SIST EN 1811:2011
(Main)Reference test method for release of nickel from post assemblies which are inserted into pierced parts of the human body and products intended to come into direct and prolonged contact with the skin
Reference test method for release of nickel from post assemblies which are inserted into pierced parts of the human body and products intended to come into direct and prolonged contact with the skin
This European Standard specifies a method for simulating the release of nickel from all post assemblies which are inserted into pierced ears and other pierced parts of the human body and articles intended to come into direct and prolonged contact with the skin in order to determine whether such items are in compliance with the European Directive 76/769/EEC as amended by 94/27/EC and 2004/96/EC. DRAFTING REMARK Subject to the final positive decision of the European Commission, CEN/TC 347/TG 1 supports the following wording to be included in the scope of this standard: Spectacle frames and sunglasses are excluded from the scope of this European Standard.
Referenzprüfverfahren zur Bestimmung der Nickellässigkeit von sämtlichen Stäben, die in durchstochene Körperteile eingeführt werden und Produkten, die unmittelbar und länger mit der Haut in Berührung kommen
Diese Europäische Norm legt ein Verfahren fest, um die Nickellässigkeit von sämtlichen Stäben, die in
durchstochene Ohren und in sonstige durchstochene Teile des menschlichen Körpers eingeführt werden
sowie von Gegenständen, die dafür bestimmt sind, in unmittelbaren und länger andauernden Kontakt mit der
Haut zu kommen, zu simulieren, um zu bestimmen, ob diese Gegenstände der Europäischen
Richtlinie 76/769/EWG, geändert durch 94/27/EG und 2004/96/EG entsprechen.
BEMERKUNG ZUM ENTWURF Vorbehaltlich der abschließenden positiven Entscheidung der Europäischen
Kommission, unterstützt CEN/TC 347/TG 1, den nachfolgenden Wortlaut in den Anwendungsbereich der vorliegenden
Norm aufzunehmen:
Brillenfassungen und Sonnenbrillen sind von dem Anwendungsbereich dieser Europäischen Norm ausgeschlossen.
Méthode d'essai de référence relative à la libération du nickel par les assemblages de tiges qui sont introduites dans les parties percées du corps humain et les produits destinés à entrer en contact direct et prolongé avec la peau
La présente norme européenne spécifie une méthode pour simuler la libération du nickel par tous les
assemblages de tiges insérés dans les oreilles percées et d’autres parties percées du corps humain et les
articles destinés à entrer en contact direct et prolongé avec la peau, dans le but de déterminer si ces produits
sont conformes à la Directive européenne 76/769/CEE amendée par les Directives 94/27/CE et 2004/96/CE.
NOTE Sous réserve de la décision positive finale de la Commission européenne, le CEN/TC 347/TG 1 souhaite que
l’énoncé suivant soit inclus dans le domaine d’application de la présente norme :
Les montures de lunettes et les lunettes de soleil sont exclues du domaine d’application de la présente Norme
européenne.
Primerjalna preskusna metoda za sproščanje niklja iz izdelkov, vstavljenih v prebodene dele človeškega telesa, in izdelkov, ki so v neposrednem in daljšem stiku s kožo
Ta evropski standard določa metodo za simulacijo sproščanja niklja iz vseh izdelkov, vstavljenih v prebodene dele človeškega telesa, in izdelkov, ki so v daljšem neposrednem stiku s kožo, da se določi, ali so ti izdelki v skladu z Evropsko direktivo 76/769/EGS, kot jo spreminjata direktivi 94/27/ES in 2004/96/ES. PRIPOMBA O PRIPRAVI OSNUTKA: CEN/TC 347/TG 1, ki je obravnavan v končni sprejeti odločitvi Evropske komisije, podpira vključitev naslednjega besedila v področje uporabe tega standarda: Okvirji očal in sončna očala so izključeni s področja uporabe tega evropskega standarda.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 1811:2011
01-september-2011
1DGRPHãþD
SIST EN 1811:1999
SIST EN 1811:1999+A1:2008
3ULPHUMDOQDSUHVNXVQDPHWRGD]DVSURãþDQMHQLNOMDL]L]GHONRYYVWDYOMHQLKY
SUHERGHQHGHOHþORYHãNHJDWHOHVDLQL]GHONRYNLVRYQHSRVUHGQHPLQGDOMãHP
VWLNXVNRåR
Reference test method for release of nickel from post assemblies which are inserted into
pierced parts of the human body and products intended to come into direct and
prolonged contact with the skin
Referenzprüfverfahren zur Bestimmung der Nickellässigkeit von sämtlichen Stäben, die
in durchstochene Körperteile eingeführt werden und Produkten, die unmittelbar und
länger mit der Haut in Berührung kommen
Méthode d'essai de référence relative à la libération du nickel par les assemblages de
tiges qui sont introduites dans les parties percées du corps humain et les produits
destinés à entrer en contact direct et prolongé avec la peau
Ta slovenski standard je istoveten z: EN 1811:2011
ICS:
39.060 Nakit Jewellery
SIST EN 1811:2011 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
SIST EN 1811:2011
---------------------- Page: 2 ----------------------
SIST EN 1811:2011
EUROPEAN STANDARD
EN 1811
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2011
ICS 39.060 Supersedes EN 1811:1998+A1:2008
English Version
Reference test method for release of nickel from all post
assemblies which are inserted into pierced parts of the human
body and articles intended to come into direct and prolonged
contact with the skin
Méthode d'essai de référence relative à la libération du Referenzprüfverfahren zur Bestimmung der Nickellässigkeit
nickel par les assemblages de tiges qui sont introduites von sämtlichen Stäben, die in durchstochene Körperteile
dans les parties percées du corps humain et les produits eingeführt werden und Erzeugnissen, die unmittelbar und
destinés à entrer en contact direct et prolongé avec la peau länger mit der Haut in Berührung kommen
This European Standard was approved by CEN on 5 February 2011.
