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Surface & Coatings Technology 202 (2008) 2384 2388

www.elsevier.com/locate/surfcoat

Structural, mechanical and corrosion properties of TiOxNy/ZrOxNy

multilayer coatings
M. Balaceanu a,, V. Braic a , M. Braic a , A. Kiss a , C.N. Zoita a , A. Vladescu a , P. Drob b ,
C. Vasilescu b , D. Dudu c , O. Muresanu c
a
National Institute for Optoelectronics, Magurele - Bucharest, RO 77125, Romania
Institute of Physical Chemistry I.G.Murgulescu, Romanian Academy, Bucharest, RO 60021, Romania
National Institute for Physics and Nuclear Engineering Horia Hulubei, Magurele - Bucharest, RO 77125, Romania
b

Available online 3 October 2007

Abstract
Results on the deposition and characterization of TiOxNy/ZrOxNy multilayers, with bilayer periods of 20 and 400 nm, are presented. The
coatings were deposited on TiNiNb alloy substrates by the pulsed magnetron sputtering method. The elemental composition, hardness, adhesion
and corrosion resistance of the coatings were analyzed.
As resulted from the XPS analysis, the individual layers consisted of a mixture of titanium or zirconium oxynitrides and corresponding oxides.
X-ray analysis revealed that the coatings were amorphous. Only slight differences between the microhardness and adhesion values of the coatings
with small and large bilayer period were found. The experiments also showed that the multilayered coatings improved the corrosion resistance
of the uncoated alloy and reduced the amount of ion release in artificial body fluids.
2007 Elsevier B.V. All rights reserved.
Keywords: Coatings; Corrosion resistance; Pulsed magnetron sputtering; Multilayer oxynitrides

1. Introduction
It is well known that nickel-containing alloys are indispensable in a vast number of major biomedical applications [1,2].
The existing in vitro studies show that the metal implants release
ions that can lead to various adverse physiological effects [35].
Therefore, there are needed new solutions to tackle the problem
of ion diffusion from the metallic alloys into the body fluids.
Recently, intense efforts have been made to produce
multilayer biocompatible coatings since multilayer structures
are known to reduce stress, cross-sectional cracks and
dislocations in the coatings [6,7]. This work aims to study the
characteristics of TiOxNy/ZrOxNy multilayers, with small
(20 nm) and large (400 nm) bilayer periods. The coatings
were deposited on TiNiNb alloy (37 wt.% Ti, 48 wt.% Ni and
15 wt.% Nb) substrates, using the pulsed magnetron sputtering
method. The experimental work was focused on the corrosion
behavior of the multilayered coatings in two different artificial
Corresponding author. Tel./fax: +40 21 457 57 59.
E-mail address: balaceanu@inoe.inoe.ro (M. Balaceanu).
0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.09.032

body fluids. Additional information on the multilayer properties

was obtained by RBS and XPS methods, XRD analysis,
microhardness measurements and adhesion tests. For comparison, the properties of ZrOxNy and TiOxNy single-layer coatings
were also investigated. These types of coatings were intensively
studied during the past few years due to their excellent
combination of high hardness, chemical stability, optical and
electrical properties, wear and corrosion resistance [813].
2. Experimental procedure
TiNiNb alloy samples were coated with alternate titanium
and zirconium oxynitride multilayers TiOxNy/ZrOxNy using the
pulsed magnetron sputtering technique [14], in an Ar + O2 + N2
gas mixture. The base pressure in the deposition chamber was of
about 5 10 4 Pa. Prior to deposition, the samples were
sputtered by Ti or Zr ion bombardment (1000 V; 5 min). To
improve the adhesion, a pure metal (Ti or Zr) interlayer with a
thickness of 0.1 m was deposited (except for the samples used
in RBS analysis). The magnetron cathodes were made of Ti and
Zr (both 99.6% purity) and fed by a pulsed bipolar generator-

M. Balaceanu et al. / Surface & Coatings Technology 202 (2008) 23842388

Fig. 1. RBS spectrum of the RBS spectrum of the TiOxNy/ZrOxNy coating.

type ENI RPG5 (positive pulse length 1936 ns, repetition rate
100 kHz). The magnetron current and the negative d.c. substrate
bias were of 3 A and 60 V, respectively. The O2/N2 mass flow
ratios were controlled to be of about 1 and the working pressure
was approximately 5 10 1 Pa. The argon pressure was
adjusted in order to keep a constant overall pressure. These
parameters were kept constant for the deposition of both
monolayers and multilayers with different bilayer periods.
Considering that oxygen is more reactive than nitrogen with
regard to Ti and Zr [8,10], under our deposition conditions,
TiOxNy and ZrOxNy monolayers with relatively high O/N ratios
and characteristics close to those of the corresponding oxides
were expected to be produced. The multilayer coatings
consisted of alternate films with bilayer periods of 20 and
400 nm. From the deposition rates of the films, the ratio of the
thicknesses of ZrOxNy/TiOxNy individual layers was estimated
to be of about 3:1. All the coatings (mono or multilayered
structured) had the same thicknesses (1.2 m), except for the
multilayers used for RBS analysis, which was performed to
evidence the periodic structure of the coating. In this case, the
coatings, deposited on Si substrates, consisted of 8 individual
layers with estimated bilayer periods of about 40 nm. For the
RBS analysis, the value of and the number of layers were
deliberately chosen, so that, considering the overall coating

