Screening tests for nickel release from alloys and coatings in items that come into direct and prolonged contact with the skin

This European Standard presents a quick screening method, based on the use of dimethylglyoxime, sutable for the evaluation of nickel release from items that come into direct and prolonged contact with the skin, with special reference to nickel allergy.

Schnelltest für die Nickelabgabe aus Legierungen und Auflagen auf Gegenständen, die mit der Haut in direkte und länger andauernde Berührung kommen

Die vorliegende Europäische Norm bietet einen Schnelltest, der auf Anwendung von Dimethylglyoxim beruht und zur Bewertung der Nickelabgabe aus Gegenständen geeignet ist, die, besonders im Hinblick auf die Nickelallergie, für einen längeren Zeitraum direkt mit der Haut in Berührung kommen.

Méthode de tri pour la libération du nickel des alliages et revêtements présents sur les articles de consommation entrant en contact direct et prolongé avec la peau

La présente norme européenne expose une méthode de tri rapide basée sur l'utilisation de la diméthyglyoxime, convenant pour l'évaluation du nickel libéré par les objets entrant en contact direct et prolongé avec le peau, avec une référence particulière pour les allergies au nickel.

Hitri preskusi sproščanja niklja iz zlitin in prevlek, ki prihajajo v neposreden in daljši stik s kožo

General Information

Status
Withdrawn
Publication Date
13-Aug-2002
Current Stage
9960 - Withdrawal effective - Withdrawal
Completion Date
23-Feb-2022

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Schnelltest für die Nickelabgabe aus Legierungen und Auflagen auf Gegenständen, die mit der Haut in direkte und länger andauernde Berührung kommenMéthode de tri pour la libération du nickel des alliages et revetements présents sur les articles de consommation entrant en contact direct et prolongé avec la peauScreening tests for nickel release from alloys and coatings in items that come into direct and prolonged contact with the skin39.060NakitJewelleryICS:Ta slovenski standard je istoveten z:CR 12471:2002SIST CR 12471:2004en01-januar-2004SIST CR 12471:2004SLOVENSKI

STANDARD
SIST CR 12471:2004
CEN REPORTRAPPORT CENCEN BERICHTCR 12471August 2002ICS

39.060English versionScreening tests for nickel release from alloys and coatings initems that come into direct and prolonged contact with the skinMéthode de tri pour la libération du nickel des alliages etrevêtements présents sur les articles de consommationentrant en contact direct et prolongé avec la peauSchnelltest für die Nickelabgabe aus Legierungen undAuflagen auf Gegenständen, die mit der Haut in direkte undlänger andauernde Berührung kommenThis CEN Report was approved by CEN on 13 April 2002. It has been drawn up by the Technical Committee CEN/TC 283.CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36

B-1050 Brussels© 2002 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CR 12471:2002 ESIST CR 12471:2004

CR 12471:2002 (E)2ContentspageForeword......................................................................................................................................................................3Introduction.................................................................................................................................................................41Scope..............................................................................................................................................................52Short description of the methods................................................................................................................53Reagents.........................................................................................................................................................54Equipment.......................................................................................................................................................55Procedure.......................................................................................................................................................65.1Preparation of solutions................................................................................................................................65.2Sample preparation.......................................................................................................................................65.3Test methods..................................................................................................................................................76Interpretation of results.................................................................................................................................86.1Positive result.................................................................................................................................................86.2Negative result...............................................................................................................................................96.3Uncertain result..............................................................................................................................................97Test report......................................................................................................................................................9Bibliography..............................................................................................................................................................10SIST CR 12471:2004

CR 12471:2002 (E)3ForewordThis document (CR 12471:2002) has been prepared by Technical Committee CEN/TC 283 "Precious metals -Applications in jewellery and associated products", the secretariat of which is held by UNI.SIST CR 12471:2004

CR 12471:2002 (E)4IntroductionThis document has been developed as a simple, quick and inexpensive means for qualitatively testing for nickelrelease from (mainly) consumer items.

It has particular relevance in relation to allergic contact dermatitis due tonickel allergy. The tests described are quick and easy to conduct and two of them are suitable for applicationoutside of the laboratory.European Parliament and Council Directive 94/27/EC (OJ No. L 188 of 22.7.94) has set a nickel release ratethreshold of 0,5 µg/cm2/week.

Although the present document will give information concerning nickel release,results obtained from its application do not constitute confirmation or otherwise of compliance with the directive.