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, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 1811:2011: E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
Contents Page
Foreword .4
Introduction .5
1 Scope .6
2 Normative references .6
3 Terms and definitions .6
4 Principle of the procedure .7
5 Reagents .7
6 Apparatus .8
7 Samples .9
7.1 Sample area .9
7.1.1 Definition of sample area .9
7.1.2 Determination of sample area .9
7.1.3 Masking of areas other than sample area .9
7.2 Sample degreasing before testing .9
7.3 Quality control samples .9
8 Procedure . 10
8.1 Preparation of test solution . 10
8.2 Release procedure . 10
8.3 Determination of nickel . 11
8.3.1 General . 11
8.3.2 Calibration solutions . 11
8.3.3 Detection limit and quantification limit . 11
8.3.4 Number of test samples . 11
8.3.5 Number of replicate measurements. 11
8.4 Blank tests . 11
9 Calculations . 11
9.1 Nickel release . 11
9.2 Interpretation of results . 12
9.2.1 General . 12
9.2.2 Assessment of non-compliance . 12
9.2.3 Uncertainty budget . 13
10 Test report . 13
Annex A (informative) Expanded measurement uncertainty of the test procedure and compliance
assessment . 14
Annex B (normative) Requirements for quality control material . 16
Annex C (normative) Requirements for preparation of all post assemblies which are inserted into
pierced parts of the human body and articles intended to come into direct and prolonged
contact with the skin prior to nickel testing . 18
C.1 General . 18
C.2 Requirements and principle . 18
C.3 Determination of the nickel release test method . 18
C.4 Determination of surfaces coming into direct and prolonged contact with the skin or
pierced parts of the body . 18
C.4.1 Procedures for homogeneous and inhomogeneous articles . 18
C.4.2 Jewellery products . 20
2
---------------------- Page: 4 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
C.4.3 Other articles such as textiles, footwear, garments, leather goods and mobile phones . 25
C.5 Methods of determining the surface areas . 26
C.5.1 Surface area measurements . 26
C.5.2 Minimum surface area . 26
C.5.3 Simplification of surface area determination using common shapes of consumer
products . 26
C.6 Testing apparatus prior to nickel release testing . 26
Annex D (informative) Articles made from composite materials . 28
Bibliography . 29
3
---------------------- Page: 5 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
Foreword
This document (EN 1811:2011) has been prepared by Technical Committee CEN/TC 347 “Methods for
analysis of allergens”, the secretariat of which is held by DS.
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 September 2011, and conflicting national standards shall be
withdrawn at the latest by March 2013.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
This document, together with EN 16128:2011, supersedes EN 1811:1998 +A1:2008.
This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association.
This document supports essential requirements of Commission Regulation (EC) No 1907/2006 (REACH) of
the European Parliament and the Council.
List of the significant technical changes that have been made in this new version of EN 1811 in comparison
with the former edition EN 1811:1998+A1:2008:
The scope of the former European Standard was divided: EN 1811:2011 is applicable for all products but
spectacle frames and sunglasses; EN 16128:2011 is applicable for spectacle frames and sunglasses;
List of the significant technical changes of EN 1811:2011 as compared to the former European Standard:
• The scope was expanded to include all post assemblies which are inserted into pierced parts of the
human body;
• The preparation of the test solution was tested and changed;
• The correction factor was eliminated and the concept of measurement uncertainty introduced;
• The Standard contains a new normative Annex C on the preparation of articles prior to nickel testing;
EN 16128:2011 is technically unchanged as compared to the former European Standard
EN 1811:1998+A1:2008.
According to the CEN/CENELEC Internal Regulations, the national standards organizations 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, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.,
4
---------------------- Page: 6 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
Introduction
Adverse skin reaction to nickel has been known for many decades. Nickel is the most frequent cause of
contact allergy in Europe, and 10 % to 20 % of the patch tested female population and 1 % to 3 % of the patch
tested male population are allergic to nickel. Skin absorption of nickel ions, which are released from some
nickel-containing materials which are inserted into pierced ears or other pierced parts of the human body or
which are in direct and prolonged contact with the skin, causes sensitisation. Further exposure to soluble
nickel salts results in allergic contact dermatitis. It is known that sensitisation to nickel requires higher
exposure levels than does the elicitation in already sensitised individuals. There is a large variation in the
degree of sensitivity to nickel between individuals. This widespread health problem has forced the introduction
of a number of measures designed to reduce its prevalence. These measures include the requirements of this
standard which provides an in-vitro chemical test that correlates as far as possible with the variable human
biological reactions that occur when metallic articles containing nickel are in direct and prolonged contact with
the skin and pierced parts of the body. The standard provides a measure of the amount of nickel release from
an article immersed for one week in artificial sweat. The standard also describes the preparation of a quality
control material intended to assist a laboratory in achieving an acceptable precision.