2385

thickness (320 nm) and the depth resolution of RBS, the signal
from the coating does not overlap with that from Si substrate
and also to have no interference between the signals from the
individual layers. The RBS measurements used a 3 MeV He+
ion beam, at an incident angle of 60.
Chemical composition of the films was determined by X-ray
Photoelectron Spectroscopy (XPS), using a VG ESCA 3 MK II
spectrometer.
Crystallographic structure was investigated by X-ray
diffraction (XRD), using a Philips PW 1340/30 diffractometer
(with CuK radiation).
Microhardness (Vickers) measurements were performed by
means of a microhardness tester at 0.05 N load. To evaluate the
coatings' adhesion, scratch tests under standard conditions
(indenter 0.2 mm radius diamond tip, load continuous
increase from 0 to 100 N, scratching speed 10 mm/min,
scratching distance 10 mm) were undertaken. Critical load Lc
was determined by microscope examination of the scratch trace, Lc
being considered the load at which lateral cracking and spallation at
the edges of the scratch track were observed.
The equipment Voltalab 80, with a saturated calomel electrode
(SCE) as the reference electrode, and the VoltaMaster 4 program
were used to investigate the corrosion behaviour of the coatings.
The following electrochemical techniques were applied: cyclic
potentiodynamic and linear polarisation measurements. Cyclic
potentiodynamic measurements started from the open circuit
potential to positive direction, with a scan rate of 10 mV/s. The
scan was reversed in the negative direction after reaching a potential
of +0.8 V. The following electrochemical parameters were
determined: Ei = 0 corrosion potential (like zero current
potential), Eb breakdown (pitting) potential when the current
density increases; Epp pitting protection potential at which the
current density on the negative sweep equals the passive current
density (below this potential no pit could be initiated); ip passive
current density.
To obtain Tafel curves, linear polarization was applied for
0.2 V around the corrosion potential (Ei = 0), with a scan rate of
10 mV/s. From Tafel curves, the polarization resistance (Rp),
corrosion current densities (icorr), corrosion rates (Vcorr) and the
total ion release were determined.
CarterBrugirard artificial saliva (composition: NaCl
0.79 g/l, NaH2PO4 0.26 g/l, KSCN 0.33 g/l, Na2HPO4
0.19 g/l, NaHCO3 1.5 g/l, urea 0.13 g/l) and Ringer solution
(composition: NaCl 6.8 g/l; KCl 0.4 g/l; CaCl2 0.2 g/l;

Fig. 2. Ti 2p XP spectra of TiOxNy coating: C, D, G, H TiON; B, F Ti suboxide; A, E TiO2.

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M. Balaceanu et al. / Surface & Coatings Technology 202 (2008) 23842388

Fig. 3. Zr 3d XP spectra of ZrOxNy coating: C, D ZrON; A, B ZrO2.

MgSO47H2O 0.2048 g/l; NaH2PO4H2O 0.143 g/l;

NaHCO3 2.2 g/l; glucose 1 g/l) at 37 C temperature
were used for corrosion tests.
3. Results and discussion
3.1. Modulation periodicity
The coatings, deposited on Si substrates, consisted of 4
alternating TiOxNy and ZrOxNy layers (ZrOxNy the outer
layer) with estimated thicknesses ratio of the individual ZrOxNy
and TiOxNy layers of about 3:1. A RBS spectrum for a TiOxNy/
ZrOxNy coating presenting the periodic structure of the film is
shown in Fig. 1. The arrows labeled Zr and Ti mark the signals
from the outer ZrOxNy layer and the TiOxNy layer located
bellow it, respectively. The value (3.5) obtained for the
thickness ratio of ZrOxNy and TiOxNy individual layer was not
significantly different from the value ( 3) estimated from the
deposition rates. The experimental results demonstrated that the
deposition method can lead to the preparation of TiOxNy/
ZrOxNy multilayers with controlled periodical structures.

