Materials Characterization 168 (2020) 110565

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Nanoscale characterization of corrosion mechanisms in advanced Zr/ZrxN T

and Zr/ZrxN+a-C:H nano-multilayer coatings for medical tools
⁎
L. Majora, , H. Krawiecb, J.M. Lacknerc, M. Dynerd, B. Grysakowskib, B. Majora
a
Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 30-059 Krakow, 25 Reymonta Street, Poland
b
AGH-University of Science and Technology, Faculty of Foundry Engineering, Reymonta 23 street, 30-059 Krakow, Poland
c
Joanneum Research–Materials, Institute for Surface Technologies and Photonics Forschungsgesellschaft mbH, Niklasdorf, Austria
d
CHIRMED-Manufacturer of Surgical and Medical Instruments, 8a Mstowska Street, 42-240 Rudniki, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: Bio-tribological multilayer PVD coatings deposited on stainless steel substrates have been studied on multiple
Protective multilayer coatings scales. Anodic dissolution as a precursor of the pitting corrosion mechanisms operating in layers was described.
Anodic dissolution Advanced Zr/ZrxN and Zr/ZrxN+a-C:H nano-multilayer coatings with different layer thickness ratios (metallic
Pitting corrosion to ceramic) were subjected to corrosion-resistant properties analysis. Materials protected by the Zr/Zr2N(1:4
Microstructure characterization
ratio) + a-C:H coating exhibited the lowest corrosion resistance in the test solution because of the corrosion
Corrosion mechanisms characterization
Biomedical analysis
behaviour of this coating was controlled by the defects content, while corrosion of coatings without additional a-
C:H layer was controlled by oxidation of the nitride to form an oxide over-layer.
Microstructure characterization was performed on the micro, nano and atomic scales using transmission
electron microscopy techniques. It allowed to described the differences of corrosion protection of applied dif-
ferent coatings. The possibility of the corrosion of metallic biomaterials and their contribution to biocompat-
ibility represents the most important consideration in the selection of metals for implants or surgical tools.

1. Introduction microcracks occur in coatings, which in consequence can lead to loca-

Metallic materials are the most widely used for biomaterials appli-
cation as well as for medical tools [1–4]. They are characterized by a
characteristic metallic bond which is responsible for elasticity, plasti-
city, toughness and stiffness [5]. This allows metals to adopt to various
bone plates, screws, nails or to different shapes of medical tools. One of
the main factors that limits the performance of metallic implants or
tools is the corrosion, particularly in physiological environment [6,7]. It
has been noted that the physiological environment may change dyna-
mically in pH and such change can have a significant influence on the
corrosion [2,3]. Therefore, a protective coatings are being used to solve
these problems [8–10]. Potential applications of coatings used in the
presented research results are for the protection of metallic medical
tools, like for example surgical tweezers with teeth enabling them to
grasp and manipulate tissues and fascia.
They have been produced by the use of a magnetron sputtering
technique [11]. The technique belongs to the physical vapour deposi-
tion methods (PVD). PVD it is a general term used to describe any of a
variety of methods to deposit thin solid films by condensation of the
vaporized form of a solid material onto various surfaces. Usually,
lized corrosion. The occurrence of local corrosion in coatings, especially
pitting corrosion, is a dangerous phenomenon because it leads to the
formation of small and deep holes in the material [6,7]. The presence of
local corrosion is usually much more difficult to diagnose than general
corrosion. In order to minimize the risk of imperfections in coatings in
the form of e.g. microcracks, in the framework of this study, the applied
protective coatings were in the form of a multilayer system where
ceramic and metallic layers were deposited sequentially [12–15].
Nanocrystalline multilayer coatings are characterized by excellent
physical, mechanical and chemical properties what opens a range of
new applications in advanced technologies. However, most of these
systems contain metallic layers that, similar to metallic substrates, can
be subjected to corrosion, in particular to pitting corrosion. Multilayer
coatings also allow corrosion process control.
Corrosion of metallic substrates has already been extensively de-
scribed in literature [16,17], however there is no microstructural de-
scription of pitting corrosion mechanisms amongst the layers them-
selves. In particular the formation of cracks in ceramic layers and the
occurrence of pitting corrosion in metallic layers. Research, the results
of which are presented in the paper, were aimed at explaining the

