Transactions of the IMF
The International Journal of Surface Engineering and Coatings
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‘Nickel Allergy’ arising from decorative nickel
plated and alloyed articles: prevention at source
C. M. Whittington & W. Y. Lo
To cite this article: C. M. Whittington & W. Y. Lo (2019) ‘Nickel Allergy’ arising from decorative
nickel plated and alloyed articles: prevention at source, Transactions of the IMF, 97:2, 64-66,
DOI: 10.1080/00202967.2019.1570737
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TRANSACTIONS OF THE IMF
2019, VOL. 97, NO. 2, 64–66
https://doi.org/10.1080/00202967.2019.1570737
‘Nickel Allergy’ arising from decorative nickel plated and alloyed articles:
prevention at source
C. M. Whittingtona and W. Y. Lob
a
C. M. Whittington & Associates Ltd., Hong Kong; bHong Kong Productivity Council, Kowloon, Hong Kong
ABSTRACT KEYWORDS
This work builds on papers published in Transactions during 2015 and 2018 reporting research into Nickel allergy; allergic contact
low-cost commercial methods for the prevention of nickel release from decorative nickel plated dermatitis; prevention of
articles, rendering them suitable for placement on the European market in accordance with the nickel release; nickel-plated
requirements of REACH. ‘Nickel Allergy’ sometimes occurs when nickel-containing articles are in articles; REACH
direct and prolonged contact with the skin, leading to corrosion of elemental nickel by sweat,
liberating sufficient nickel ions to be absorbed through the skin and initiate an allergenic effect.
The EU ‘Nickel Restrictions’ impose limits on the amount of nickel released from articles intended
for use in this application, but permits a non-nickel surface coating that can ensure the rate of
nickel release does not exceed 0.5 µg cm−2 week−1 after 2 years of normal use. The official tests for
coated items are simulated wear and corrosion under EN 12472 followed by determination of
nickel release under EN 1811. Earlier work concluded that suitable barrier coatings over bright
electrodeposited nickel are regular chromium deposited from a hexavalent electrolyte, microporous
trivalent chromium from a chloride electrolyte and UV cured PU electrophoretic coatings. Further
tests reported here focused on nickel release from examples of wearable articles such as costume
jewellery and watch cases. A typical flash coating of gold over bright nickel is thin and porous and
being more noble, causes the rate of nickel release to be accelerated; but this can be prevented by
an intermediate barrier coating of electrodeposited palladium. To round out the relevance of this
study on wearable articles, nickel release tests were also conducted on nickel-containing Grades
304 (UNS S30400) and 316 (UNS S31600) austenitic stainless steels, plus a typical gold alloy
containing nickel. All passed the nickel release tests satisfactorily.
1. Background 3 Non-occupational sensitisation release. Testing was carried out accord-
sometimes occurs when skin is in ing to CEN (Comité Européen de Nor-
Recent papers on the allergenic effects
contact with nickel-plated haber- malisation, European Committee for
of nickel were published in this journal
dashery items such as clothing Standardization) EN 12472:2005 +
by Whittington et al.1 in 2015, Gabe
hooks, clasps and zippers, and may A1:2009 ‘Method for the simulation of
and Larson2 in 2017 and Whittington
also arise from costume jewellery wear and corrosion for the detection
and Lo3 in 2018, where the following
and body piercing. In 1994, the EU of nickel release from coated items’ fol-
was reported:
issued the ‘Nickel Directive’ as a regu- lowed by EN 1811:2011 and amended
latory control that places limits on EN 1811:2011 + A1:2015 ‘Test method
1 Decorative nickel-containing articles the amount of nickel released from for release of nickel from all post assem-
may release nickel ions when in articles intended to come into direct blies which are inserted into pierced
direct and prolonged contact with and prolonged contact with the parts of the human body and articles
skin, causing the immune system to skin. This was subsumed into the EU intended to come into direct and pro-
become nickel-sensitised if sufficient Commission’s Regulation on Regis- longed contact with skin’ the latter
nickel ions are absorbed through tration, Evaluation, Authorisation stating that articles with a migration
the skin repeatedly in the same and Restriction of Chemicals limit of 0.5 µg cm−2 week−1 shall be
area. This can cause allergic contact (REACH), Annex XV11, Item 27 in accepted and permitted to be placed
dermatitis (ACD), appearing as a 2007, the relevant part of which is on the market if the measured value is
rash, itch, redness or dry skin in reproduced in an earlier paper.1 <0.88 µg cm−2 week−1.
nickel-sensitised persons, often
referred to as ‘Nickel Allergy’.
