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Acta Biomaterialia 4 (2008) 680–685

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Anisotropy of nickel release and corrosion in austenitic stainless steels

a,*
L. Reclaru , H. Lüthy c, R. Ziegenhagen b, P.-Y. Eschler a, A. Blatter a

a
PX Holding S.A., R&D Department, Boulvard des Eplatures 42, CH-2304 La Chaux-de-Fonds, Switzerland
b
Cartier Horlogerie, Chemin des Aliziers, CH-2300 La Chaux-de-Fonds, Switzerland
c
School of Dentistry, Department of Dental Materials Science, University of Basel, CH-4056 Basel, Switzerland

Received 13 June 2007; received in revised form 11 October 2007; accepted 11 October 2007
Available online 20 November 2007

Abstract

The study of 316L-type stainless steel reveals a significant anisotropy of nickel release that is dependent on the orientation of the test
surface with respect to the casting and rolling direction. Cross-sectional specimens (transversal cuts with respect to the rolling direction)
show a substantially higher sensitivity to corrosion phenomena compared with longitudinal cuts and they release nickel ions at rates 10–
100 times higher. These findings indicate that orientation needs to be taken into account when interpreting test results, in particular when
comparing different grades of austenitic stainless steel, as well as in product and production design.
 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Nickel release; Austenitic stainless steel; 316L; Anisotropy; Orientation

1. Introduction 0.5 lg cm2 week1 for objects intended for permanent

Stainless steel, just like any other material destined for
medical applications, is subject to preclinical and biological
evaluations in order to ensure compliance with the specifi-
cations relating to patient safety. The preclinical evaluation
comprises, on the one hand, biological evaluations as
described in ISO 10993-1, along with physico-chemical
testing relating to localized corrosion and the release of
metallic cations on the other hand. Nickel ions are of par-
ticular interest in this respect since they may not only cause
biological effects [1,2], but are also at the origin of the most
widespread contact allergy.
Consumer products in contact with the body do not
underlie the regulations for medical devices. Yet the health
impact is confirmed: in Europe, 10–15% of adult females
and 1–3% of adult males are allergic to nickel [3–5], and
it is believed that the prevalence of nickel allergy is increas-
ing in the North American population [6,7].
It is for this reason that the European Directive 94/27/
EC was issued, limiting the rate of nickel release to
*
Corresponding author. Tel.: +41 32 924 02 90; fax: +41 32 924 02 10.
E-mail address: lucien.reclaru@pxgroup.com (L. Reclaru).
contact with the skin. Recently, a second Directive, 2004/
96/EC ‘‘Piercing in the Human Body’’, was issued, limiting
the rate of nickel release in this case to 0.2 lg cm2 week1.
We report here on a thorough assessment of nickel
release and corrosion of austenitic stainless steels com-
monly used in the domains of medical devices and objects
in contact with the skin. In particular, it is shown that the
release of nickel, driven by corrosion phenomena, is aniso-
tropic. Surfaces along the processing direction release sig-
nificantly less nickel and resist corrosion better than
surfaces transversal to this direction.
2. Materials and methods
The chemical compositions of the steel grades tested are
listed in Table 1. All these austenitic steels are based on the
316L standard, containing 12–15 wt.% nickel. Table 1 mer-
its a few comments.
Steel #1 is a specialty grade, very much used over the
past 25 years in watch-making (contact with skin). It is
basically a 316L matrix with increased sulfur content
(0.1–0.13 wt.%) for improved machining. The additional
sulfur forms MnS inclusions that lubricate the tool and

