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A study of the effects of nickel release in alloy products

Cite this: Anal. Methods, 2013, 5, 2237
Feifei Xu,*ab Meirong Zhao,b Deng Hong,b Shilei Jiang,b Mingqing Chaib
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and Jingke Zhu*c

Because of nickel's high corrosion resistance and heat resistance, it is widely used in alloy products. It has
Received 18th December 2012
Accepted 4th March 2013
been shown that skin contact with these materials on a daily basis may cause nickel allergy. The objective of
this work is to investigate the effects of nickel release in alloy products. The results show that the amount of
DOI: 10.1039/c3ay26575g
nickel release was significantly affected by metal composition and interestingly, can be effectively
www.rsc.org/methods restrained by the addition of noble metals.

Introduction
Nickel is a metallic element naturally present in the Earth's
crust. Due to its unique physical and chemical properties,
nickel and nickel-based alloys are used in a wide variety of
products. However, it has been known for decades that adverse
skin reactions can be caused by skin contact with nickel. To
date, items made from nickel and nickel-based alloys e.g. coins,
jewellery, stainless steels, bra fasteners and eyeglass frames,
have become the most frequent causes of skin contact allergy in
Europe. Liden and Norberg1 reported that about 10–15% of
women and 2–4% of men in Europe were found to be allergic to
nickel. Double-blind placebo-controlled studies have shown
that nickel-allergic individuals, but not healthy individuals, may
develop hand dermatitis if they are repeatedly exposed to nickel
in low concentrations (10 ppm),2–4 or if they are orally exposed to
nickel.5
The wide spread of nickel allergy has become a driving force
to the development of a number of analysis methods and
regulations designed to reduce its prevalence. For instance, in
1994, Northern European countries introduced nickel regula-
tions aimed at the reduction of nickel exposure and prevention
of nickel allergy.6,7 The “94/27/EC”8 regulation prescribed a
nickel release rate of 0.5 mg cm
2 per week as an upper limit for
items to be in prolonged contact with the skin, and a maximum
content of 0.05 wt% nickel for piercing jewellery during
epithelialization. In addition, two corresponding test standards,
EN1811 (ref. 9) and EN12472 (ref. 10), were published in 1998.
In 2004, the European Union modied the requirement of the
nickel release of piercing jewellery and formulated a new
directive, “2004/96/EC”, which did not limit the use of nickel in
a
Yiwu Entry-Exit Inspection and Quarantine Bureau, 299 Chengbei Road, Yiwu
322000, P. R. China. E-mail: xufeizj@126.com; Fax: +86-0579-81579009; Tel: +86-
0579-81579085
b
Yiwu Academy of Science & Technology for Inspection & Quarantine, Yiwu, P. R. China
c
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China
jewellery materials, but required that nickel release rate must be
below 0.2 mg cm
2 per week.11 Other countries,12–17 such as
America and China, have also established corresponding regu-
lations on nickel release for jewellery.
In this work, we investigated the variation of nickel release
with different metal compositions and the inuence of different
immersing conditions to test nickel release. Herein, we report
that the nickel release rate is signicantly affected by metal
compositions, and noble metals (e.g. Au and Ag) play an
important role in restraining the nickel release in alloys. We
believe that this nding will have great importance in reducing
the prevalence of nickel allergy from the very rst step.
Experimental
Chemicals
Lactic acid, urea, nitric acid, sodium dodecylbenzene sulfate,
sodium chloride (analytical pure, commercial available), Nickel
Standard Solution (1000 mg L
1, analytical pure, NSI Company
of USA).
Degreasing solution: dissolved 5 g sodium dodecylbenzene
sulfate in 1000 mL deionised water.
Testing solution: mixed 900 mL deionised water, 100 g urea,
500 g sodium chloride and 100 g lactic acid together in a 1000
mL beaker with stirring until dissolved. The testing solution
should be prepared daily.
Apparatus
s20 pH meter, Mettler Toledo.
Inductively Coupled Plasma-Atomic Emission Spectrometry
(ICP-AES), Optima7300DV, PerkinElmer Company, USA.
Wb/ob Thermostat Water Bath, Memmert Company,
Germany.
Sample preparation
Cu, Zn and Ni powders were added, in weight proportion to the
intermediate frequency induction equipment. The mixture was