Clinical patch-testing of a small selection of nickel-containing alloys and coatings on nickel-sensitized persons
indicates that high and low results achieved with the present analytical method correspond closely with
2
patch-test reactivity. Moreover, a nickel migration limit of 0,5 µg/cm /week for articles intended to come into
2
direct and prolonged contact with the skin and a nickel migration limit of less than 0,2 µg/cm /week for all post
piercing assemblies inserted into pierced ears and other pierced parts of the human body has been set in
Commission Regulation (EC) No 1907/2006 of the European Parliament and the Council (in the current
version).
5
---------------------- Page: 7 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
1 Scope
This European Standard specifies a method for simulating the release of nickel from all post assemblies which
are inserted into pierced ears and other pierced parts of the human body and articles intended to come into
direct and prolonged contact with the skin in order to determine whether such articles are in compliance with
No. 27 Annex XVII of Regulation (EC) No 1907/2006 of the European Parliament and of the Council
(REACH).
Spectacle frames and sunglasses are excluded from the scope of this European Standard.
NOTE Spectacle frames and sunglasses are subject to the requirements of EN 16128:2011 which provides an
unchanged re-publication of the technical requirements that had previously been specified in EN 1811:1998, but restricted
in scope to apply only to spectacle frames and sunglasses.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 12472, Method for the simulation of wear and corrosion for the detection of nickel release from coated
items
EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
barrette
component used to secure the watchstrap to the case
3.2
homogeneous
consisting of a single material having a common surface finish
3.3
post assembly
ear stud or body piercing article
3.4
release solution
solution resulting from the release procedure according to 8.2
3.5
representative
best estimate for the effective release rate of all surfaces which are in direct and prolonged contact with the
skin or pierced parts of the body under normal conditions of use
NOTE This property is defined with respect to the release rate.
6
---------------------- Page: 8 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
3.6
sample area
a
surface(s) that is(are) immersed in the test solution and not covered with a masking agent
3.7
test solution
solution as prepared according to 8.1
3.8
watch crown
winder used to alter the time/date
4 Principle of the procedure
The article to be tested for nickel release is placed in an artificial sweat test solution for one week. The
concentration of dissolved nickel in the solution is determined by an appropriate analytical method, for
example inductively-coupled plasma spectrometry. The nickel release is expressed in micrograms per square
2
centimetre per week (µg/cm /week).
NOTE Indicative information on the extent of nickel release can be obtained by performing one of the tests specified
in CR 12471.
5 Reagents
Except where indicated, all reagents shall be of recognized pro analysis, p.a., grade or better and shall be free
of nickel.
5.1 Deionised water according to EN ISO 3696:1995, grade 2.
5.2 Sodium chloride.
5.3 DL-lactic acid, ρ = 1,21 g/ml, > 88 % (m/m).
5.4 Urea.
5.5 Sodium hydroxide in solid tablets, min 98 % pure dehydrate.
5.6 Preparation of 1 M sodium hydroxide solution.
Weigh 4 g ± 0,01 g of sodium hydroxide (5.5) and transfer into a 100 ml beaker and add 50 ml of deionised
water (5.1). Stir and cool to room temperature. Transfer the solution to a 100 ml volumetric flask and make up
to volume with deionised water (5.1).
5.7 Preparation of 0,1M sodium hydroxide solution.
Add 25 ml of 1 M sodium hydroxide (5.6) in a 250 ml volumetric flask and make up to volume with deionised
water (5.1).
5.8 Hydrochloric acid, ρ = 1,16 g/ml, 32 % v/v.
5.9 Preparation of 0,1 M hydrochloric acid solution.
Transfer 10 ml of hydrochloric acid (5.8) into a 100 ml volumetric flask and make up to volume with deionised
water (5.1).
7
---------------------- Page: 9 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
5.10 Nitric acid, ρ = 1,40 g/ml, 65 % (m/m).
5.11 Dilute nitric acid, approximately 5 % (m/m).
Transfer 30 ml of nitric acid (5.10) into a 500-ml beaker containing about 350 ml of deionised water (5.1). Stir
and cool to room temperature. Transfer the solution to a 500-ml volumetric flask and make up to volume with
deionised water.
5.12 Degreasing solution.
Dissolve 5 g of an anionic surface-active agent such as sodium dodecylbenzene sulfate or sodium alkylaryl
sulfate in 1 000 ml deionised water (5.1). An appropriately diluted, neutral, commercially available detergent
may be used.
5.13 Wax or lacquer (suitable for electroplating purposes) capable of protecting a surface from nickel
release.
The wax or lacquer shall be shown to prevent nickel release from a nickel-releasing surface when one or more
coats of the wax or lacquer are applied in the same manner as on a test sample and shall not affect the nickel
content of the release solution. The suitability of the wax / lacquer shall be tested.
NOTE Information on sourcing of a suitable wax or lacquer is available from the CEN/CENELEC Management
Centre.
6 Apparatus
6.1 A pH-meter, accurate to ± 0,05 pH.
6.2 An analytical instrument capable of detecting a concentration of 0,01 mg nickel per litre in the final
release solution.
It is recommended that either an inductively-coupled plasma spectrometer (ICP-OES, optical emission, or
ICP-MS, mass spectrometer) or an electro thermal excitation atomic absorption spectrometer (GFAAS) is
used.
