25/06/2015. Release of nickel from products Dr. Ansgar Wennemer. Ggf. Kundenlogo einbauen 25/06/2015

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1 Ggf. Kundenlogo einbauen Release of nickel from products Dr. Ansgar Wennemer 1

2 Release of nickel from products Dr. Ansgar Wennemer TÜV Rheinland LGA Products GmbH Release of nickel from products What products in prolonged contact to skin are tested. Why nickel is used, how it is applied. What boosts the release of nickel. What are the practical challenges of testing. 2

3 Legal Requirement: REACH Annex XVII Nickel and its compounds 1. Shall not be used: (a) in (body piercings) 0,2 μg/cm²/week (migration limit) (b) in articles intended to come into direct and prolonged contact with the skin such as: - earrings, - necklaces, bracelets and chains, anklets, finger rings, - wrist-watch cases, watch straps and tighteners, - rivet buttons, tighteners, rivets, zippers and metal marks, when these are used in garments, if the rate of nickel release from the parts of these articles coming into direct and prolonged contact with the skin is greater than 0,5 μg/cm²/week. (Nickel-free coatings have to be durable for 2 years.) Tested products at TÜV Rheinland ordered by retailers: - Jewellery - Watches - Metal parts of clothing (with and without prolonged skin contact?) belts, shoes, zippers - Metal parts of bags (in prolonged contact to skin?) - Spectacles (parts in prolonged contact to skin), EN Toys (in prolonged contact to skin?) metal parts in continous contact to the same part of the skin for hours 3

4 Metal surface in contact to skin Nickel-containing electroplating Top coat Middle layer Chromium 0,2-0,5 µm / gold 0,02 2 µm / Ro, Pd, Ru, Pt, lacquer microporous nickel, 1 µm, pores/cm² 2. Layer Nickel; semi-gloss, gloss, µm each 1. Layer Copper, 5-15 µm, max. 30µm (silver) Base material Iron, copper alloy, die casting (Al, Zn, Sn, ) polymers Results : < 0,1 µg/cm²/week 360 µg/cm²/week, variation often >46% Metal surface in contact to skin Nickel - Free electroplating Top coat Ro, Pd, Ru, Pt, / gold 0,02 2 µm / laquer 1. Layer Zn, Cu, Sn (Cd, Sb, Bi) 2-3 µm Base material Iron, copper alloy, die casting (Al, Zn, Sn, ) polymers Results : < 0,1 µg/cm²/week, stable test results 4

5 Metal surface in contact to skin Steel High alloy steel (18/10, 18/8) 18 % chromium, 7-10% nickel Low-alloy steel 2-7% nickel nickel free? Results : High alloy steel < 0,1 µg/cm²/week but critical parts, surfaces Low-alloy steel often > 0,1 µg/cm²/week Nickel release Nickel release caused by corrosion, influenced by: - Pores, cracks and chinks in the surface, e.g.: - chromium plating >2µm - cracks from production and transport - Inhomogeneity in electroplated coating (nicks, hollow, undercut) - differing nobel alloys within a product, incorporations, impurities - e.g. gold in contact with high alloy steel - high alloy steel contaminated with iron, brushed welding and soldering joints damage of the passivation layer 5

6 Test methode, scheme EN 12472:2009 Abrasion- and corrosion test - Corrosion method (5.2) - Abrasion method (5.3) - Fixing of the test sample (5.3.2, Annex A) EN 1811:2011 test method for release of nickel - Identification of sample area, sample material - Masking of area without contact to skin (7.1.3), - Determination of surface area - Migration for one week - Determination of nickel concentration of migration solution - Calculation of test result - Interpretation of test result Challenges of sample preparation Many different materials combined in one product identification by XRF 6

7 Challenges of sample preparation Each type of material has to be tested separately: - separate material by cutting (do not bend!) - if not possible -> test it together Challenges of sample preparation Masking of areas without contact to skin and cutting edges example: piercing 7

8 Challenges of sample preparation Masking of areas without contact to skin Example: surface areas inside Challenges of sample preparation Masking of areas without contact to skin Example: surface areas inside 8

9 Challenges of determination of the surface Test results, EN 1811:2011 [µg/cm²/week] > 0,5 μg/cm²/week % % % % % % N >

10 Test results, EN 1811:2011 [µg/cm²/week] µg/cm²/week / % ,0 < 0,2 33,7 69,5 63,7 67,2 0,2-0,28 4,9 1,9 1,8 3,3 > 0,28-0,5 5,6 6,0 11,0 3,7 > 0,5-0,88 6,3 3,1 4,2 3,1 > 0, ,8 6,3 7,3 4,0 > ,9 7,4 5,7 3,3 > ,0 2,3 2,0 1,4 > ,9 3,6 4,4 3,9 > Limit 55,9 22,6 23,6 15,7 Test method CR 12471:2002 Pre-test: Quicktest for nickel release in different variations - corresponds with the Rubbing -Test according to the old BGVO (quick-test) Laboratory - soaking in synthetic sweat solution, 15 min.; 50 C application: - determination of the nickel release comparable with pre-test - in presence of Fe II, oxidation with H 2 O 2 to Fe III On-site: - as laboratory application except for the following deviation: drying with hair-blower or incadescent light bulb thermometer 10

11 TÜV Rheinland LGA Products GmbH Dr. Ansgar Wennemer Am Grauen Stein D Köln Nickel Interpretation of the results according to DIN EN 1811:

12 Interpretation of the results Interpretation of the results according to DIN EN 1811: The limit value is clearly exceeded. 2. It is not possible for authorities to prove exceedance of the limit value. It is possible that authorities find results of > 0,88 mg/kg. 3. It is not possible for the manufacturer to irrefutably prove that the limit value is met. Complaint from the authorities is not possible. 4. The limit value is unequivocally met. Interpretation of the results Interpretation of the results according to EN 1811:2011/FprA1:2015 in preparation Limit value: 0,5 µg/cm²/week Measured value: < 0,88 µg/cm²/week pass Critical situation in the following examples: Result: 0,7 µg/cm²/week pass Possible result obtained by authorities considering 46% variance: 0,95 µg/cm²/week fail regular objection 12