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Analytical Methods Paper

then melted under the protection of inert gases. The resulting P

n
di
liquid was poured into a rod graphite mould aer smelting. The
Test result d ¼ i¼1 ðn ¼ 6Þ
rods was cut into F 20  1.3 mm plate samples using spark n
cutting, and then polished smooth to thickness of 1.2 mm with
where, a represents the sample area of the test article (cm2), V
no. 400 diamond abrasive paper. Then the samples were
represents the release solution volume aer dilution (mL), and
washed with ethyl alcohol and dried over heated air.
C1 and C2 are the mean nickel concentration in the diluted
release solution and in the blank solutions aer immersing,
Release procedure respectively (mg L
1).
The samples were gently swirled for 2 min in the degreasing
solution at room temperature then rinsed thoroughly with Results and discussion
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deionised water and dried using an absorbing cloth. Aer

degreasing, the samples should be handled using plastic
forceps or clean protective gloves. Each sample was placed,
suspended by its holder, in the test vessel. The amount of
testing solution added corresponds to approximately 1 mL per
cm2 of sample area. The suspended sample area should be
totally immersed in the test solution. The vessels were properly
covered with a lid in order to prevent evaporation of the test
solution. The vessels were le in a thermostatically controlled
water bath without agitation for 168 h before being slowly
removed from the release solution. The release solution was
quantitatively transferred to an appropriately sized volumetric
ask, washed with dilute nitric acid. The different composition
samples were measured six times separately.
Conditions of ICP-AES
The testing solutions were directly injected into the ICP-AES.
ICP-AES parameters are referred to in EN1811, as listed in
Table 1.
The sample area is calculated using the equation:
a ¼ 2pr2 + 2prh
where a represents the surface(s) that is(are) immersed in the
test solution and not covered with a masking agent (cm2), and r
and h, however, are denoted as the radius and height of a
circular sample, respectively (cm).
Nickel release calculations
The nickel release of a sample, d, expressed in micrograms per
square centimeter per week (mg cm
2 per week), is given by the
equation:
ðC1
C2 Þ  V
d¼
a  1000
Effect of different metal composition
The metal compositions of samples are listed in Table 2. All
samples were handled according to the release procedure given
in the experimental section, with a bathing temperature of 30 
2  C, a bathing time of 168 h, and a pH value of 6.5. The results
of tests are shown in Table 2. With increasing nickel content,
the nickel release is signicantly increased (entry 1–5 and entry
7–11). Interestingly, the amount of nickel release is dramatically
reduced with an increase of Au in the alloys (Fig. 1). We
supposed that with the increasing content of nickel, the small
atomic weight of nickel can weaken the metallic bonding forces
and thus promote nickel release, whereas the addition of large
atomic weight noble metals like Au can strengthen the metallic
bonding forces and restrain the nickel release. In addition, the
release of nickel was noticeably restrained by silver (entry 1
and 6).
Effect of pH
The testing solution was adjusted separately to pH values of 6.2,
6.4, 6.5, 6.6, 6.8. No. 8 samples (listed in Table 2) were treated
according to the Release procedure separately at different pH,
with an immersing temperature of 30  C and an immersing
time of 168 h. The testing results are listed in Table 3. In Fig. 2,
it is shown that with the increase of pH value from 6.2 to 6.5, the
released nickel is signicantly increased, while continuing to
increase the pH value to 6.6 unexpectedly decreased the amount
of the nickel released. When the pH of the solution value was
increased to 6.8, the result was almost the same as for 6.6. This
demonstrates that a pH value of 6.5 is optimal for the nickel
release.
Table 2 Nickel release of samples in different metal compositions
Nickel release
Sample no. Au% Ag% Cu% Zn% Ni% (mg cm
2 per week)

Table 1 ICP-AES parameters 1 73.6 0 15.9 6.1 4.4 0.38

2 76.3 0 17.9 2.0 3.8 0.25
Item ICP-AES parameter 3 75.3 0 9.9 3.9 10.9 0.75
4 75.7 0 14.0 3.3 7.0 0.43
Power (kW) 1.30 5 75.1 0 15.5 3.0 6.4 0.36
Plasma ow (L min
1) 15.0 6 75.6 2.1 15.3 2.1 4.9 0.28
Nebulizer gas ow (L min
1) 0.80 7 0 0 73.8 23.6 2.6 1.02
Height of observation (mm) 10 8 0 0 75.1 19.5 5.4 2.9
Reading duration (s) 5 9 0 0 74.3 21.5 4.2 1.6
Reading time (s) 3 10 0 0 74.2 17.7 8.1 4.8
Auxiliary gas ow (L min
1) 0.20 11 0 0 73.2 16.0 10.8 6.7

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Fig. 2 Effect of pH.