6.3 Thermostatically controlled water-bath or oven with or without cooling option, capable of
maintaining a temperature of (30 ± 2) °C.
6.4 A vessel with lid, both composed of a non-metallic, nickel-free and nitric-acid-resistant material, such
as glass and/or polypropylene and/or polytetrafluoroethylene and/or polystyrene.
The sample shall be suspended in the liquid by a holder made from the same materials as listed above, so as
to avoid contact of the sample area (7.1.1) with the walls and base of the vessel. The size and shape of vessel
and holder shall be chosen so as to minimize the volume of test solution required to completely cover the
article to be tested.
In order to remove any trace of nickel, the vessel and holder shall be pre-treated by being stored in a solution
of dilute nitric acid (5.11) for at least 4 h. After acid cleaning, rinse the vessel and holder with deionised water
and dry.
6.5 Device for length measuring, for example a digital calliper with a minimum resolution of 50 µm or a
micrometer with a minimum resolution of 5 µm.
8
---------------------- Page: 10 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
7 Samples
7.1 Sample area
7.1.1 Definition of sample area
Only the surface(s) that come(s) into direct and prolonged contact with the skin and/or that have contact with
the pierced parts of the body shall be tested (sample area).
In case of articles which are made of uniform material(s), consideration should be given to testing the whole
surface (whether or not it is all in direct and prolonged contact with the skin or with pierced parts of the body)
since errors can be introduced by the masking process (see 7.1.3).
The test laboratory shall refer to C.4 in order to determine which surfaces are to be tested.
7.1.2 Determination of sample area
Determination of the sample area (a) in square centimetres is achieved by marking the contour of the sample
area assuming that the article is worn or used as intended (refer to Annex C) and measuring it by an
appropriate measuring device (6.5). In order to achieve the required degree of analytical sensitivity, a
2
minimum sample area of 0,2 cm shall be tested. If necessary, identical articles may be tested together to
obtain this minimum area.
The closer the nickel release is to the limits laid down in the regulation, or the smaller the sample area is, the
more precise the surface measurement needs to be.
7.1.3 Masking of areas other than sample area
In order to prevent release of nickel from areas other than the sample area, such areas shall be removed or
protected from the test solution. This can be achieved after degreasing (refer to 7.2) by the application of one
or more coatings of a wax or lacquer (5.13) which has been shown to protect from nickel release.
The test laboratory shall refer to C.4 in order to determine which surfaces are to be tested.
7.2 Sample degreasing before testing
Gently swirl the sample for 2 min in degreasing solution (5.12) at room temperature. Rinse thoroughly with
deionised water and dry using an absorbing cloth. After degreasing, articles shall be handled with plastic
forceps or clean protective gloves.
NOTE This cleaning stage is intended to remove extraneous grease and skin secretions due to handling, but not any
protective coatings.
7.3 Quality control samples
As a quality control check, the nickel release from a quality control sample shall be determined (refer to
Annex B) on a frequent basis.
The quality control sample shall be degreased in the same way as the sample according to 7.2 and shall be
used only once.
9
---------------------- Page: 11 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
8 Procedure
8.1 Preparation of test solution
The test solution consists of deionised water (5.1) containing:
0,5 % (m/m) sodium chloride (5.2);
0,1 % (m/m) lactic acid (5.3);
0,1 % (m/m) urea (5.4); and
1 M (5.6) and 0,1 M (5.7) sodium hydroxide solution.
The test solution shall be prepared as follows:
Pour 900 ml of freshly prepared deionised water (5.1) to a 1 000 ml beaker. Add 1,00 ± 0,01 g of urea (5.4),
5,00 ± 0,05 g of sodium chloride (5.2) and 1,00 ± 0,01 g of lactic acid (5.3), and stir until dissolved.
Calibrate a pH meter in accordance with the manufacturer’s instructions using freshly prepared buffer
solutions.
Immerse the pH electrode into the test solution and measure the pH. Slowly and gently, add drop by drop a
volume of 1 M sodium hydroxide (5.6) until a pH of 5,5 ± 0,05 is reached and subsequently with continuous
stirring, add slowly and gently drop by drop a volume of 0,1 M sodium hydroxide (5.7) until a pH 6,5 ± 0,05 is
reached and remains stable.
Measure the pH after 10 min from the last addition of 0,1 M sodium hydroxide to ensure that the pH is in the
range 6,5 ± 0,05.
Transfer the solution to a 1 000 ml volumetric flask and make up to volume with deionised water. Before use,
ensure that the pH of the test solution is in the range of pH 6,5 ± 0,05.
If it is necessary to reduce the pH of the solution to 6,5 ± 0,05 before testing, this shall be done by adding
slowly and gently with continuous stirring drop by drop a volume of 0,1 M hydrochloric acid (5.9).
The test solution shall be prepared daily.
8.2 Release procedure
NOTE In the following text the term "test solution" represents the solution as prepared according to 8.1, the "release
solution" is the solution resulting from the release procedure. See also definitions.
Place the sample, suspended by its holder, in the test vessel (6.4). Add an amount of test solution
2
corresponding to approximately 1 ml per cm sample area. The suspended sample area shall be totally
immersed. It is not necessary to immerse areas which are completely protected by wax or lacquer (see 7.1.3).