⁎
Corresponding author.
E-mail address: l.major@imim.pl (L. Major).

https://doi.org/10.1016/j.matchar.2020.110565
Received 21 February 2020; Received in revised form 28 July 2020; Accepted 9 August 2020
Available online 13 August 2020
1044-5803/ © 2020 Elsevier Inc. All rights reserved.
L. Major, et al. Materials Characterization 168 (2020) 110565

corrosion mechanisms of advanced protective multilayer coatings. They

have been described on the micro, nano and atomic scales by the ap-
plication of transmission electron microscopy techniques. The release of
corrosion products and corrosion current flow, especially during cor-
rosion process of elements used in medicine like implants or tools, can
cause inflammation, allergic reactions, local necrosis and many other
health problems.
In addition to the analysis of corrosion mechanisms (in particular
bio-corrosion), the research was also focused on the analysis of cyto-
toxicity (cell necrosis) of corrosion products.

2. Materials and methods

2.1. Coating deposition

In this study, the corrosion mechanisms in multilayer Zr/ZrxN

coatings with different phase ratios were characterized. To enhance the
mechanical properties, especially hardness and wear resistance, on
some of the coatings, an additional hydrogenated amorphous carbon (a-
C:H) outer layer was applied. Generally, a-C:H films have been at-
tracting attention due to their high hardness, low friction coefficient,
and high wear resistance [18,19], and because of the inert influence on
biological tissues, it also has many biomedical applications [20].
Magnetron sputtering with high purity zirconium targets was used for
coating deposition. Zr/ZrxN multilayers were deposited using a Zr
target and in alternating non-reactive and reactive gas flows. Zr layers
were deposited in the non-reactive (argon) gas flow, while ceramic ZrxN
layers were deposited in the reactive (nitrogen) flow. Stainless steel
(316 L) was used as the substrate material. All substrates were cleaned
before coating deposition in an industrial washing machine with sur-
factant-based washing agents to remove contaminants from the surface.
Next, the substrates were inserted into a vacuum chamber (Leybold
Univex 450) under laminar flow conditions in order to prevent dust
contamination on the substrate surfaces. Initially, a pre-treatment
method was used to remove the oxide layer from the substrate surfaces
by neutralized plasma of an anode layer ion source (ALS 340, Veeco)
[11]. After the preparation stage, ~2300 nm thick coatings were de-
posited by a pulsed DC sputtering technique. The deposition process
began at room temperature and ultimately reached a substrate tem-
perature of 40 °C. Homogeneity in the chemical composition and
coating thickness were achieved by rotating the substrates in the
chamber. The coatings were deposited at JOANNEUM RESEA-
RCH-Materials, Institute for Surface Technologies and Photonics, Nik-
lasdorf, Austria.
2.2. Corrosion testing
Corrosion resistance tests were performed using a classical three-
electrode corrosion cell. The following electrodes were used: working
electrode (sample), reference electrode (silver chloride electrode-Ag/
AgCl (saturated KCl)) and counter electrode (platinum mesh). To de-
termine the corrosion resistance of the coatings, the polarization curves
were plotted, and the evolution of the open circuit potential (OCP) for
each specimen was monitored for 24 h in Ringer's solution. The po-
larization curves were performed using the linear sweep voltammetry
(LSV) technique. The curves were determined in the potential range
from −1000 to +500 mV vs. the Ag/AgCl (saturated KCl) electrode.
The potential scanning rate was 1 mV/s. The corrosion tests were
performed in Ringer's solution (pH = 7.20 ± 0.02) at 37 °C, simu-
lating human body fluids. The Autolab model PGStat128 potentiostat
was used for the corrosion tests. The corrosion tests were conducted
with free access to oxygen from the air.
2.3. Biological testing
The potential cytotoxic effect was determined according to the ISO
Fig. 1. Corrosion testing was performed in Ringer's solution at a temperature
(T) of 37 °C; a) potentiodynamic polarization curves with a potential scan rate
of 1 mV/s; and b) the evolution of open circuit potential over time.
10993-5:2009 “Biological evaluation of medical devices – Part 5: Tests
for in vitro cytotoxicity” standards. Samples with diameters of 14.4 mm
were placed in medium for human fibroblast cell culture, supplemented
with FBS and were incubated at 37 °C for 48 h with shaking. Then, the
50% extracts, obtained from sample incubation, were added to 70%
confluent human fibroblast cell cultures (NHDF, Lonza Ltd.) and were
incubated for 48 h at 37 °C. Next, the cells were stained by MitoTracker
and propidium iodide (PI) in order to distinguish live/dead cells.
Extracts from the samples were analysed in comparison with control
cultures. Images were acquired with an AxioObserver Z1 inverted mi-
croscope equipped with a camera and quantified using AxioVision 4.6
software (Carl Zeiss MicroImaging). A statistical analysis (one-way
ANOVA and Tukey's post hoc test; a P-value less than 0.05 was con-
sidered statistically significant using Statistica 10.0 PL software) was
performed on five replicates from each treatment group.
2.4. Microstructural characterization
Microstructural characterization of pitting corrosion mechanisms in
the multilayer coatings was conducted using scanning and transmission
electron microscopy techniques (SEM and TEM) on QUANTA 200 3D
and TECNAI G2 F20 FEG (200 kV) microscopes, respectively. TEM
characterization was performed on cross-sections of coatings using
bright field (TEM BF), scanning-transmission (STEM) and high-resolu-
tion (HRTEM) TEM techniques. Phase analysis was conducted by the
application of the selected area electron diffraction pattern (SAEDP) as
well as HRTEM methods. The qualitative and quantitative chemical
composition was evaluated by energy dispersive X-ray spectroscopy
(EDS). The analysis was conducted along a specified line (line-scan) of a
selected area (results were obtained in the form of maps of the selected
element distribution) and from selected points (mainly for quantitative
analysis). The microstructural characterization of coatings required a