Fig. 1 Comparing the nickel release from nickel alloys with Au and those
without Au.

0.02 mg cm
2 per week was found for a necklace (as shown
in Table 4).
Effect of immersing temperature
No. 8 samples (listed in Table 2) were treated according to the
Summary
standard release procedure at different immersing tempera-
tures, 20  C, 30  C, 38  C, with an immersing time of 168  2 h, EN1811 was applied to analyze the nickel release of different
at pH 6.5. The testing results are listed in Table 3. With compositions of alloys. The inuence of different immersing
increasing immersing time, the resulting released nickel is conditions to test nickel release were studied as well. It was
observably increased. shown that the nickel release rate is mainly inuenced by the
compositions of metals in the alloy. The addition of noble
metals which strengthen the inter-atomic forces can effectively
Effect of immersing time
restrain nickel release. The results showed that the nickel
The results of nickel release from No. 8 samples (listed in Table release increases drastically with increasing immersing
2) immersed in the testing solution for 96 h, 120 h, 168 h, 360 h, temperature. Considering that the inuence of the temperature
480 h, and 600 h are shown in Table 3. From Table 3 we could of the human body affects nickel release, detecting nickel
easily see that the amount of nickel release increased signi-
cantly with increasing duration of extraction with the testing
solution. The largest amount of nickel ions was released aer
Table 4 Results obtained for the nickel release from commercial samples
600 h of immersion in testing solution at 30  C.
Results (mg
Samples cm
2 per week)
Nickel release from commercial samples
Earring-1 1.74
Real commercial samples were analyzed using the developed
Earring-2 0.50
procedure and the concentrations were found to be 1.74 and Bracelet-1 0.06
0.50 mg cm
2 per week for two types of earrings, and 0.06 and Bracelet-2 0.01
0.01 mg cm
2 per week for two different types of bracelets, while Necklace 0.02

Table 3 Nickel release at different conditions

Effect of pH Effect of immersing temp. Effect of immersing time

Nickel release Nickel release Nickel release

pH (mg cm
2 per week) Temp. ( C) (mg cm
2 per week) Time (h) (mg cm
2 per week)

6.2 2.54 20 0.86 96 0.60

6.4 2.71 30 1.10 120 0.91
6.5 2.97 38 1.94 168 1.10
6.6 2.30 360 1.45
6.8 2.32 480 1.83
600 2.10

This journal is ª The Royal Society of Chemistry 2013 Anal. Methods, 2013, 5, 2237–2240 | 2239

Analytical Methods
release at 37  C is more reasonable than the requirement of
EN1811, at 30  2  C.
Acknowledgements
This work was supported by grants from the Certication and
Accreditation Administration of the People's Republic of China
(no. CNCA-2012-B07) and the Science Technology Department
of Zhejiang Province (2012C37009). We are grateful to Mr
Haiping Lin for technical advice.
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Notes and references
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3 C. Lidén, T. Menné and D. Burrows, Br. J. Dermatol., 1996,
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4 S. Sommer and S. M. Wilkinson, Contact Dermatitis, 2001, 44,
178–199.
5 C. S. Jensen, T. Menné and S. Lisby, Contact Dermatitis, 2003,
49, 124–132.
2240 | Anal. Methods, 2013, 5, 2237–2240
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Paper
6 C. Lidén, Contact Dermatitis, 1992, 26, 73–75.
7 T. Menné and K. Rasmussen, Contact Dermatitis, 1990, 23,
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8 European Communities, Off. J. Eur. Communities: Legis.,
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9 European Standard, EN 1811, 2011.
10 European Standard, EN 12472, 2005.
11 European Commission, Off. J. Eur. Communities: Legis., 2004,
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14 C. Lidén and S. Johnsson, Contact Dermatitis, 2001, 44, 7–12.
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