2. Introduction 2.1. Chromium top coats
2 Once affected, further exposure to
nickel ions can cause repeated The authors’ previous studies1,3 evalu- Early work1 determined that a regular
nickel-allergic reactions, although ated non-nickel surface coatings that (conventional) chromium top coat
the symptoms will dissipate after would enable consumer products likely from a hexavalent electrolyte over a
removal of the source and the to come into direct and prolonged bright nickel deposit will prevent
outcome may vary greatly from one contact with skin to be safely placed nickel release when applied according
individual to another. on the market without fear of nickel to the relevant ISO specifications for
© 2019 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License (http://creativecommons.org/licenses/by-nc-nd/4.0/),
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TRANSACTIONS OF THE IMF 65
plating on metal and plastics sub- Table 1. Nickel release from bright nickel / flash gold electroplated copper discs.
strates.4,5 But given environmental Nickel release rate/
concern about the use of hexavalent Specimen Nickel deposit Flash gold Test µg cm−2 week−1 Result*
chromium electrolytes, the alternative A Bright Not plated 1 8.81 Fail
2 10.38
of chromium deposited from a trivalent 3 8.22
electrolyte was examined. These pro- B Bright Plated <0.1 µm 1 50.36 Fail
cesses are available as chloride and sul- 2 45.86
3 37.32
phate based proprietary electrolytes,
*Deemed to pass if Ni release rate is <0.88 µg cm−2 week−1 for articles under Clause 1c of the REACH
each with specific properties and oper- directive.
ating conditions. It was found that
microporous chromium deposited from Table 1 reports nickel release rates corrosion resistance. A thin, porous flash
a chloride trivalent electrolyte having (µg cm−2 week−1) for tests on samples deposit of gold <0.1 µm thick, being
10,000–20,000 or 50,000 pores cm−2 in triplicate of two specimens tested more noble than the bright nickel under-
with minimum local thickness of according to CEN methods EN coat, greatly accelerated the rate of nickel
0.30 µm, would prevent nickel release 12472:2005 + A1:2009 simulating wear release to 37–50 µg cm−2 week−1.
according to the CEN test methods.3 and corrosion, followed by EN
1811:2011 + A1:2015. These specimens
4. Nickel release from wearable
2.2. Coloured top coats were discs of copper with electrodepos-
articles
ited bright nickel, one without a
For wearable consumer items, coloured topcoat, and the other having a flash A selection of typical wearable articles
or clear topcoats are often applied coating of gold with thickness <0.1 µm. manufactured from base metals includ-
over bright nickel electrodeposits. Pre- The specimens with bright nickel ing wrought copper alloy, zinc based
vious work3 examined the following alone exhibited release rates of approxi- die castings and nickel-containing aus-
two methods of achieving this under mately 8 to 10 µg cm−2 week−1 and thus tenitic stainless steels, with a variety of
conditions that prevented Ni release. failed the tests badly. This is because the decorative top coats common in the
addition agents used to produce bright- industry were studied next. The
1 Electrophoretic top coats: Articles ness in the deposit, incorporate sulphur purpose was to determine those with
having a UV cured cathodic electro- into the deposit and greatly reduce base material and/or decorative
phoretic polyurethane coating
applied directly over a bright nickel Table 2. Nickel release from bright nickel/precious metal plated and alloyed articles.