The minimum volume of test solution shall be 0,5 ml irrespective of the surface area. Note the sample area
and the amount of the test solution used. Close the vessel with a tight lid in order to prevent evaporation of the
test solution. Leave the vessel undisturbed in a thermostatically controlled water-bath or oven (6.3) at
(30 ± 2)°C for (168 ± 2) h without agitation.
The quality control sample (7.3) shall be determined and suspended in an appropriate volume of test solution.
It shall be treated in the same manner as a sample.
After (168 ± 2) h, slowly remove the sample from the release solution. To collect solution contained in cavities
of the sample, the sample shall be turned appropriately. The sample shall not be rinsed.
10
---------------------- Page: 12 ----------------------
SIST EN 1811:2011
EN 1811:2011 (E)
Quantitatively transfer the release solution to an appropriately sized volumetric flask washed with dilute nitric
acid (5.11). In order to prevent redeposition of dissolved nickel, add dilute nitric acid (5.11), to achieve a
concentration of about 1 % nitric acid, when the flask is made up to volume (V in ml) using the test solution.
The choice of volumetric flask size shall take into account the sensitivity of the instrumentation used for the
nickel determination (refer to 6.2). The minimum final volume to which the release solution may be diluted is
2 ml.
Filtering should be avoided if possible as the expected concentration change and the possibility of
contamination can influence the result.
Test solution shall be stored in a refrigerator below 10 °C if used in the preparation of calibration solutions.
8.3 Determination of nickel
8.3.1 General
Determine the nickel content of the release solution using an analytical spectrometer (refer to 6.2).
For the determination of nickel using an analytical spectrometer the following procedures shall be applied.
8.3.2 Calibration solutions
The calibration solutions used for the nickel determination shall match the matrix of the test solution plus any
added nitric acid and adequately cover the concentrat
...
SLOVENSKI STANDARD
oSIST prEN 1811:2009
01-oktober-2009
3ULPHUMDOQDSUHVNXVQDPHWRGD]DVSURãþDQMHQLNOMDL]L]GHONRYYVWDYOMHQLKY
SUHERGHQDXãHVDDOLGUXJHSUHERGHQHGHOHþORYHãNHJDWHOHVDNLVRY
QHSRVUHGQHPLQGDOMãHPVWLNXVNRåR
Reference test method for release of nickel from post assemblies which are inserted into
pierced parts of the human body and products intended to come into direct and
prolonged contact with the skin
Referenzprüfverfahren zur Bestimmung der Nickellässigkeit von sämtlichen Stäben, die
in durchstochene Körperteile eingeführt werden und Produkten, die unmittelbar und
länger mit der Haut in Berührung kommen
Méthode d'essai de référence relative à la libération du nickel par les assemblages de
tiges qui sont introduites dans les parties percées du corps humain et les produits
destinés à entrer en contact direct et prolongé avec la peau
Ta slovenski standard je istoveten z: prEN 1811
ICS:
39.060 Nakit Jewellery
oSIST prEN 1811:2009 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
oSIST prEN 1811:2009
---------------------- Page: 2 ----------------------
oSIST prEN 1811:2009
EUROPEAN STANDARD
DRAFT
prEN 1811
NORME EUROPÉENNE
EUROPÄISCHE NORM
July 2009
ICS 39.060 Will supersede EN 1811:1998
English Version
Reference test method for release of nickel from post
assemblies which are inserted into pierced parts of the human
body and products intended to come into direct and prolonged
contact with the skin
Méthode d'essai de référence relative à la libération du Referenzprüfverfahren zur Bestimmung der Nickellässigkeit
nickel par les assemblages de tiges qui sont introduites von sämtlichen Stäben, die in durchstochene Körperteile
dans les parties percées du corps humain et les produits eingeführt werden und Produkten, die unmittelbar und
destinés à entrer en contact direct et prolongé avec la peau länger mit der Haut in Berührung kommen
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee CEN/TC 347.
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 Management Centre has the
same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
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
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2009 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 1811:2009: E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
Contents Page
Foreword .4
Introduction .5
1 Scope .6
2 Normative references .6
3 Reagents .6
4 Apparatus .7
5 Samples .7
5.1 Sample area .7
5.1.1 Definition of sample area .7
5.1.2 Determination of sample area .8
5.1.3 Areas other than sample areas .8
5.2 Sample degreasing before testing .8
5.3 Quality control samples .8
6 Procedure .8
6.1 Principle of the procedure .8
6.2 Preparation of test solution .9
6.3 Release procedure .9
6.4 Determination of nickel . 10
6.4.1 General . 10
6.4.2 Calibration solutions . 10
6.4.3 Detection limit . 10
6.4.4 Number of test samples . 10
6.4.5 Number of replicate measurements. 10
6.5 Blank tests . 10
7 Calculations . 11
7.1 Nickel release . 11
7.2 Interpretation of results . 11
7.2.1 General . 11
7.2.2 Compliance assessment . 11
7.2.3 Uncertainty budget . 12
8 Test report . 12
Annex A (informative) Measurement uncertainty of the test procedure and compliance
assessment . 13
Annex B (normative) Requirements for quality control material . 15
Annex C (normative) A guide for preparation prior to nickel release testing for post assemblies
which are inserted into pierced parts of the human body and products intended to come
into direct and prolonged contact with the skin . 17
C.1 Introduction . 17
C.2 Terms and definitions for Annex C . 17
C.3 Requirements and principle . 18
C.4 Determination of the nickel release test method . 18
C.5 Determination of surfaces coming into direct and prolonged contact with the skin or
pierced parts of the body . 18
C.5.1 General . 18
C.5.2 Jewellery products . 19
C.5.3 Spectacle frames and sunglasses . 25
2
---------------------- Page: 4 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
C.5.4 Textiles, footwear, garments and leather goods . 25
C.6 Methods of determining the surface areas . 25
C.6.1 Surface area measurements . 25
C.6.2 Minimum surface area . 25
C.6.3 Simplification of surface area determination using common shapes of consumer
products . 26
C.7 Testing apparatus prior to nickel release testing . 26
Annex D (informative) Articles made from composite materials . 27
Bibliography . 28
3
---------------------- Page: 5 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
Foreword
This document (prEN 1811:2009) has been prepared by Technical Committee CEN/TC 347 “Methods for
analysis of allergens”, the secretariat of which is held by DS.