1742-7061/$ - see front matter  2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actbio.2007.10.008
 L. Reclaru et al. / Acta Biomaterialia 4 (2008) 680–685
Table 1
Codes and chemical compositions (wt.%) of the 316L-type stainless steels tested
Code DIN AISI/ASTM C Si Mn
#1 1.4427So – <0.03 <1 <2
#2 1.4441 F 138–97 <0.03 <1 <2
#3 1.4435 316L <0.03 <1 <2
#4 1.4435 316L <0.03 <1 <2
break the chip during machining, but also reduce the steel’s
resistance to pitting corrosion.
Steel #2 represents the 316L grade of highest corrosion
resistance. It refers to the medical grade (DIN 1.4441;
ASTM F138-97), for which a remelting process is added
to the standard metallurgy in order to enhance corrosion
resistance by reducing the inclusion content and notably
the sulfur concentration.
The grades #3 and #4 represent typical wire material on
the market, with defined sulfur content at about
0.02 wt.%.. The basic difference between these grades is
that #3 contains a substantial amount of calcium-alumi-
no-silicates whereas #4 does not.
2.1. Nickel release
The nickel release test performed is based on the EN
1811 standard ‘‘reference test method for release of nickel
from products intended to come into direct and prolonged
contact with the skin’’, but with more severe test conditions
in order to accelerate the nickel release. The following
quantitative results should therefore not be compared with
either the limit quoted in EN 1811 or other results obtained
under standard conditions. Artificial sweat was used with a
composition of NaCl 5 g l1, urea 1 g l1, racemic lactic
acid (90%) 940 lg l1, pH 4.5 (instead of pH 6.5 as speci-
fied in the standard). Extraction was carried out over 7
days at 37 C (instead of 30 C as per the standard) and
solution volume/sample area ratio was 1 ml cm2.
After 7 days, the samples were taken out of the artificial
sweat and the nickel released into the solution was ana-
lyzed by ICP-OES (Thermo-Optek PQ2+).
The samples for the release tests are 10 mm diameter cyl-
inders of various lengths so as to obtain transversal/longi-
tudinal area ratios (Strans/Slong) of 0.3, 0.7, 1 and 5. For
each ratio, a series of four samples is tested in order to
detect and discard apparent erroneous measurements.
Two series of tests are performed: (i) with samples
annealed and recrystallized at 1020 C, 60 min under
reducing H2 atmosphere; and (ii) with samples 23% cold
drawn to a diameter of 8.8 mm after recrystallization.
The as-prepared cylinder samples are then immersed
into the electrolyte for the extraction procedure. A mathe-
matical model as described below is applied to separate the
relative contributions from the transversal and longitudinal
faces, respectively, to the measured nickel release. We pre-
fer this approach rather than covering one face with a pro-
tective layer to extract the nickel from the other face for the
following reasons. Firstly, a perfect dielectric coating
681
P S Cr Mo Ni Others
<0.045 0.10–0.13 16.5–18.5 2.0– 2.7 12.0–14.0 N < 0.11
<0.025 0.002 17.0–19.0 2.5–3.2 13.0–15.5 Cu < 0.5
<0.045 0.020 17.0–18.5 2.5–3.0 12.5–15.0 N < 0.11
<0.045 0.018 17.0–18.5 2.5–3.0 12.5–15.0 N < 0.11
exempt of any porosity would be needed for such protec-
tion. Secondly, such a layer, at its edges, presents the risk
of initiating crevice corrosion at the sample–layer interface.
The possible localized corrosion (pitting and crevice) would
contribute to the nickel release in an uncontrolled manner.
2.2. Corrosion tests
Electrochemical measurements were carried out on a
PAR Model 273 A potentiostat, using a rotating electrode
at a speed of 300 rpm. The counter-electrode was made of
platinum and the reference electrode of saturated calomel
(SCE).
The electrolyte for the corrosion tests is the same artifi-
cial sweat as for the nickel release tests. It was de-aerated
with nitrogen in order to control the quantity of dissolved
oxygen during the test at a level of 0.2 mg l–1. The control
was performed with a Visocolor ECO Oxygen Test Kit
from Machery-Nagel Gmbh&Co KG, Germany.
Samples in the form of 10 mm disks are machined in such
a way that the test surface corresponds to either a transver-
sal or a longitudinal face with respect to the wire direction.
The samples are then immersed in the electrolyte for 16 h
before polarization curves were recorded in the potential
range from –1000 to +1000 mV vs. SCE with a scanning
rate of 0.25 mV s–1. Tafel slopes and corrosion current
(icorr) were calculated from curves recorded between
(±150 mV) vs. SCE with a scanning rate of 0.1 mV s–1 [8].
3. Results and discussion
3.1. Extraction results
The release of nickel depends on the shape of the sam-
ple. Thus, for sample #1 in the annealed condition, the
release increases from 3 to 10 lg cm2 week1 when going
from an Strans/Slong ratio of 0.3–5, and from 20 to
32 lg cm2 week1 when cold-drawn by 23%.
The results expressed in Table 2 reveal two phenomena:
– The degree of cold drawing significantly increases the
release of nickel, except for steel #2.
– The release of nickel also increases significantly when
the Strans/Slong ratio increases, except for steel #2.
Note that sample #2 is the medical grade, purified by
remelting. Its nickel release rate is so low (in fact, close
to the detection limit of OCP-OES) that measurement
uncertainty may mask the possible shape dependence.
682 L. Reclaru et al. / Acta Biomaterialia 4 (2008) 680–685