deposit passed the nickel release Surface & Nickel release rate/
tests convincingly. Specimen Article Base Alloy Thickness /µm Test µg cm−2 week−1 Result*
2 Coloured PVD topcoats: The authors 1 Golden Zn base Cu56/Ni8/Au flash 1 1.86 Fail
bangle die casting 2 0.01 Pass
tested bright nickel with hexavalent 3 1.36 Fail
chromium plus a coloured PVD 2 Rose gold 60–40 brass Cu undercoat/ 1 0.01 Pass
topcoat of compositions giving the bangle 61%Au, 38%Cu 2 0.01
flash 3 0.01
following colours – blue, imitation containing 0.4%
rose gold, gunmetal, TiN gold colour, Ni
TiN with PVD Au + electroplated flash 3 Golden tag Zn base Cu25/Ni10/Pd0.3/ 1 < 0.01 Pass
die casting TiN0.2/Au flash 2 < 0.01
Au and finally, Cu-Au rose gold – as 3 < 0.01
used by manufacturers of costume 4 Golden link Zn base Cu25/Ni10/Pd0.3/ 1 < 0.01 Pass
jewellery and related consumer die casting TiN0.2/Au flash 2 0.17
3 0.02
articles. All passed the nickel release 5 Half disc Zn base Cu25/Ni5/Pd0.3/ 1 0.04 Pass
tests except the last mentioned, prob- die casting TiN0.2/Au flash 2 0.41
ably because that colour was achieved 2 0.04
6 Half disc Zn base Cu25/Ni10/Pd0.3/ 1 0.05 Pass
by deposition of gold–copper. die casting TiN0.2/Au flash 2 0.05
3 0.05
7 Half disc Zn base Cu25/NiP10/Pd0.3/ 1 0.05 Pass
3. Flash gold topcoat – die casting TiN0.2/Au flash 2 0.05
influence upon nickel release 3 0.03
8 Half disc Zn base Cu25/Ni10/Pd0.3/ 1 0.02 Pass
This study centred on costume jewellery die casting Au flash 2 0.02
3 0.02
items that are common wearable 9 Pendant Zn base Cu25/Ni10/Pd0.3 1 0.05 Pass
articles made from low-cost base die casting 2 0.01
metals, having a bright nickel deposit 3 0.03
10 Pendant Zn base Cu25/NiP10/Pd0.3/ 1 0.01 Pass
as the principal layer for base metal cor- die casting TiN0.2/Au flash 2 0.01
rosion protection, brightness and level- 3 0.01
ling, followed by a flash coating of 11 Gold alloy 76%Au-16% Not plated 1 0.24 Pass
disc Cu- 2 0.32
gold with thickness <0.1 µm. Such pro- 6%Ni-2%Zn 3 0.32
ducts may be the source of nickel ions Alloy
released when in direct and prolonged *Deemed to pass if Ni release rate is <0.88 µg cm−2 week−1 for articles under Clause 1c of the REACH direc-
contact with skin, causing nickel allergic tive.
Base alloy abbreviations: Wrought 60–40 brass; Zinc alloy base die casting.
contact dermatitis (NACD) in sensitised Flash gold deposit having thickness <0.1 μm; NiP is a proprietary electrodeposited coating of Ni with 6–10%
persons. P content.
66 C. M. WHITTINGTON AND W. Y. LO
(typically <0.1 µm thickness) as
common for wearable items such as
costume jewellery and watch cases.
(2) A variety of costume jewellery
pieces with precious metal surface
coatings passed the CEN nickel
release tests when an electrodepos-
ited palladium barrier coating was
applied, either as a top coat or an
Figure 1. Stainless steel watch cases, showing the reverse side of each specimen with blue masking paint
intermediate layer over bright
applied to the non-significant surfaces before testing for nickel release.1
nickel while a control specimen
Table 3. Nickel release from austenitic stainless steel articles. without such a barrier coating
Nickel release rate / failed the nickel release tests.
Specimen Base alloy Coating & Thickness1 Test µg cm−2week−1 Result* (3) A gold alloy containing 6% nickel
12 304 Stainless steel Not coated 1 0.01 Pass passed the tests.