Inorder to show compliance with the directive, it is necessary that items are tested in accordance with EuropeanStandards EN 1810, EN 1811 or EN 12472, as appropriate, depending upon the nature of the item to be tested.SIST CR 12471:2004

CR 12471:2002 (E)51 ScopeThis document presents a screening procedure, based primarily on the use of dimethylglyoxime, for the detectionof nickel release from items that come into direct and prolonged contact with the skin.The tests provide qualitative, not quantitative, results.NOTE - EN 1811 specifies a quantitative reference test for the release of nickel.2 Short description of the methodsThe test methods are based on the formation of a coloured complex when nickel ions come into contact withdimethylglyoxime or dithiooxamide.

In order to increase the sensitivity of the method, pre-treatment with artificialsweat and heat is used to induce corrosion of the surface, simulating the influence of sweat when the item is incontact with the skin.

This screening method gives a result in a short time.

The result is indicative and providesguidance when evaluating items for nickel release.3 ReagentsAll reagents shall be of pro analysi grade or better.3.1Deionized water3.2Ammonia solution, about 10 % (m/m) NH3NOTE - This solution may be prepared from a more concentrated ammonia solution; for example, one containing 24 % or 30 %(m/m) NH3.3.3Sodium chloride, NaCI3.4Lactic acid, CH3CHOHCOOH, r = 1,21 g/ml, > 88 %3.5Urea, CO(NH2)23.6Dimethylglyoxime, C4H8N2O2, 99 %, or test strips for the detection of nickel, containing dimethylglyoxime orother colorimetric reagent(s) with approximately equivalent selectivity and sensitivity to nickel.3.7Ethanol, C2H5OH, > 95 %3.8Hydrogen peroxide, H202, approximately 30 % (m/V) solution (100 volume).

(Not required for the pre-test,5.3.4 or the field test, 5.3.6)3.9Dithiooxamide (rubeanic acid), C2H4N2S2.

(Not required for the pre-test or the field test)3.10Sodium acetate trihydrate, C2H3NaO23H2O.

(Not required for the pre-test or the field test)3.11Acetic acid, glacial, C2H4O2.

(Not required for the pre-test or the field test)4 Equipment4.1Flat-bottomed dish, made of glass or other non-metallic material.

(Not required for the pre-test)4.2Thermometer, (0°C - 100°C) ± 1°CSIST CR 12471:2004

CR 12471:2002 (E)64.3Pasteur pipette or, for the field test, a drop-dispensing bottle capable of dispensing drops with anapproximate volume of 50 µI.4.4Cotton-wool-tipped sticks (white)4.5pH meter or narrow-range pH paper4.6Laboratory oven, capable of maintaining a temperature of 50°C ± 3°C

(required for the laboratory test, 5.3.5)4.7Heating/drying apparatus

(required only for the field test)4.7.1Hand-held hair dryer, or4.7.2Apparatus consisting of a light bulb, reflector type, (IEC 887: R80; 60 W to 100 W) mounted verticallydownwards in a lamp holder positioned above a flat base, such that the distance of the face of the bulb above theflat base may be varied between approximately 40 mm and 120 mm.5 Procedure5.1 Preparation of solutionsUnless otherwise specified, the following solutions are stable for 6 months at temperatures below 25°C.5.1.1Dimethylglyoxime, 0,8% (m/V) alcoholic solution. Weigh 0,8 g ± 0,05 g of dimethylglyoxime (3.6), dissolveand make up to 100 ml in ethanol (3.7).5.1.2Artificial sweat. Transfer 1g ± 0,02 g urea (3.5), 5 g ± 0,1 g sodium chloride (3.3) and 1,13 g ± 0,02 g (940µl ± 20 µl) lactic acid (3.4) into a 2-litre beaker.

Add 1000 ml deionized water (3.1) and stir.

Using a pH meter orpH paper (4.5), adjust the pH to 6,5 ± 0,2 by the dropwise addition of ammonia solution (3.2) with stirring.

Artificialsweat is stable for 6 months when kept in the dark below 8°C in a closed container.NOTE - The use of a pH meter is preferable to the use of narrow-range pH paper.5.1.3Dithiooxamide, 0,5% (m/V) alcoholic solution. Weigh 0,5 g ± 0,05 g of dithiooxamide (3.9), dissolve andmake up to 100 ml in ethanol (3.7).5.1.4Sodium acetate buffer solution, pH 4.5. Weigh 5,6 g sodium acetate trihydrate (3.10) and add 2,4 ml glacialacetic acid (3.11).

Dissolve

and make up to 10 ml with water.5.2 Sample preparation5.2.1The surfaces to be tested are those that come into direct and prolonged contact with the skin.