Table 2
Mean values and standard deviation of nickel release (lg cm2 week1) from four measurements at each (Strans/Slong) ratio
Sample Annealed (diameter = 1 cm) Ratio Strans/Slong Cold-worked 23% (diameter = 0.88 cm) Ratio Strans/Slong
0.3 0.7 1 5 0.3 0.7 1 5
# 1 3.1 ± 0.3 5.7 ± 1.0 5.2 ± 0.3 10.4 ± 1.5 19.6 ± 2.3 23.8 ± 4.3 25.1 ± 1.1 31.7 ± 0.6
# 2 0.18 ± 0.02 0.13 ± 0.01 0.14 ± 0.03 0.24 ± 0.05 0.16 ± 0.01 0.15 ± 0.03 0.10 ± 0.02 0.20 ± 0.06
# 3 0.15 ± 0.01 0.28 ± 0.01 0.26 ± 0.02 0.44 ± 0.10 3.81 ± 0.05 4.65 ± 0.43 5.42 ± 0.84 7.83 ± 0.37
# 4 0.22 ± 0.03 0.39 ± 0.04 0.59 ± 0.05 1.22 ± 0.05 2.28 ± 0.14 3.06 ± 0.18 3.41 ± 0.18 5.28 ± 0.05
The detection limit is close to 0.02 lg cm2 week1.

The measured release of nickel, C, is the sum of the 12

#1
release from the transversal, a, and longitudinal, b, faces,
#4 23%
i.e. C = a + b. On the hypothesis that the release of nickel 10
from one type of face is not influenced by the other type of #3 23%

Ni (ug/cm2/week)
face – in other words, the contributions to the nickel release 8
from transversal (Strans) and longitudinal (Slong) faces a and
b are independent – we can write 6

CS tot ¼ aS trans þ bS long

For cylindrical samples of diameter D and length L, this
gives
2 2
C½ðpD =2Þ þ ðpDLÞ ¼ aðpD Þ þ bpDLÞ
Whence
C ¼ ðaD þ 2bLÞ=ðD þ 2LÞ
With the help of the Mathematica 5.1 software (Wolfram
Research), the best curve is fitted to the data from Table
2 by adjusting parameters a and b (correlation coefficients
(R2) were between 0.98 and 0.99). The best estimates for a
and b are given in Table 3, and the fitted functions are
shown in Figs. 1 and 2 for samples with a rate of nickel re-
lease higher than 1 lg cm2 week1. Below this value, i.e.
for sample #2 as well as samples #3 and #4 in the annealed
condition, the rates are too close to the detection limit to
allow for a reliable estimate. Nonetheless, the measured
values in Table 2 clearly confirm the tendency for increas-
ing nickel release with increasing Strans/Slong ratio also for
the annealed samples #3 and #4.
Table 3 reveals that the contributions of the transversal
(a) and longitudinal (b) faces to the total nickel release (C)
are very different for the different samples (Fig. 1). Thus,
for sample #1, the transversal face releases
12 lg cm2 week1 while the longitudinal face releases
0.2 lg cm2 week1. Cold working significantly alters the
nickel release, too. Thus, for sample #1, the release from
4
2
0
0 2 4 6 8 10
Strans/Slong
Fig. 1. Nickel release of samples #1, #3 and #4. Shown are the measured
mean values (Table 2) together with the curves fitted according to the
model function (Table 2).
the transversal face (a) increases from 12 to
35 lg cm2 week1 and release from the longitudinal face
(b) increases from 0.2 to 16 lg cm2 week1 when going
from the annealed state to the 23% cold-worked state
(Fig. 2).
Since one can reasonably assume that the release of
nickel is related to some degradation process of the mate-
rial, it is interesting to study the corrosion behavior of these
steels.
3.2. Corrosion tests
Potentiodynamic curves were recorded for both faces
from 1000 to +1000 mV vs. SCE. By way of an example,
Fig. 3 displays the polarization curves for steel #3 in the
passive region to breakdown potential Ebd. Ebd is the