ly); Ti 2p1/2 (461.6 eV) and Ti 2p3/2 (456.7 eV) to TiO

suboxides; Ti 2p1/2 (463.6 eV) and Ti 2p3/2 (458.2 eV) to TiO2.
In Fig. 3, a Zr 3d XP spectrum for a ZrOxNy film is shown.
The ZrOxNy coating consists of a mixture of zirconium oxides
(ZrO2), zirconium oxynitride species (ZrON) and adsorbed O2.
According to the literature data [18,19], the Zr 3d peaks were
associated with Zr oxynitride species and ZrO2 as follows: Zr
3d5/2 (180.1 eV) and Zr 3d3/2 (182.3 eV) to ZrON; Zr 3d5/2
(183.1 eV) and Zr 3d3/2 (185.0 eV) to ZrO2.
From the XPS analysis, the elemental compositions of the
monolayers were found to be: Ti 28.3 at.%, O 56.5 at.%
and N 15.2 at.% for TiOxNy; Zr 32.8 at.%, O 48.7 at.%
and N 18.5 at.% for ZrOxNy. Neglecting the adsorbed oxygen

3.2. Chemical bonding state, elemental composition and

crystallographic structure
The XPS results are consistent with the following chemistry
models of the TiOxNy and ZrOxNy monolayers. Fig. 2 shows the
Ti 2p XP spectrum of TiOxNy film. It can be seen that on the
coating surface, a mixture of two titanium oxynitride species
with different oxygen content, titanium oxides (TiO suboxides
and TiO2), together with some amounts of adsorbed O2, are
present. According to the literature data [1517], the Ti 2p peaks
were associated with TiON species, Ti suboxides and TiO2 as
follows: Ti 2p1/2 (459.7 eV; 460.6 eV) and Ti 2p3/2 (454.3 eV;
455.4 eV) to TiON species (less and more oxidized, respective-

Table 1
Mechanical characteristics of TiOxNy, ZrOxNy and TiOxNy/ZrOxNy coatings
Coating

HV (GPa)

Lc (N)

(nm)

TiO1.37N0.54
ZrO1.05N0.56
TiO1.37N0.54/ZrO1.05N0.56
TiO1.37N0.54/ZrO1.05N0.56

16
20
22
26

16
32
30
35

400
20

Fig. 4. Tafel curves in Ringer solution at 37 C for bare (a) and coated TiNiNb
alloy with ZrOxNy (b) and with ZrOxNy/TiOxNy (c).

M. Balaceanu et al. / Surface & Coatings Technology 202 (2008) 23842388

2387

Table 2
The main electrochemical parameters of the uncoated and coated samples in CarterBrugirard solution at 37 C
Material

Ei = 0 (V) Eb (V) Epp (V) ip (A/cm2) Rp (k cm2) icor (A/cm2) Vcorr (mm/year) Ion release (g/cm2)

Bare TiNiNb
TiNiNb + TiO1.37N0.54
TiNiNb + ZrO1.05N0.56
TiNiNb + TiO1.37N0.54/ZrO1.05N0.56 = 400 nm

0.37
0.33
0.31
0.24

0.13
0.68
0.75
0.80

0.15
0.10
0.12
+0.48

7.00
1.20
0.70
0.15

(17.8 at.% and 14.4 at.% for TiOxNy and ZrOxNy, respectively),
the O/N ratio values in the corresponding films were of 2.5 and
1.9, respectively. As a result of these determinations, the
obtained Zr and Ti oxynitrides will be denoted in the following
by the formulas TiO1.37N0.54 and ZrO1.05N0.56. In the case of
TiO1.37N0.54, the (O + N)/Ti ratio was of about 1.9, in agreement
with the values (1.82) reported in Refs. [12,13]. For
ZrO1.05N0.56, the (O + N)/Zr ratio was of 1.6. These results
show that the oxynitrides films prepared under our depositions
conditions have relatively high oxygen content, as found in some
of the TiOxNy coatings previously analyzed in the references
[9,11,13].
The XRD analysis showed that all deposited coatings were
amorphous.