This document is currently submitted to the CEN Enquiry.
This document will supersede EN 1811:1998.
4
---------------------- Page: 6 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
Introduction
Adverse skin reaction to nickel has been known for many decades. Nickel is the most frequent cause of
contact allergy in Europe, and 10 % - 20 % of the patch tested female population and 1 % - 3 % of the patch
tested male population are allergic to nickel. Skin absorption of nickel ions, which are released from some
nickel-containing materials which are inserted into pierced ears or other pierced parts of the human body or
which are in direct and prolonged contact with the skin, causes sensitisation. Further exposure to soluble
nickel salts results in allergic contact dermatitis. It is known that sensitisation to nickel requires higher
exposure levels than does the elicitation in already sensitised individuals. There is a large variation in the
degree of sensitivity to nickel between individuals. This widespread health problem has forced the introduction
of a number of measures designed to reduce its prevalence. They include this standard which attempts to
provide an in-vitro chemical test that correlates as far as possible with the variable human biological reactions
that occur when metallic articles containing nickel are in direct and prolonged contact with the skin and
pierced parts of the body. The standard provides a measure of the amount of nickel release from an article
immersed for one week in artificial sweat. The standard also describes the preparation of a quality control
material intended to assist a laboratory in achieving an acceptable precision.
Clinical patch-testing of a small selection of nickel-containing alloys and coatings on nickel-sensitized persons
indicates that high and low results achieved with the present analytical method correspond closely with patch-
2
test reactivity. Moreover, a nickel release rate threshold of 0,5 µg/cm /week has been set in European
Parliament and Council Directive 94/27/EC (OJ No. L188 of 22.7.94) for products intended to come into direct
and prolonged contact with the skin. For all post piercing assemblies inserted into pierced ears and other
2
pierced parts of the human body a nickel release rate threshold of less than 0,2 µg/cm /week has been set in
Commission Directive 2004/96/EC (OJ No. L 301/51 of 27.9.2004).
5
---------------------- Page: 7 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
1 Scope
This European Standard specifies a method for simulating the release of nickel from all post assemblies which
are inserted into pierced ears and other pierced parts of the human body and articles intended to come into
direct and prolonged contact with the skin in order to determine whether such items are in compliance with the
European Directive 76/769/EEC as amended by 94/27/EC and 2004/96/EC.
DRAFTING REMARK Subject to the final positive decision of the European Commission, CEN/TC 347/TG 1 supports
the following wording to be included in the scope of this standard:
Spectacle frames and sunglasses are excluded from the scope of this European Standard.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 12472, Method for the simulation of wear and corrosion for the detection of nickel release from coated
items
ISO 3696, Water for analytical laboratory use - Specification and test methods
3 Reagents
Except where indicated, all reagents shall be of recognized pro analysis, p.a., grade or better and shall be free
of nickel.
3.1 Deionised water according to ISO 3696
3.2 Sodium chloride
3.3 DL-Lactic acid, ρ = 1,21 g/ml, > 88 % (m/m)
3.4 Urea
3.5 Sodium Hydroxide in solid tablets, 99,8 % pure dehydrate
3.6 Preparation of 1 M sodium hydroxide solution
Weigh 4 g of sodium hydroxide (3.5) ± 0,01 g and transfer into a 100 ml beaker containing 50 ml of deionised
water (3.1). Stir and cool to room temperature. Transfer the solution to a 100 ml volumetric flask and make up
to volume with deionised water (3.1).
3.7 Preparation of 0,1M sodium hydroxide solution
Add 25,0 ml of 1 M sodium hydroxide (3.6) in a 250 ml volumetric flask and make up to volume with deionised
water (3.1).
3.8 Hydrochloric acid, ρ = 1,18 g/ml, 37 % v/v
3.9 Preparation of 0,1 M hydrochloric acid solution
Transfer 10 ml of hydrochloric acid (3.8) into a 100 ml volumetric flask and make up to volume with deionised
water (3.1).
6
---------------------- Page: 8 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
3.10 Nitric acid, ρ = 1,40 g/ml, 65 % (m/m)
3.11 Dilute nitric acid, approximately 5 % (m/m)
Transfer 30 ml of nitric acid (3.10) into a 500-ml beaker containing about 350 ml of deionised water. Stir and
cool to room temperature. Transfer the solution to a 500-ml volumetric flask and make up to volume with
deionised water.