2
L. Major, et al. Materials Characterization 168 (2020) 110565

Fig. 2. Topographical SEM images of multilayer coatings showing several regions with visible preferential dissolution a). an image of the Zr/Zr2N (1:1 ratio)
multilayer coating; b). an image of the Zr/Zr2N (1:2 ratio) multilayer coating; c). an image of the Zr/Zr2N (1:4 ratio) multilayer coating.
and d). an image of the Zr/Zr2N (1:4 ratio) + a-C:H multilayer coating with visible pitting corrosion.

Fig. 3. A cross-section image showing the anodic dissolution in the Zr/Zr2N (1:1 ratio) multilayer coating performed by TEM; a) TEM BF image; and b) STEM image.

thin foil preparation (to make materials transparent for the electron
beam). Thin foils were prepared using a focused ion beam technique
(FIB) equipped with an in situ OmniProbe lift-out system on a QUANTA
200 3D dual beam microscope. It allowed for the acquisition of mi-
crostructural information from a precise region of interest. This was
crucial for the microstructural and pitting corrosion mechanism ana-
lyses of the coatings after corrosion testing. The foils were prepared
from selected regions of the coating.
All microstructural characterizations by TEM were performed at the
Institute of Metallurgy and Materials Science, Polish Academy of
Sciences, Cracow, Poland.
3. Results and discussion
The potentiodynamic polarization curves showed that the tested
coatings and the uncoated substrate (316L stainless steel) exhibited
pitting corrosion in Ringer's solution (Fig. 1(a)). An increase of the
anodic current density at potentials above 0 mV vs. Ag/AgCl (3 M KCl)
informed about pits formation on the surface of the coatings and un-
coated material. Regarding the cathodic part of curves, the highest
current values were noticed for the uncoated substrate. The coated
materials exhibited lower currents in the cathodic region, what in-
formed that the cathodic reaction (oxygen reduction reaction (1)) was
difficult.
O2 + 2H2 O + 4e → 4OH− (1)
Critical pitting potentials are usually characterized from anodic
polarization curves. Potentiostatic technique is the most reliable ap-
proach in which a constant potential is applied, and the current is re-
corded as a function of time. At electrode potentials below the pitting
potential, the current increases with time as corrosion pits initiate and