Table 3
Best estimates of the parameters a (transversal face) and b (longitudinal face) for the model of total nickel release C, C = (aD + 2bL)/(D+2L)
Sample Annealed (D = 10 mm) Cold-worked 23% (D = 8.8 mm)
Ratio Strans/Slong Ratio Strans/Slong
a b a b
#1 12.12 0.21 35.45 15.80
#3 N/A N/A 9.00 2.28
#4 N/A N/A 6.16 1.19
D: diameter of the sample cylinder, L: length of the sample cylinder, N/A: not applicable (see text).
 L. Reclaru et al. / Acta Biomaterialia 4 (2008) 680–685 683

40 Table 4
#1 Corrosion current density values icorr calculated from Tafel slopes as
derived from the polarization curves and breakdown potential Ebd
#1 23%
Sample Corrosion current density icorr Breakdown potential Ebd
30
(lA cm–2) (mV)
Ni (ug/cm2/week)

Transversal Longitudinal Transversal Longitudinal

20 #1 5.00 1.06 50 150

#2 0.06 0.02 300 515
#3 3.32 1.73 45 120
#4 4.26 1.61 154 210
10

Table 5
Coulometric zone analysis
0
0 2 4 6 8 10 Sample Ecorr300 mV (mC cm2) 300–600 mV (mC cm2)
Strans/Slong Transversal Longitudinal Transversal Longitudinal
#1 336 182 2660 2200
Fig. 2. Effect of cold working on nickel release for sample #1. According
#2 27 3 198 106
to the model function in Table 2.
#3 171 70 5719 1786
#4 43 31 1166 800
potential at which the anodic current increases sharply. It is
defined by ASTM as being ‘‘the least noble potential where to +300 mV, and the second zone, zone II from +300 to
pitting or crevice corrosion or both will initiate and prop- +600 mV. The areas under the polarization curves are inte-
agate’’ [9]. grated for each zone. The result is converted into charge
Table 4 lists the corrosion current density values (icorr) density units (mC cm–2) by division through the scan speed.
calculated from the Tafel slopes derived from the recorded Thus the obtained values (Table 5) reveal again that the
Tafel curves (±150 mV vs. SCE). icorr is representative of corrosion process is accelerated on the transversal face,
the degree of degradation of the alloy under the very test consistent with the other tests.
conditions. For the steels tested, icorr is always greater on
the transversal face than on the longitudinal face – in other 3.3. The role of inclusions
words, the corrosion process is accelerated on the transver-
sal face. Various authors have highlighted the influence of non-
Again it is found that for all samples the breakdown metallic inclusions in the localized corrosion process [11].
potential is lower for the transversal faces than for the lon- Discussions relate primarily to manganese sulfides (MnS),
gitudinal faces. which play a particularly detrimental role in this respect
Coulometric analysis provides a simple method for the [12–14]. In the present study, the re-sulfured grade #1 show
assessment of corrosion risk at lower potentials such as the highest inclusion content, and also the highest rates of
prevailing, e.g. in clinical situations [10]. It consists of corrosion and nickel release. By contrast, grade #2 shows
dividing the anodic polarization curves into two (somewhat the lowest sulfur and inclusion content, and also the lowest
arbitrary) zones, the first zone, zone I, extending from Ecorr rates of corrosion and nickel release. Grades #3 and #4 do

20
#3T #3L
Transversal
Current I/area (uA/cm2)

10

Longitudinal
0

breakdown potential

-200 -100 0 100 200

Potential E(mV)

