electrolyte or an electrolyte recommended by the
instrument manufacturer
For the hydrochloric acid electrolyte, dilute 170 ml of hydrochloric acid (HCl), ρ = 1,18 g/ml, to 1 000 ml
with deionised water.
NOTE The unalloyed tin coating dissolves anodically at an efficiency of nearly 100 %; for determination of the
electrolyte efficiency, see 4.5.6.
WARNING — Hydrochloric acid causes burns and is irritating to the respiratory system. Avoid
breathing the vapour and prevent contact with eyes and skin.
This electrolyte dissolves tin coatings at very low cell voltages at which there is no anodic attack on the
substrates when they are exposed at the end of the test.
4.1.2.2 Tin, tin grade in accordance with EN 610
4.1.3 Apparatus
Suitable instruments may be constructed from readily available components. Alternatively, a
proprietary instrument may be used.
4.1.3.1 Direct reading instruments
Proprietary direct reading instruments are available for use with electrolytes recommended by the
manufacturer.
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The calculation of thickness of tin coating from current density is made electronically. The instrument
shall have some means of indicating when the unalloyed tin coating has been fully removed.
4.1.3.2 Other instruments
Instruments other than proprietary direct reading instruments record the quantity of electricity, in
coulombs, used in dissolving the unalloyed coating from the measuring area, usually in arbitrary units,
from which the thickness can be calculated using factors or tables.
4.1.3.3 Electrolytic cell
The electrolytic cell consists of a container for the electrolyte, a cathode and an anode, which is the test
sample. If the container is made of metal, such as stainless steel, the container can serve as the cathode.
If the container is made of insulating material, a separate cathode is required.
Also required are a device for supporting the appropriate length of the test sample and an agitation
mechanism. Depending on the wire diameter, the test sample may be a straight length of wire or, if
necessary to obtain sufficient surface area for smaller diameter wires, a holding device such as that
shown schematically in Figure 1 is required. A magnetic stirrer or similar system shall be used to
provide agitation.
Key
1 tee-frame to support test piece of non-conducting material, manufactured from nylon or other plastics
2 test piece
3 test piece connection (anode)
4 cathode connection
5 electrolyte level
6 test piece length L
7 electrolyte
8 non-metallic pin
9 cathode (stainless steel or lead), container (beaker)
Figure 1 — Alternative method for supporting fine wire or wire which cannot be straightened
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4.1.4 Preparation of the test piece
Select a suitable length of test sample in order to provide the appropriate test piece area for exposure to
the electrolyte. If necessary, clean the test surface with a suitable organic solvent (see 5.5).
Care should be taken to avoid removal of metal during the cleaning operation.
4.1.5 Procedure for determining the thickness of unalloyed tin coatings
4.1.5.1 General
If commercial equipment is used, follow the manufacturer’s instructions with respect to the operating
procedure for measurement, the electrolyte and, if necessary, calibration. Appropriate attention shall be
given to the factors listed in 4.1.5.4. The performance of the instrument shall be checked using a
reference specimen of pure tin wire. A tin grade in accordance with EN 610 shall be used. The test shall
be carried out in accordance with 4.1.5.6.
If the instrument readings or the calculation of K give an electrolytic efficiency of equal to or greater
than 98 %, the instrument may be used without further adjustment. Otherwise, the cause of
discrepancy shall be remedied. Proprietary instruments shall be calibrated in accordance with the
manufacturer's instructions.
4.1.5.2 Determination of measuring area
For the determination of the measuring area, the length L of the test piece in millimetres shall be
determined with an accuracy of 1 % and the diameter d of the test piece for wires with a nominal
diameter of < 0,6 mm shall be determined with an accuracy of 1 % and for wires with a nominal
diameter of ≥ 0,6 mm with an accuracy of 0,5 %. The measuring area A in square centimetres is given by
the Formula (1):
d ×L × π
A=
100
(1)
NOTE An exact area of stripping is necessary for accuracy and the main source of error is due to the meniscus
and current field at the electrolyte surface.
4.1.5.3 Electrolysis (Dissolution of the unalloyed tin coating)
The electrolyte (4.1.2.1) and test piece shall be introduced into the cell so that a known area is exposed
to the electrolyte. Efforts shall be made to ensure that no gas bubbles occur on the measuring area by
use of the agitation mechanism. The electrical connections shall be made and the agitator operated.
Electrolysis shall be continued until dissolution of the unalloyed tin coating is complete, as indicated by
a sharp change in the anode potential or cell voltage, or by the operation of the automatic cut-out.