3
L. Major, et al.
Fig. 4. Anodic dissolution mechanism of the Zr/Zr2N (1:1 ratio) multilayer coating determined by using the STEM image.
Fig. 5. Qualitative chemical analysis of the Zr/Zr2N (1:1 ratio) multilayer
coating that was conducted in the region of anodic dissolution by EDS; a) STEM
image marked with the region of analysis; and b) maps of selected element
distribution.
grow. At potentials sufficiently beyond the pitting potential, the anodic
current sometimes increases to a limit value. This is because the current
within the propagation pit becomes diffusion-limited due to the for-
mation of a concentrated solution within the pit [6]. The polarization
curves in the anodic area for the uncoated steel as well as for the ma-
terials with protective coatings were very similar. These curves ex-
hibited a wide passive range from −0.2 V up to 0.2 V vs. Ag/AgCl (3 M
KCl) (Fig. 1(a)). At potentials above 0.2 V vs. the Ag/AgCl electrode, a
sudden increase in the anodic current density was noticed, and a
breakdown in the passive film was observed. The current density in the
passive range for the uncoated 316 L steel was approximately 2 μA/
cm2, while for the coated materials, it was approximately 0.4 μA/cm2.
Relatively low values of the anodic current density confirmed the for-
mation of an oxide layer at the specimen surface. First information for
4
Materials Characterization 168 (2020) 110565
three-dimensional oxide film was described in the 1920s in literature by
U.R. Evans [21]. The breakdown potentials of coated materials reached
almost equivalent or lower values than the uncoated material
(Fig. 1(a)). An exception to these results was the polarization curve,
which was measured for the material coated with the Zr/Zr2N (1:4
ratio) + a-C:H coating (blue curve, Fig. 1(a)), where it was possible to
observe a continuous increase of the anodic current density without a
pronounced passive area. It indicated that the material coated with Zr/
Zr2N (1:4 ratio) + a-C:H exhibited the lowest corrosion resistance in
the test solution.
The lowest anodic current density in the passive domain was found
for materials coated with Zr/Zr2N (1:1 ratio, yellow curve), Zr/Zr2N
(1:2 ratio, red curve) and Zr/Zr2N (1:4 ratio, green curve). The highest
value of breakdown potential that was measured for the material coated
with Zr/Zr2N (1:2 ratio) indicated that the coating was less prone to
pitting corrosion than the other materials (red curve on Fig. 1(a)).
Fig. 1(b) shows the evolution of the open circuit potential (OCP)
that was measured for 24 h in Ringer's solution. The samples protected
by the Zr/Zr2N (1:1 ratio), Zr/Zr2N (1:2 ratio) and Zr/Zr2N (1:4 ratio)
coatings showed similar corrosion resistance in Ringer's solution. The
open circuit potentials that were measured for materials coated with
Zr/Zr2N (1:4 ratio) + a-C:H showed very high potential oscillations
(~150 mV amplitude). Within 24 h, it was impossible to achieve a
stationary state, i.e., a stable value. These results suggested that the
material covered with this coating exhibited the worst corrosion re-
sistance in the Ringer's solution environment. The reason is that the
corrosion behaviour of Zr2N in coatings without additional a-C:H top
layer, was controlled by oxidation of the nitride to form an oxide over-
layer, whereas the corrosion behaviour of the coating with additional a-
C:H top layer was controlled by the defects content of the coating [22].
The OCP measured for the uncoated material did not reach a stable
value (black curve, Fig. 1(b)). The following OCP values after 24 h of
exposure of specimens in Ringer's solution were obtained: 40 mV,
−4 mV, 30 mV, and 68 mV for Zr/Zr2N (1:1 ratio), Zr/Zr2N (1:2 ratio),
Zr/Zr2N (1:4 ratio) and the uncoated substrate, respectively. The evo-
lution of open circuit potential measurements and potentiodynamic
polarization curves indicated that the best corrosion resistance in
Ringer's solution was found for the coating Zr/Zr2N (1:2 ratio). How-
ever, the coatings Zr/Zr2N (1:1 ratio) and Zr/Zr2N (1:4 ratio) were
characterized by similar corrosion resistance. The lowest value of the
passive current and the highest breakdown potential were measured for
the Zr/Zr2N (1:2 ratio) coating, red curve (Fig. 1(a)). The worst cor-
rosion resistance was demonstrated for the Zr/Zr2N (1:4 ratio) + a-C:H
L. Major, et al. Materials Characterization 168 (2020) 110565