3.12 Degreasing solution
Dissolve 5 g of an anionic surface-active agent such as sodium dodecylbenzene sulfonate or sodium alkylaryl
sulfonate in 1000 ml water. An appropriately-diluted, neutral, commercially available detergent may be used.
3.13 Wax or lacquer (suitable for electroplating purposes) capable of protecting a surface from nickel
release.
The wax or lacquer shall be shown to prevent nickel release from a nickel-releasing surface when one or more
coats of the wax or lacquer are applied in the same manner as on a test sample, and tested for nickel release
according to clause 6 (see Annex C).
NOTE Information on sourcing of a suitable wax or lacquer is available from the CEN Management Centre.
4 Apparatus
4.1 A pH-meter, accurate to ± 0,05 pH
4.2 An analytical spectrometer capable of detecting a concentration of 0,01 mg nickel per litre in the final
test solution. It is recommended that either an inductively-coupled plasma spectrometer (optical emission or
mass spectrometer) or an electrothermal excitation atomic absorption spectrometer is used.
4.3 Thermostatically controlled water-bath or oven with or without cooling option, capable of
maintaining a temperature of (30 ± 2) °C.
4.4 A vessel with lid, both composed of a non-metallic, nickel-free and nitric-acid-resistant material, such
as glass and/or polypropylene and/or polytetrafluoroethylene and/or polystyrene. The sample shall be
suspended in the liquid by a holder made from the same materials as listed above, so as to minimize contact
of the sample area (5.1.1) with the walls and base of the vessel. The size and shape of vessel and holder
shall be chosen so as to minimize the volume of test solution required to completely cover the object to be
tested.
In order to remove any trace of nickel, the vessel and holder shall be pre-treated by being stored in a solution
of dilute nitric acid (3.11) for at least 4 h. After acid treatment, rinse the vessel and holder with deionised water
and dry.
4.5 Digital caliper with a minimum resolution of 50 µm or a micrometer with a minimum resolution of
5 µm.
5 Samples
5.1 Sample area
5.1.1 Definition of sample area
The surfaces that are immersed in the test solution and that are not covered with a masking agent are defined
as "sample area" and shall be used for calculation purposes (7.1).
7
---------------------- Page: 9 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
As far as possible, only the surface(s) that come(s) into direct and prolonged contact with the skin and / or that
have contact with the pierced parts of the body should be tested.
However, where articles appear to be made from uniform material(s), consideration should be given to testing
the whole surface (whether or not it is all in direct and prolonged contact with the skin or with pierced parts of
the body) since errors are introduced by the masking process (see also C.5.1).
The test laboratory shall consult Annex C.5 in order to determine which surfaces are to be tested.
5.1.2 Determination of sample area
Determination of the sample area (a) in square centimetres is achieved by marking the contour of the sample
area assuming that the item is worn or used as intended (see Annex C) and measuring it by an appropriate
measuring device (4.5). In order to achieve the required degree of analytical sensitivity, a minimum sample
2
area of 0,2 cm shall be tested. If necessary, identical items may be treated together to obtain this minimum
area.
NOTE If an item is being tested to ascertain its conformity with Directives 94/27/EC and 2004/96/EC, the accuracy
with which the sample area of the item has to be determined is dependent on the nickel release of this item.
The closer the nickel release is to the limit laid down in the directive, the more accurately the surface area has
to be determined.
5.1.3 Areas other than sample areas
In order to prevent release of nickel from areas other than the sample area, such areas shall be removed or
protected from the test solution. This may be achieved after degreasing (see 5.2) by the application of one or
more coatings of a wax or lacquer (3.13) which has been shown to protect from nickel release.
The test laboratory shall consult Annex C.5 in order to determine which surfaces are to be tested.
5.2 Sample degreasing before testing
Gently swirl the sample for 2 min in degreasing solution (3.12) at room temperature. Rinse thoroughly with
deionised water and dry using an absorbing cloth. After degreasing, items should be handled with plastic
forceps or clean protective gloves.
NOTE This cleaning stage is intended to remove extraneous grease and skin secretions due to handling, but not any
protective coatings. It will also substantially remove any nickel contamination that might be present on the surface of the
item. If there is a requirement to determine this nickel contamination, the cleaning stage should be omitted. Omission of
this cleaning stage might affect the nickel release from the item.
5.3 Quality control samples
As a quality control check, the nickel release from a quality control sample shall be determined (see Annex A
and Annex B).
The quality control sample shall be degreased in the same way as the sample according to 5.2 and shall be
used only once.
6 Procedure
6.1 Principle of the procedure
The item to be tested for nickel release is placed in an artificial sweat test solution for one week. The
concentration of dissolved nickel in the solution is determined by an appropriate analytical method, for
8
---------------------- Page: 10 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
example inductively-coupled plasma spectrometry. The nickel release is expressed in micrograms per square
2
centimetre per week (µg/cm /week).
6.2 Preparation of test solution
The test solution consists of deionised water (3.1) containing:
0,5 % (m/m) sodium chloride (3.2);
0,1 % (m/m) lactic acid (3.3);
0,1 % (m/m) urea (3.4); and
NaOH, in solid tablets, 99,8 % pure dehydrate (3.5)
The test solution shall be prepared as follows:
Add 900 ml of freshly prepared deionised water (3.1) to a 1000 ml beaker. Add 1,00 ± 0,01 g of urea (3.4),
5,00 ± 0,05 g of sodium chloride (3.2) and 1,00 ± 0,01 g of lactic acid (3.3), and stir until dissolved.