2 0.00 (4) Watch cases as common examples
3 0.00
13 304 Stainless steel TiN 0.2 µm 1 0.01 Pass of wearable articles made of
2 0.00 nickel-containing stainless steel
3 0.01 Grades 304 (UNS S30400) and 316
14 316 Stainless steel Not coated 1 0.00 Pass
2 0.00 (UNS S31600) passed the CEN
3 0.00 nickel release tests convincingly.
15 316 Stainless steel TiN 0.2 µm 1 0.00 Pass (5) Previous work demonstrated non-
2 0.00
3 0.01 nickel top coats of regular hexava-
*Deemed to pass if Ni release rate is <0.88 µg cm−2 week−1 for articles under Clause 1c of the REACH lent chromium or micro-porous tri-
directive. valent chromium, will pass the CEN
nickel release tests.1,3
topcoats that prevent nickel release, 4.2. Nickel-containing austenitic (6) Similarly, a pore-free electrophoretic
versus those that failed the CEN tests. stainless steel articles coating over bright nickel also
passes. Such organic non-nickel top-
The nickel-containing austenitic watch
coats may be dyed to produce a
4.1. Bright nickel/precious metal cases shown in Figure 1 of Grades 304
variety of colours in the surface finish.
plated and alloyed articles (UN S304000) and 316 (UN S31600) were
(7) These studies show that nickel-con-
submitted to the normal CEN nickel
Table 2 gives nickel release test results taining decorative alloys such as
release tests, with nonsignificant surfaces
on the 11 bright nickel/precious metal stainless steel and gold plus bright
masked as shown, following the method-
plated and alloyed articles studied here. nickel plated articles with a non-
ology described in previous work.1
These showed: nickel barrier layer of electrodepos-
Table 3 shows these stainless steel
ited chromium, palladium or elec-
articles without any topcoat as well as
. A control article (Specimen 1) having trophoretic coatings will ensure
those with a PVD TiN coating of
a bright nickel electrodeposit plus the rate of nickel release does not
0.2 µm thickness, all passed the nickel
gold flash coating without a non- exceed 0.5 µg cm−2 week−1 for a
release tests convincingly.
nickel barrier layer, failed the nickel period of at least 2 years of normal
release tests. use. This enables such articles to
. A top coat of electroplated palladium 5. Conclusions be placed in the market.
deposited directly over bright nickel,
This study demonstrates that appropri-
acted as a barrier to prevent nickel
ate selection of materials and surface
release, having the same beneficial Disclosure statement
finishes for the manufacture of articles
effect as other non-nickel coatings,
which are likely to come into direct and No potential conflict of interest was reported by
including regular chromium depos- the authors.
prolonged contact with skin, can
ited from a hexavalent electrolyte
prevent corrosion of elemental nickel
and microporous trivalent chromium
by sweat in service, which may liberate References
with controlled pores described in
sufficient nickel ions to be absorbed
previous papers.1,3 1. C. M. Whittington, W. Y. Lo and M. Y. Yau:
through the skin and initiate an aller-
. An intermediate coating of electro- Trans. IMF, 2015, 93, 176–179.
genic effect commonly known as 2. D. R. Gabe and C. Larson: Trans. IMF, 2017,
deposited palladium prevented Ni
‘Nickel Allergy’. 95, 71–72.
release from a variety of wearable
In summary: 3. C. M. Whittington and W. Y. Lo: Trans. IMF,
articles studied here, including 2018, 96, 63–70.
those with bright nickel plus PVD (1) Electrodeposits of sulphur-contain- 4. ISO 1456:2009. Metallic and other inorganic
TiN and/or the same with a flash ing bright nickel will release nickel coatings – Electrodeposited coatings of
coating of gold. All passed the Ni ions at a rate exceeding acceptable nickel, nickel plus chromium, copper plus
nickel and of copper plus nickel plus
release tests comfortably. limits, when evaluated by the CEN
chromium.
. An unplated gold alloy containing test methods. This is accelerated 5. ISO 4525:2003. Metallic Coatings –
6% nickel (Specimen 11) passed the when a thin, porous flash top coat Electroplated coatings of nickel plus chro-
nickel release tests satisfactorily. of more noble gold is applied, mium on plastics materials.