Fig. 6. Microstructural characterization and chemical analysis of the corrosion products by TEM; a) TEM BF image; b) STEM image with marked places of chemical
EDS analysis; c). diagram of the qualitative point chemical analysis; d). maps of selected elements distribution .

Fig. 7. A cross-section image showing pitting corrosion in the Zr/Zr2N (1:4 ratio) multilayer coating performed by TEM; a) TEM BF image; and b) higher magni-
fication of the image shown in a).

coating. Considering the anodic branch of the LSV curve, the Zr/Zr2N
(1:4 ratio) + a-C:H coating underwent active dissolution (blue curve,
Fig. 1(a)), whereas the OCP exhibited very high oscillation (blue curve,
Fig. 1(b)). These results confirmed that the surface of the Zr/Zr2N (ratio
1:4) + a-C:H coating is not stable and easily undergoes active
dissolution. A sharp increase of the anodic current density at potentials
above 0 mV vs. Ag/AgCl (3 M KCl) was related with the dissolution of
the coatings and uncoated steel. The SEM images performed on the
specimens surfaces of Zr/Zr2N (1:1 ratio), Zr/Zr2N (1:4 ratio) and Zr/
Zr2N (1:4 ratio) + a-C:H multilayers after polarization curves have

5
L. Major, et al. Materials Characterization 168 (2020) 110565

Fig. 8. Qualitative chemical analysis of the Zr/Zr2N (1:4 ratio) multilayer coating conducted in the anodic dissolution region by EDS; a) STEM images marked with
the regions of analysis; b). maps of selected element distribution.

Fig. 9. A cross-section image showing pitting corrosion as a consequence of the anodic dissolution of the Zr/Zr2N (1:4 ratio) multilayer coating with a-C:H top-layer
coating performed by TEM.

6
L. Major, et al. Materials Characterization 168 (2020) 110565

Fig. 10. Higher magnification than presented on Fig. 9 of the pitting corrosion mechanism of the Zr/Zr2N (1:4 ratio) multilayer coating with a-C:H top-layer coating
by using a TEM BF technique presented the penetration channels through a-C:H layer; a). TEM BF image with the zoom marker of 500 nm; b). TEM BF image with the
zoom marker of 100 nm, more concentrated on the penetration channels in Zr2N layer; c). TEM BF image with the zoom marker of 100 nm, more concentrated on the
penetration channels in a-C:H layer.