Fig. 3. Potentiodynamic polarization curves on linear axes recorded on the longitudinal (L) and transversal (T) faces of sample #3. Arrows indicate the
position of the breakdown potential Ebd.
684 L. Reclaru et al. / Acta Biomaterialia 4 (2008) 680–685
Fig. 4. Optical micrograph of sample #1 after corrosion test showing the initiation of pitting at the MnS inclusion (·100). (a) Longitudinal face, showing
elongated pittings; and (b) transversal face, showing a higher density of pittings and of circular shape.
have inclusion content somewhat higher than grade #2, but
clearly have much lower MnS inclusions than grade #1.
Their corrosion and nickel release rates lie in-between those
of grades #1 and #2. The somewhat higher rates for #3 as
compared with #4 can also be explained by inclusion con-
tent: the particularity of grade #3 is the presence of a sig-
nificant number of calcium-alumino-silicates inclusions in
addition to the MnS inclusions, which are comparable
for the two grades.
Microscopic examination of the sample #1 after the
rotating electrode technique again reveals the anisotropic
sensitivity to corrosion: as seen in Fig. 4, the transversal
face exhibits a higher density of pittings as compared with
the longitudinal face.
With regard to inclusions, their shape is different on the
longitudinal and transversal faces. During wire processing,
soft inclusions like sulfides deform with the metal matrix
and hence are elongated into longitudinally oriented fibers.
Now Poyet et al. have previously studied the reactivity of
inclusions in terms of their contribution to the initiation
of pitting corrosion in austenitic stainless steel [15]. They
found not only that the reactivity depends on their chemi-
cal association, with MnS inclusions in the lead, but that
their shape also influences the corrosion behavior.
3.4. Anisotropy in wrought stainless steel
While the different total release of nickel and corrosion
of the various steel grades may be understood on the basis
of slightly different compositions and their distinct inclu-
sion content, these factors cannot explain the pronounced
anisotropic behavior observed. The anisotropic shape of
the soft MnS inclusions alone may not explain the phenom-
enon either, since anisotropy is also found in grades that
are apparently exempt of such inclusions (grade #2 in this
study). There are other types of anisotropy prevailing in
wrought steel.
Anisotropic corrosion in austenitic stainless steel has
previously been reported for the grades 304 [16], 304L
[17,18] and 316L [19].
It is reasonable to assume that the origin of such orien-
tation-dependence resides in some anisotropy of the mate-
rial. Continuous casting of steel billets produces a radial
anisotropic microstructure and segregation profile. The bil-
lets are then hot rolled into wires and solution annealed.
Wire material delivered in this condition therefore is theo-
retically free from segregations and with uniform micro-
structure. In the following fabrication process, the wire
usually undergoes further cold deformation and recrystalli-
zation processes.
Mechanical deformation like rolling or drawing, how-
ever, produces new anisotropy. On the one hand, it gen-
erates a crystallographic texture dependent on the
deformation mode and the crystal structure of the mate-
rial. In the case of austenite, cold drawing orients the
<1 1 0> and <1 1 1> directions of the face-centered cubic
crystallites parallel to the wire direction. The crystallo-
graphic texture is partly preserved upon subsequent
annealing, because the newly formed crystals nucleate in
an orientation matched with the prevailing texture. Now
physical and chemical properties, including corrosion
activity and hence nickel release, generally depend on
crystal orientation.
Cold forming also introduces microstructural defects
and internal stresses into the material that enhance the cor-
rosion activity and the associated nickel release.
4. Conclusion
The present study of various 316L-type stainless steel
wire materials reveals orientation-dependent corrosion
and associated release of nickel. The tests performed on
samples of different shapes show that the release of nickel
varies depending on the Strans/Slong ratio, and increases
with cold working. On the hypothesis that the nickel