26.39
389.46
436.82
1670.0

0.52
0.08
0.05
0.01

4.54 10 3
0.76 10 3
0.47 10 3
0.08 10 3

461.26
77.21
47.75
8.84

Fig. 4. In Tables 2 and 3 are shown the main electrochemical

parameters in the above mentioned solutions, for uncoated and
coated samples.
The values from Tables 2 and 3 clearly show that the
corrosion resistance of TiNiNb alloy is improved by the
deposited films. The corrosion potentials (Ei = 0) of the coated
alloy are more electropositive than of the bare alloy in both types
of the physiological solutions, confirming the favorable,
protective effects of the coatings. A decrease of the dissolution
current in the passive range (ip) was observed for all coatings, as
result of the barrier effects of these coatings. Of the monolayers, a
slightly better corrosion behavior was found for the ZrO1.05N0.56
films.
In comparison with monolayer coating, higher values for the
breakdown potential (Eb) were measured in the case of the
TiO1.37N0.54/ZrO1.05N0.56 multilayer coating, indicating a better
resistance to pitting corrosion. Also, for the multilayer coatings,
the pitting protection potentials (Epp) had improved values,
showing very good repassivation of pits for both test solutions.
For the corrosion current (icorr), no significant differences
between the values for the mono and multilayers were evidenced.
Comparing with the bare substrate, all coatings presented a
significant decrease of the corrosion current densities (icorr) and
corrosion rates (Vcorr). Therefore, the corrosion resistance
increased from very stable for bare alloy to perfect stable
for coated alloy. According to ISO 8044, materials are considered
to be very stable and perfect stable if the corrosion rate Vcorr
is between 1 10 3 and 1 10 2 mm/year and lower than
1 10 3 mm/year, respectively.
Also, the polarization resistance (Rp) is higher in the presence
of the coatings due to their good anticorrosive properties.
It can be seen that the total amount of ion release in biofluids
was lower for coated samples than for the uncoated ones,
indicating that coatings act as an efficient diffusion barrier.
Taking into account all electrochemical parameters and corrosion
rates, it can be concluded that the TiO1.37N0.54/ZrO1.05N0.56
multilayer coatings present good protective properties in Carter
Brugirard artificial saliva and Ringer solution.

3.3. Mechanical characteristics

Vickers microhardness and critical load values for various
single layer and multilayer coatings are summarized in Table 1.
ZrO1.05N0.56 monolayers exhibited microhardness with
about 4 GPa higher than that of the TiO1.37N0.54 films. In the
case of multilayers, the microhardness depended on the bilayer
period, being slightly superior to those of the TiO1.37N0.54 and
ZrO1.05N0.56 monolayers. Anyhow, the hardnesses observed for
the multilayers are higher than those predicted by the rule of
mixture [20]. Since the indentation depths were ranging
between 0.22 and 0.28 of the coating thickness, the measured
microhardness values were to some extent influenced by the
substrate hardness (61 HRC).
As for the adhesion, no systematic dependence of the critical
load on the bilayer period was evidenced. Lc values similar to
those for the monolayers were measured.
3.4. Corrosion resistance
Examples of Tafel curves in body simulated fluids (Ringer
solution) of the bare and coated with mono and multilayer
oxynitrides (with = 400 nm) TiNiNb alloy are presented in

Table 3
The main electrochemical parameters of the uncoated and coated samples in Ringer solution at 37 C
Material

Ei = 0 (V) Eb (V) Epp (V) ip (A/cm2) Rp (k cm2) icor (A/cm2) Vcorr (mm/year) Ion release (g/cm2)

Bare TiNiNb
TiNiNb + TiO1.37N0.54
TiNiNb + ZrO1.05N0.56
TiNiNb + TiO1.37N0.54/ZrO1.05N0.56 = 400 nm

0.42
0.36
0.33
0.32

0.37
0.40
0.42
0.47

0.04
0.01
0.007
0.02

6.0
4.8
4.0
0.5

31.66
510.20
466.89
996.10

0.82
0.04
0.04
0.02

7.18 10 3
0.43 10 3
0.37 10 3
0.22 10 3

729.49
43.68
37.99
22.35

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M. Balaceanu et al. / Surface & Coatings Technology 202 (2008) 23842388

4. Conclusions
TiOxNy/ZrOxNy multilayer coatings were prepared by pulsed
magnetron sputtering technique on TiNiNb alloys, intended to
be used in medical applications. XPS analysis showed that the
individual layers consisted of a mixture of metal (Ti or Zr)
oxynitrides and oxides, together with adsorbed oxygen. The
oxynitride compounds had a relatively high oxygen content, the
O/N ratio being of 2.5 and 1.9 for TiO1.37N0.54 and ZrO1.05N0.56
films, respectively. The modulation periodicity of the multilayers was evidenced by RBS, the thicknesses of the individual
layers determined by this technique being in a satisfactory
agreement with the values predicted from the deposition rates of
the layers. Vickers microhardnesses of the multilayers were
ranging from 22 to 26 GPa, higher than those of the single layer
coatings. A good adhesion of all the coatings was found (critical
loads of 3035 N were obtained), taken into account the data in
literature for transition metal oxides and the intended applications of the coatings.
The experimental results showed the favourable influence of
the tested coatings on the corrosion resistance of the TiNiNb
alloy in CarterBrugirard artificial saliva and Ringer solution.
The main electrochemical parameters presented better values
revealing the favorable, protective effects of the coatings. Also,
the decrease of the ion release amount confirms that the coatings
are efficient barriers to prevent ion diffusion.
Acknowledgements
The work was supported under the Romanian Projects PN06-250301 and Biosmeta-25/2005.
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