Fig. 11. Pitting corrosion mechanism of the Zr/Zr2N (1:4 ratio) multilayer coatingwith a-C:H top-layer coating demonstrated by using an HRTEM image; a). TEM BF
image showing the enlarged cracks in Zr2N layer; b). HRTEM image showing cleavaged nano-fragments of the Zr2N layer; c). HRTEM image showing formation of Ca
layer in Zr2N cracks as a remain of the Ringer solution interaction.

7
L. Major, et al.
Fig. 12. Qualitative chemical analysis of the Zr/Zr2N (1:4 ratio) multilayer coating with a-C:H top-layer coating performed on pitting corrosion region by EDS; a)
STEM image with the marked region of analysis; and b) maps of selected element distribution.
revealed the structural dissolution and pitting corrosion of the coatings
(Fig. 2). Structural defects are usually areas of corrosion initiation
[23–25]. For example, microcracks in ceramic layers can form channels
for the corrosive media penetration to reach the metallic layers or
metallic substrate and to start the corrosion process. In the corrosion
test the Ringer solution was used which contain the aggressive Cl− ions.
Studying potentiodynamic polarization curves it has been observed
wide passive potentials range. The presence of chloride ions at the
surface caused the breakdown of passive layer. Destruction of the
passive layer accelerated the corrosion of the coating (in particular
metallic layers) caused a sharp increase in the current density visible at
the polarization curves at the potentials values above 0.2 V, Fig. 1(a).
Formation of the pits caused deep and narrow holes into the coating.
Considering the Zr/Zr2N (1:1 ratio) coating, the precursors for pitting
corrosion were the regions where preferential anodic dissolution was
observed. Considering the Zr/Zr2N (1:2 ratio), Zr/Zr2N (1:4 ratio) and
Zr/Zr2N (1:4 ratio) + a-C:H coatings, it has been noticed that their
topographies were similar to each other. The anodic dissolution was not
so essential in comparison to the pits observed in the Zr/Zr2N (1:1 ratio)
coating. Furthermore as a consequence of anodic dissolution the pitting
corrosion of the Zr/Zr2N (1:2 ratio) and Zr/Zr2N (1:4 ratio) + a-C:H
coatings surfaces was observed. Relying on the SEM images of surfaces
topography, it has been assumed that the anodic dissolution process
was the most intense for the Zr/Zr2N (1:1 ratio) coating. The TEM
characterization was performed in order to characterize the cross-sec-
tions of these defects and to describe anodic dissolution mechanisms in
the particular multilayer coatings. A thin foil was prepared from a
precisely defined region on the Zr/Zr2N (1:1 ratio) coating surface, i.e.,
regions where anodic dissolution was observed.
The microstructure was analysed in TEM BF and STEM modes
(Fig. 3). Anodic dissolution areas had a triangular shape looking in the
8
Materials Characterization 168 (2020) 110565
cross-sections. In the dissolution process, during the interaction of
corrosive fluid (Ringer solution), aggressive chloride ions (Cl−) ad-
sorbed on the coating surface and then formed surface complexes with
the coating, which led to localized dissolution and thinning of the
coating. The mechanism of Cl− transport has been described by Bockris
and co-workers, who suggested that chloride ions migrate through lo-
calized channels in hydrous oxide films [26,27]. A similar mechanism
may be suggested to dissolution processes in individual metallic layers
of protective multilayer systems, which has been suggested and applied
to the results reported in this study. It has been noticed that a relatively
high amount of cracks appeared in the ceramic Zr2N top-layer (Fig. 4).
Cracks have become an easy way to penetrate chloride ions. The ions
went through cracks in the first ceramic top layer to the metallic layer
that was situated directly underneath. The chloride ions permeation to
the metallic layer through the cracks initiated an anodic reaction in the
metallic layer (Fig. 4). Consequently the dissolution of zirconium from
the zirconium layer through Zr2N cracks occurred (as shown on the
image in Fig. 4). The anodic reaction was not homogenous in the Zr
layer. It was directly connected with the size of cracks formed in the
Zr2N top-layer. As a result of the anodic reaction, portions of the Zr