After completion of the test, the test piece shall be removed from the cell, rinsed with water and
examined to ensure that complete removal of the unalloyed tin coating has occurred over the
measuring area (see 4.1.5.4.9).
4.1.5.4 Factors affecting the measuring accuracy
4.1.5.4.1 Coating thickness
The optimum accuracy is achieved with coating thicknesses in the range 0,2 μm up to 50 μm.
4.1.5.4.2 Current variation
For instruments using the constant current and time measuring technique, current variation will cause
errors. For instruments using a current-time integrator, too large a change in current can change the
anode current efficiency or interfere with the end-point, causing an error.
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4.1.5.4.3 Area variation
The accuracy of the thickness measurement will be no better than the accuracy to which the measuring
area is known. Area variations due to electrolyte level (excessive agitation), can lead to measurement
errors. In some cases it can be advantageous to measure the length after electrolysis is complete and re-
calculate the area.
4.1.5.4.4 Agitation
Agitation (i.e. the rate of stirring) shall be sufficient to remove any gas bubbles formed during the test,
which can adhere to the test piece or cathode. Excessive agitation shall be avoided to prevent
interference with the length of test piece submerged.
4.1.5.4.5 Condition of the test piece surface
Oil, grease, paint, corrosion products, staining or other surface chemical treatments can interfere with
the test.
4.1.5.4.6 Cleanliness of the cell
Deposition of tin can take place on the cathode in some electrolytes. This deposit can alter the cell
voltages. It is, therefore, essential to keep the cathode clean.
4.1.5.4.7 Cleanliness of the electrical connections
In the case of instruments other than the constant current type, if the electrical connections are not
clean, the current/potential relationship will be disturbed and false end-points obtained.
4.1.5.4.8 Calibration standards
Measurements made using calibration standards are subject to the additional error of the calibration
standards.
4.1.5.4.9 Non-uniform dissolution
If the rate of dissolution is not uniform over the measuring area, a premature end-point can be obtained
and yield low results. Examination of the surface shall be made after the test (see 4.1.5.3) to verify that
most of the coating has dissolved.
The presence of other matter in the coating, the roughness of the coating surface and the presence of
porosity in the coating can cause fluctuation of the cell voltage. Such fluctuation can affect the end-point.
4.1.5.4.10 Electrolyte efficiency
The determination of tin thickness by this method depends upon the efficiency of the electrolyte K
being at least 98 %. The value of K should be determined periodically (see 4.1.5.6).
4.1.5.5 Measurement uncertainty
The test equipment and the procedure shall be such that the coating thickness can be measured to
within a 5,0 % uncertainty under the following conditions:
• the electrical current shall be controlled within 10 mA;
• the time shall be controlled within 1 s;
• the area shall be controlled within the accuracy given in 4.5.2;
• the efficiency of the electrolyte K shall be greater than 98 % (see 4.1.5.6).
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4.1.5.6 Determination of electrolyte efficiency
Where a manufacturer of apparatus recommends the use of a particular electrolyte for determining tin
thickness on copper wire, the control of electrolyte efficiency shall be in accordance with the
manufacturer's instructions. In other cases, the value of K shall be determined periodically using the
following procedure:
a) a suitable test anode shall be manufactured comprising wire in the range of diameter 0,5 mm up to
and including 2,00 mm, of suitable length, coated with pure, unalloyed tin (4.1.2.2) to a thickness of
at least 4 μm;
b) the test anode shall be accurately weighed and its mass recorded;
c) the test anode shall be immersed in the cell containing the electrolyte using either the same length
as that recommended by the instrument manufacturer or used in the routine determination of tin
thickness;
d) the current shall be either that recommended by the instrument manufacturer or used in the
routine determination of tin thickness;
e) the duration of the test shall be sufficient to ensure a significant removal of tin but not so long that
the tin coating is completely removed;
f) the duration of the test in seconds and the current in amperes shall be noted;
g) the anode shall be removed, washed, rinsed and dried without wiping;
h) the anode shall be re-weighed to the same accuracy as before;
i) the electrolytic efficiency K shall be calculated as follows:
m
K=
E ×I ×t
(2)
where
m is the loss in mass of anode, in milligram (mg);
E is the electrochemical equivalent = 0,615 2 mg Sn/coulomb;
I is the current, in amperes (A);
t is the duration, in seconds (s).
In order to maintain precision in weighing, the ratio of the mass of the anode to the mass of tin removed
should be 1 000 : 1.