Calibrate a pH meter in accordance with the manufacturer’s instructions using freshly prepared buffer
solutions.
Immerse the pH electrode into the test solution and measure the pH. Slowly and gently, add drop by drop a
volume of 1 M sodium hydroxide (3.6) until a pH of 5,5 ± 0,05 is reached and with continuous stirring, add
slowly and gently drop by drop a volume of 0,1 M sodium hydroxide (3.7) until a pH 6,5 ± 0,05 is reached and
remains stable.
Measure the pH after 10 minutes from the last addition of 0,1 M sodium hydroxide to ensure that the pH is in
the range 6,5 ± 0,05.
Transfer the solution to a 1000 ml volumetric flask and make up to volume with deionised water. Before use,
ensure that the pH of the test solution is in the range of pH 6,5 ± 0,05.
If it is necessary to reduce the pH of the solution to 6,5 ± 0,05 before testing, this shall be done by adding
slowly and gently with continuous stirring drop by drop a volume of 0,1 M Hydrochloric acid (3.9).
The test solution shall be used within 3 hours of preparation.
6.3 Release procedure
In the following text the term "test solution" represents the solution as prepared according to 6.2, the "release
solution" is the solution resulting from the release procedure.
Place the sample, suspended by its holder, in the test vessel (4.4). Add an amount of test solution
2
corresponding to approximately 1 ml per cm sample area. The suspended sample area shall be totally
immersed. It is not essential to immerse areas which are completely protected by wax or lacquer. The
minimum volume of test solution added shall be 0,5 ml irrespective of the surface area. Note the sample area
and the amount of the test solution used. Close the vessel with a tight lid in order to prevent evaporation of the
test solution. Leave the vessel undisturbed in a thermostatically-controlled water-bath or oven (4.3) at
(30 ± 2°C) for 168 ± 2 h without agitation.
If a quality control sample (5.3) is to be determined, it should be suspended in an appropriate volume of test
solution and treated in the same manner as a sample.
After 168 ± 2 h, slowly remove the sample from the release solution. To remove solution contained in cavities
of the sample, the sample shall be turned appropriately. The sample shall not be rinsed.
Quantitatively transfer the release solution to an appropriately-sized (see note) volumetric flask washed with
dilute nitric acid (3.11). In order to prevent redeposition of dissolved nickel, add dilute nitric acid (3.11), to
9
---------------------- Page: 11 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
achieve a concentration of about 1 % nitric acid, when the flask is made up to volume (V in ml) using the test
solution (6.2). The minimum final volume to which the release solution may be diluted is 2 ml.
NOTE The choice of volumetric flask size should take into account the sensitivity of the instrumentation used for the
nickel determination (see 4.4).
If filtering of the release solution is required, special attention should be given to the small volume of solution,
the expected concentration and possible contamination. Filters should be rinsed with test solution (6.2) before
filtering the release solution to avoid contamination of the release solution.
Test solution shall be stored in a refrigerator below 10 °C if used for the production of calibration solutions.
6.4 Determination of nickel
6.4.1 General
Determine the nickel content of the test solution using an analytical spectrometer (see 4.2).
For the determination of nickel using an analytical spectrometer the following recommendations shall be
considered.
6.4.2 Calibration solutions
The calibration solutions used for the nickel determination shall match the matrix of the test solution plus any
added nitric acid and adequately cover the concentration range of the release solutions.
6.4.3 Detection limit
For the limit of detection and quantification determination it is recommended to apply an established method
such as the IUPAC standard as described in publication [1] and to report concentration values close to the
detection limit in terms of release rate. If it is required to dilute the sample solution, the dilution factor shall
take into consideration the corresponding detection limit of the analytical spectrometer. Further information
about the analytical procedures for the determination of nickel can be obtained from a publication under
preparation.
6.4.4 Number of test samples
It is recommended to use a minimum of three test samples. However, laboratory practice shows that under
normal conditions, only one or two test samples are available.
It is recommended to ensure that the samples are of the same composition before testing by determining the
composition by an appropriate analytical method, for instance X-ray fluorescence spectrometry.
6.4.5 Number of replicate measurements
At least two replicate measurements of each release solution shall be carried out.
6.5 Blank tests
Duplicate blank tests shall be carried out at the same time as the testing of the sample. Identical vessels and
holders shall be used and the test procedure is identical except that no sample is placed in the vessels.
Identical amounts of test solution, and dilute nitric acid shall be used.
10
---------------------- Page: 12 ----------------------
oSIST prEN 1811:2009
prEN 1811:2009 (E)
7 Calculations
7.1 Nickel release
2
The nickel release of a sample, d, expressed in micrograms per square centimetre per week (µg/cm /week), is
given by the equation:
V × (C −C )
1 2
d = (7.1)
1000×a
where:
2
a is the sample area of the test object, in square centimetres (cm );
V is the dilution volume of the release solution, in millilitres (ml);
C is the mean nickel concentration in the diluted release solution after 1 week , in micrograms per litre (µg/l);
1
C is the mean value of the nickel concentration in the blank solutions after 1 week, in micrograms per litre
2
(µg/l).
2
The result is expressed in µg/cm /week and the measurement uncertainty of the laboratory has to be reported
in the test report.
7.2
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.