layer were completely removed. In these regions, the outer ceramic
layer had a contact with the underlying ceramic layer (Fig. 4). To prove
this phenomenon, a qualitative chemical analysis was performed from
the selected region on the cross-section of the coating (Fig. 5a). The
map of the nitrogen distribution clearly showed a fragment of the outer
ceramic layer having a contact with the underlying ceramic layer
(Fig. 5b). Corrosion products were formed on the coating surface as a
consequence of chipping of the outer ceramic layer and an anodic re-
action in the metallic layer (Fig. 6). Qualitative point analysis of the
chemical composition performed by EDS technique showed presence of:
Zr, O, C, N, Cl, Na, Fe (Fig. 6b,c). Zr and N came from the coating, Fe
L. Major, et al.
Fig. 13. Analysis of cytotoxicity of the corrosive fluids following corrosion testing; a). a diagram of the cell viability in relation to the type of corrosive fluid following
corrosion testing; and b) images of cells acquired by confocal microscopy.
came from the substrate, Cl and Na came from the corrosive fluid. The
unmarked peaks in the diagram refer to gallium, which is used for FIB
thin film preparation for TEM analysis. Therefore, it is an artefact that
always occurs during such a preparation. Qualitative analysis of the
chemical composition was also carried out in the appropriate area,
including a fragment of the coating and corrosion products (Fig. 6b,d).
The analysis area has been marked on the STEM image. The results of
the analysis confirmed the presence of O, Na, Cl as well as Fe in the
corrosion products.
An increased ratio of ceramic to metallic layers (1:4), caused a
different anodic dissolution process caused by corrosive fluid interac-
tions (Fig. 2b). Similar to the coating with a 1:1 ratio, the Cl− ions
penetrated through cracks in the ceramic to thin metallic layers which
were removed because of the anodic reaction. This was observed in the
TEM BF image (Fig. 7). Voids in the ceramic layers caused by this effect
are presented in the image. The depth of exposure to the corrosive fluid
is indicated on the image (Fig. 7a). The presence of the anodic reaction
in metallic layers was presented by qualitative chemical analysis per-
formed by EDS (Fig. 8). The distribution of the Cl and Na elements in
the coatings were considered because of the presence of these elements
in the corrosive fluid which was used in the experiment (Ringer solu-
tion). The Cl elements were uniformly distributed in ceramic layers,
while the Na distribution showed locally increased content of this
9
Materials Characterization 168 (2020) 110565
element in the metallic layers in regions containing large cracks and
voids in the ceramic layers. This confirmed the anodic reaction in Zr
thin layers. The content of corrosive fluid elements decreased with in-
creasing distance from the surface of the coating. It showed that the
anodic reaction of the metallic layers was weaker with the distance
from the surface of the coating. The application of amorphous carbon
(a-C:H) as a top-layer improved the tribological properties of the Zr/
Zr2N (1:4 ratio) multilayer coating. a-C:H is characterized by high
hardness and wear resistance, which is associated with a low friction
coefficient [19]. The application of a-C:H also influenced the change in
the pitting corrosion mechanism (Figs. 2c and 9). The SAEDP confirmed
the fully amorphous structure of the carbon top layer. Two blurred rings
around the main spot informed about the amorphous character of the
material. The amorphous structure generally is characterized by a lack
of long-range atomic order and the relatively low density that allowed
the penetration of Cl− through the carbon top layer (Fig. 10). The
corrosive fluid formed channels in the a-C:H structure. Penetration of
the corrosive fluid through carbon channels caused localized con-
centrations of the corrosive fluid on the first layer of the inner part of
the coating (Fig. 10). Subsequently, the corrosive fluid entered into
microcracks (which are typical for ceramic layers produced by PVD).
This caused the microcracks to be enlarged by chipping off fragments of
the ceramic layer (Fig. 11). Consequently, the first ceramic Zr2N layer
L. Major, et al.