NOTE The value of 0,615 2 for electrochemical equivalent is based on the fact that 96 485 coulomb will
2+
remove 59,35 g of Sn at 100 % efficiency.
If the value of K determined is less than 98 %, the electrolyte shall be discarded.
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4.1.6 Expression of results
The unalloyed tin coating thickness tk, in micrometres, is given by the Formula (3):
Q × E I ××t E
tk 100 ××K or 100 ××K
A ×ρ Aρ ×
(3)
where
K is the current efficiency of the dissolution process and shall be assumed to
be 100 in the case of 100 % efficiency (see 4.1.5.6);
E is the electrochemical equivalent = 0,615 2 mg Sn/coulomb;
2
A is the area, in square centimetres (cm ), from which the coating is dissolved,
i.e. the measuring area;
3
ρ is the density, in grams per cubic centimetre (g/cm ), of the unalloyed tin
3
coating which for tin shall be 7,29 g/cm ;
Q is the quantity of electricity, in coulomb, passed in dissolving the unalloyed
tin coating; if an integrating meter is not used, calculate Q from Formula (4):
Q= I×t
(4)
where
I is the current, in amperes (A);
t is the test duration, in seconds (s).
Formula (3) above may be simplified, by substitution, to Formula (5):
Q Q
tk 0,00844××K i.e. tk 0,844×
AA
(5)
4.2 Principle of the method based on XRF
4.2.1 General
The proposed measurement techniques applying the energy-dispersive XRF method relies on the
availability of certified reference material (CRM). Its structure and its composition should be equal or
close to those of the measuring sample. Only the use of CRM ensures true (traceable) and reproducible
measuring results. The proposed techniques require to difference types of CRM:
• Overlap technique: CRM as one or several wires with the same diameter and appropriate coating
thickness
• Full-spot technique: CRM as one or several wires with the same diameter and appropriate coating
thickness
or CRM as flat coated metal sheets or Sn foils on top of Cu base material
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4.2.2 Devices with measuring spots larger than the wire diameter - Overlap technique
Provided that reference standards for calibration in the form of wires with the same diameter are
available - an elegant and time-saving technique can be applied. In this method, referred to as overlap
technique, the measuring spot has to be larger than the wire’s diameter. Data thus obtained comprise
information from all areas of the wire including the rim and are not sensitive to the particular geometry
of the surface (see below).
Key
1 detector
Figure 2 — Placement of wire sample, detector and measuring spot in case of circular shaped
Key
1 detector
Figure 3 — Placement of wire sample, detector and measuring spot in case of asymmetric spots
For the application of the overlap technique precise and dedicated reference standards are required.
In case of spots with radial symmetric shapes the measurement spot has to placed such that the wire is
irradiated symmetrically to its axis (Figure 2). In case of asymmetric measuring spots, e.g. with
rectangular geometry like slits, the sample is placed perpendicular to the measuring spot (Figure 3).
The wire has to be placed such that it will be entirely covered by the measuring area. It is recommended
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to place the sample such that the detector is oriented in the same direction as the long axis of the wire
and not perpendicular to it in order to minimize the nonlinear absorption effects, i.e. the wire should be
placed on the symmetry axis of the set-up.
The XRF spectrometer has to be calibrated with a dedicated reference standard with adequate
properties. Since the measuring spot is larger than the sample the intensity for a given thickness or
concentration will be lower than expected from the size of the measuring spot. Since the common
analysis approaches in commercial XRF spectrometers rely on models with flat and infinite surface
geometry the used analysis software should be able to account for this intensity mismatch.
4.2.3 Devices with measuring spots smaller than the wire diameter – Full-spot technique
Here the measurement spot of the XRF device is much smaller, i.e. by a factor of 4 or 5 than the
diameter of the wire and is placed directly on top of the curved surface according to the rules described
in 4.2.5. In this case it is assumed that the XRF device operates in a standard mode and within the limits
of the underlying analysis model. The calibration can be performed using CRM as one or several wires
with the same diameter and appropriate coating thickness or CRM as flat coated metal sheets or Sn foils
on top of Cu base material.
4.2.4 Preparation of the test piece
The wires should be mounted on top of a hole in a sample holder serving as radiation trap from
fluorescence or scattered X-rays underneath the wire (see Figure 2 and Figure 3).
4.2.5 Factors affecting the measuring accuracy
The factors affecting the measuring accuracy besides uncertainties from t
...
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