Thesurface(s) of the item to be tested shall be cleaned with ethanol (3.7) using a cotton-wool-tipped stick (4.4).NOTE 1 - This cleaning stage is intended to remove extraneous grease and skin secretions due to handling, but not anyprotective coatings.

However, it will also substantially remove any nickel salts present on the surface of the test item.

If there isa requirement to detect the presence
...

SLOVENSKI STANDARD
SIST CR 12471:2004
01-januar-2004

Hitri preskusi sproščanja niklja iz zlitin in prevlek, ki prihajajo v neposreden in

daljši stik s kožo

Screening tests for nickel release from alloys and coatings in items that come into direct

and prolonged contact with the skin

Schnelltest für die Nickelabgabe aus Legierungen und Auflagen auf Gegenständen, die

mit der Haut in direkte und länger andauernde Berührung kommen

Méthode de tri pour la libération du nickel des alliages et revetements présents sur les

articles de consommation entrant en contact direct et prolongé avec la peau
Ta slovenski standard je istoveten z: CR 12471:2002
ICS:
39.060 Nakit Jewellery
SIST CR 12471:2004 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST CR 12471:2004
---------------------- Page: 2 ----------------------
SIST CR 12471:2004
CEN REPORT
CR 12471
RAPPORT CEN
CEN BERICHT
August 2002
ICS 39.060
English version
Screening tests for nickel release from alloys and coatings in
items that come into direct and prolonged contact with the skin

Méthode de tri pour la libération du nickel des alliages et Schnelltest für die Nickelabgabe aus Legierungen und

revêtements présents sur les articles de consommation Auflagen auf Gegenständen, die mit der Haut in direkte und

entrant en contact direct et prolongé avec la peau länger andauernde Berührung kommen

This CEN Report was approved by CEN on 13 April 2002. It has been drawn up by the Technical Committee CEN/TC 283.

CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,

Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels

© 2002 CEN All rights of exploitation in any form and by any means reserved Ref. No. CR 12471:2002 E

worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST CR 12471:2004
CR 12471:2002 (E)
Contents
page

Foreword......................................................................................................................................................................3

Introduction .................................................................................................................................................................4

1 Scope ..............................................................................................................................................................5

2 Short description of the methods ................................................................................................................5

3 Reagents.........................................................................................................................................................5

4 Equipment.......................................................................................................................................................5

5 Procedure .......................................................................................................................................................6

5.1 Preparation of solutions................................................................................................................................6

5.2 Sample preparation .......................................................................................................................................6

5.3 Test methods..................................................................................................................................................7

6 Interpretation of results.................................................................................................................................8

6.1 Positive result.................................................................................................................................................8

6.2 Negative result ...............................................................................................................................................9

6.3 Uncertain result..............................................................................................................................................9

7 Test report ......................................................................................................................................................9

Bibliography ..............................................................................................................................................................10

---------------------- Page: 4 ----------------------
SIST CR 12471:2004
CR 12471:2002 (E)
Foreword

This document (CR 12471:2002) has been prepared by Technical Committee CEN/TC 283 "Precious metals -

Applications in jewellery and associated products", the secretariat of which is held by UNI.

---------------------- Page: 5 ----------------------
SIST CR 12471:2004
CR 12471:2002 (E)
Introduction

This document has been developed as a simple, quick and inexpensive means for qualitatively testing for nickel

release from (mainly) consumer items. It has particular relevance in relation to allergic contact dermatitis due to

nickel allergy. The tests described are quick and easy to conduct and two of them are suitable for application

outside of the laboratory.

European Parliament and Council Directive 94/27/EC (OJ No. L 188 of 22.7.94) has set a nickel release rate

threshold of 0,5 μg/cm /week. Although the present document will give information concerning nickel release,

results obtained from its application do not constitute confirmation or otherwise of compliance with the directive. In

order to show compliance with the directive, it is necessary that items are tested in accordance with European

Standards EN 1810, EN 1811 or EN 12472, as appropriate, depending upon the nature of the item to be tested.

---------------------- Page: 6 ----------------------
SIST CR 12471:2004
CR 12471:2002 (E)
1 Scope

This document presents a screening procedure, based primarily on the use of dimethylglyoxime, for the detection

of nickel release from items that come into direct and prolonged contact with the skin.

The tests provide qualitative, not quantitative, results.

NOTE - EN 1811 specifies a quantitative reference test for the release of nickel.