of the inner part of the coating had a comb-like structure (Fig. 10). After
the corrosive fluid reached the first Zr metallic layer of the inner part of
the coating, the anodic reaction began. The dissolution of zirconium
from the Zr layer was also through enlarged cracks in the first layer of
Zr2N in the opposite direction of the flow of corrosive liquid (Fig. 10).
The zirconium content in the carbon layer was confirmed by EDS
qualitative chemical analysis (Fig. 12). A very important aspect was
also the interaction of the artificial element with the biological en-
vironment. The analysis was done by the biological characterization of
corrosive fluids after corrosion testing where the materials protected by
coatings were tested. Commercially available fibroblast cells to eval-
uate cytotoxicity was performed. For most of the analysed corrosive
fluids after corrosion testing, cell viability was at a similar level and
exceeded 90%. For the corrosive fluid obtained from corrosion testing
of the Zr/Zr2N (1:4 ratio) multilayer coating, significantly reduced cell
viability (Fig. 13).
4. Summary
In the frame of the presented paper the corrosion and biological test
results and the subsequent detailed microstructural characterization by
TEM of the coatings, as-deposited and after the corrosion process, have
been presented. Corrosion experiments indicated the pitting corrosion
of the tested coatings and the uncoated substrate (316 L steel) in
Ringer's solution. Materials coated with the Zr/Zr2N (1:4 ratio) + a-C:H
coating exhibited the lowest corrosion resistance in the test solution
because of the corrosion behaviour of this coating was controlled by the
defects content, while corrosion of coatings without additional a-C:H
layer was controlled by oxidation of the nitride to form an oxide over-
layer. As a result of anodic reactions in the Zr/Zr2N (1:1 ratio) coating,
portions of the Zr layer were completely removed. In these regions, the
breakdown of the outer ceramic layer occurred, and fragments of the
outer ceramic layer were in contact with the underlying ceramic layer.
The use of a greater amount of the ceramic phase, i.e., an increased
ratio of ceramic to metallic layers (1:4), caused the ceramic phase to be
crushed and removed leading to the decrease in its density, and voids in
the ceramic layers were observed. Due to the multi-layered nature of
the Zr/Zr2N (1:4 ratio) coating, the influence of aggressive corrosive
liquids, in particular, the Cl− ions, on both metallic and ceramic layers
diminished with increasing distance from the surface. To improve tri-
bological properties, the application of an amorphous carbon top-layer
(a-C:H) on the Zr/Zr2N (1:4 ratio) coating was tested, and it contributed
to a complete change in the anodic dissolution mechanism and di-
minished the corrosion resistance. The corrosive fluid formed channels
in the a-C:H structure leading to permeation of the fluid into the inner
portion of the coating, i.e., the Zr/Zr2N (1:4 ratio) multilayer coating.
The permeation of the corrosive fluid through carbon channels caused
localized concentration of the corrosive fluid on the first layer of the
inner part of the Zr2N coating. Biocompatibility analysis was performed
using commercially available fibroblast cells and showed that the cor-
rosive fluid obtained from corrosion testing of the Zr/Zr2N (1:4 ratio)
multilayer coating demonstrated significantly reduced cell viability,
which confirmed the corrosion test results as well as the qualitative
chemical analysis of corrosive fluids after the corrosion experiment.
Declaration of competing interest
I declare that all co-authors have been informed. Everyone partici-
pated in the development of the manuscript and there are no conflicts of
interest.
Acknowledgments
This work was supported by the:
10
Materials Characterization 168 (2020) 110565
- the National Science Center (pol. NCN) No: 2015/19/B/ST8/00942
- National Center of Research and Development (pol. NCBR) No:
DZP/M-ERA.NET-2015/285/2016
- Funds for statutory research implemented in the Institute of
Metallurgy and Materials Science Polish Academy of Sciences
- Austrian Research Promotion Agency (FFG) in the frame of M.ERA-
NET
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