release of each type of face is independent, a simple geo-
metric model makes it possible to extract the contributions
of the transversal and longitudinal faces. From this, it
emerges that the transversal face in general releases more
nickel than the longitudinal face.
 L. Reclaru et al. / Acta Biomaterialia 4 (2008) 680–685
This is true not only for cold-worked (and thus textured)
material, but also for material that has been properly solu-
tion-annealed and recrystallized. Several factors may con-
tribute to the anisotropic sensitivity. First, wrought
material always exhibits some degree of crystallographic
texture. The texture introduced during deformation pro-
cesses is not completely erased upon recrystallization,
because the new grains do not nucleate randomly, but in
an orientation matching the prevailing texture. Secondly,
steel is not a high-purity material but inevitably contains
some non-metallic inclusions that affect corrosion activity
and hence nickel release. Soft inclusions, like sulfides or sil-
icates, deform with the steel matrix, resulting in fibers elon-
gated in the longitudinal direction, while appearing as
round spots in a transverse cut.
References
[1] Kasprzak KS, Sunderman FW, Salnikov K. Nickel carcinogenesis.
Mutat Res 2003;533:67–97.
[2] Denkhaus E, Salnikov K. Nickel essentiality, toxicity and carcinoge-
nicity. Crit Rev Oncol/Hematol 2002;42:35–56.
[3] Nielsen NH, Menné T. Allergic contact sensitisation in an unselected
Danish population. The Glostrup allergy study, Denmark, Acta
Derm Venereol (Stockh) 1992;72:456–60.
[4] Liden C, Bruze M, Menné T. Metals. In: Rycroft RJG, Menné T,
Frosch PJ, Lepoittevin JP, editors. Textbook of contact dermatitis.
2nd ed. Heildelberg: Springer; 2001. p. 935–77.
[5] Meding B, Liden C, Berglind N. Self-diagnosed dermatitis in adults.
Results from a population survey in Stockholm, contact dermatitis
2001;45:341–5.
[6] Marks Jr JG, Belsito DV, DeLeo VA, Fowler Jr JF, Fransway AF,
Maibach HI, et al. North America contact dermatitis group, North
America contact dermatitis group patch-test results, 1998–2000. Am J
Cont Dermat 2003;14(2):59–62.
685
[7] Silveberg NB, Licht J, Friedler S, Sethi S, Laude TA. Nickel contact
hypersensitivity in children. Pediat Dermatol 2002;19(2):110–3.
[8] Standard practice for calculation of corrosion rates and related
information from electrochemical measurements G102-89. In annual
book of ASTM standard, vol. 03, Corrosion of metals; Wear and
erosion; 2007.
[9] Standard terminology relating to corrosion and corrosion testing
G15-07. In annual book of ASTM standard, vol. 03, Corrosion of
metals; Wear and erosion; 2007.
[10] Reclaru L, Meyer J-M. Zonal coulometric analysis of the corrosion
resistance of dental alloys. J Dent 1955;23:301–11.
[11] Lott SF, Alkire RC. The role of inclusions on initiation of crevice
corrosion of stainless steel. J Electrochem Soc 1989;136(4):973–9.
[12] Stewart J, Williams DE. The initiation of pitting corrosion on
austenitic stainless steel: on the role and importance of sulphide
inclusion. Corr Sci 1992;33(3):457–74.
[13] Eklund GS. Initiation of pitting at sulphide inclusions in stainless
steel.. J Electrochem Soc 1974;121(4):467–73.
[14] Wranglen G. Pitting and sulphide inclusions in steel. Corr Sci
1974;14:331–49.
[15] Poyet P, Desestret A, Coriou H, Grall L. Contribution à l’étude de la
corrosion par piqûres des aciers inoxydables du type 18–10. Influence
de divers facteurs sur le processus d’amorçage des piqûres, Mémoires
scientifiques, Revue métallurgie, février 1975; p. 133–45.
[16] Cigada A, Mazza B, Pedeferri P, Sinigaglia D. Influence of cold
working on critical pitting potential of AISI 316L and 304L
steels in an artificial physiological solution simulating the
aggressiveness of the human body. J Biomed Mater Res
1977;11:503–12.
[17] Manning E, Duquette DJ, Savage F. The effect of test method and
surface condition on pitting potential of single and duplex phase 304L
stainless steel. Corrosion 1979;35(4):151–7.
[18] Kumar R, Singh R, Mahato B, et al. Effect of texture on corrosion
behaviour of AISI 304L stainless steel. Mater Characteriz
2005;54(2):141–7.
[19] de Schiapparelli R, Caceres SP. Effect of the direction of the
inclusions on the tested surface on susceptibility to pitting corrosion
in stainless steels. J Mater Sci 1991;26:1454–8.