2 Short description of the methods

The test methods are based on the formation of a coloured complex when nickel ions come into contact with

dimethylglyoxime or dithiooxamide. In order to increase the sensitivity of the method, pre-treatment with artificial

sweat and heat is used to induce corrosion of the surface, simulating the influence of sweat when the item is in

contact with the skin. This screening method gives a result in a short time. The result is indicative and provides

guidance when evaluating items for nickel release.
3 Reagents
All reagents shall be of pro analysi grade or better.
3.1 Deionized water
3.2 Ammonia solution, about 10 % (m/m) NH

NOTE - This solution may be prepared from a more concentrated ammonia solution; for example, one containing 24 % or 30 %

(m/m) NH3.
3.3 Sodium chloride, NaCI
3.4 Lactic acid, CH CHOHCOOH, r = 1,21 g/ml, > 88 %
3.5 Urea, CO(NH )
2 2

3.6 Dimethylglyoxime, C H N O , 99 %, or test strips for the detection of nickel, containing dimethylglyoxime or

4 8 2 2

other colorimetric reagent(s) with approximately equivalent selectivity and sensitivity to nickel.

3.7 Ethanol, C H OH, > 95 %
2 5

Hydrogen peroxide, H 0 , approximately 30 % (m/V) solution (100 volume). (Not required for the pre-test,

3.8
2 2
5.3.4 or the field test, 5.3.6)

3.9 Dithiooxamide (rubeanic acid), C H N S . (Not required for the pre-test or the field test)

2 4 2 2

3.10 Sodium acetate trihydrate, C H NaO 3H O. (Not required for the pre-test or the field test)

2 3 2 2

3.11 Acetic acid, glacial, C H O . (Not required for the pre-test or the field test)

2 4 2
4 Equipment

4.1 Flat-bottomed dish, made of glass or other non-metallic material. (Not required for the pre-test)

Thermometer, (0°C - 100°C) ± 1°C
4.2
---------------------- Page: 7 ----------------------
SIST CR 12471:2004
CR 12471:2002 (E)

4.3 Pasteur pipette or, for the field test, a drop-dispensing bottle capable of dispensing drops with an

approximate volume of 50 μI.
4.4 Cotton-wool-tipped sticks (white)
4.5 pH meter or narrow-range pH paper

4.6 Laboratory oven, capable of maintaining a temperature of 50°C ± 3°C (required for the laboratory test, 5.3.5)

4.7 Heating/drying apparatus (required only for the field test)
4.7.1 Hand-held hair dryer, or

4.7.2 Apparatus consisting of a light bulb, reflector type, (IEC 887: R80; 60 W to 100 W) mounted vertically

downwards in a lamp holder positioned above a flat base, such that the distance of the face of the bulb above the

flat base may be varied between approximately 40 mm and 120 mm.
5 Procedure
5.1 Preparation of solutions

Unless otherwise specified, the following solutions are stable for 6 months at temperatures below 25°C.

5.1.1 Dimethylglyoxime, 0,8% (m/V) alcoholic solution. Weigh 0,8 g ± 0,05 g of dimethylglyoxime (3.6), dissolve

and make up to 100 ml in ethanol (3.7).

5.1.2 Artificial sweat. Transfer 1g ± 0,02 g urea (3.5), 5 g ± 0,1 g sodium chloride (3.3) and 1,13 g ± 0,02 g (940

μl ± 20 μl) lactic acid (3.4) into a 2-litre beaker. Add 1000 ml deionized water (3.1) and stir. Using a pH meter or

pH paper (4.5), adjust the pH to 6,5 ± 0,2 by the dropwise addition of ammonia solution (3.2) with stirring. Artificial

sweat is stable for 6 months when kept in the dark below 8°C in a closed container.

NOTE - The use of a pH meter is preferable to the use of narrow-range pH paper.

5.1.3 Dithiooxamide, 0,5% (m/V) alcoholic solution. Weigh 0,5 g ± 0,05 g of dithiooxamide (3.9), dissolve and

make up to 100 ml in ethanol (3.7).

5.1.4 Sodium acetate buffer solution, pH 4.5. Weigh 5,6 g sodium acetate trihydrate (3.10) and add 2,4 ml glacial

acetic acid (3.11). Dissolve and make up to 10 ml with water.
5.2 Sample preparation

5.2.1 The surfaces to be tested are those that come into direct and prolonged contact with the skin. The

surface(s) of the item to be tested shall be cleaned with ethanol (3.7) using a cotton-wool-tipped stick (4.4).

NOTE 1 - This cleaning stage is intended to remove extraneous grease and skin secretions due to handling, but not any

protective co
...

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