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In Vitro Corrosion Behavior of Selective Laser Melted Ti-35Nb-7Zr-5Ta

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DOI: 10.1007/s11665-021-05940-9

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In Vitro Corrosion Behavior of Selective Laser Melted

Ti-35Nb-7Zr-5Ta
Raghunandan Ummethala , J. Jayaraj, Phani S. Karamched, Sokkalingam Rathinavelu, Neera Singh, Kumar Babu Surreddi,
and K.G. Prashanth

Submitted: 9 April 2021 / Revised: 19 May 2021 / Accepted: 23 May 2021

Ti-35Nb-7Zr-5Ta (TNZT) alloy has been fabricated by selective laser melting (SLM) at different build
orientations with respect to the base plate and the resulting disparities in the grain shape, size, preferred
orientations and lattice strains have been determined. Potentiodynamic polarization tests performed under
in vitro conditions indicated that the specimens built at 45° orientation showed the highest polarization
resistance (24.5 kX cm2) and lowest rate of corrosion (0.23 lA cm22) compared to the specimens built at
other orientations. The corrosion behaviors of the SLM specimens have been correlated with their
microstructural features and further compared with that of its spark plasma sintered (SPS) counterpart
and commercial alloys such as Ti6Al4V and Ti6Al7Nb. Electrochemical impedance spectroscopy and
potentiostatic measurements have revealed that the passive film forming on the TNZT sample at 45°
orientation is highly stable and more protective than that of the other samples. Auger electron spectroscopy
has confirmed that both Ti and Nb participate actively in the passive film formation on the SLM TNZT
alloy.

applications due to their closer modulus match with that of

Keywords additive manufacturing, AC impedance spectroscopy,
Auger electron spectroscopy, corrosion, passivation,
Ti-35Nb-7Zr-5Ta alloy
1. Introduction
Titanium is regarded as the best choice for orthopedic and
dental implant applications owing to its excellent biocompat-
ibility, high specific strength and corrosion resistance (Ref 1).
The Food and Drug Administration (FDA)-approved commer-
cial (a+b) titanium alloys, namely Ti-6Al-4V and Ti-6Al-7Nb,
have been revealed to induce toxic effects in the long run due to
their alloying elements (Ref 2). Al and V have been replaced
with biocompatible b stabilizing elements such as Nb/Zr/Ta/Sn
(Ref 2). The b alloys are the latest family of biocompatible Ti-
based alloys under extensive investigation for orthopedic
Raghunandan Ummethala, Department of Metallurgical and
Materials Engineering, National Institute of Technology, Andhra
Pradesh, Tadepalligudem 534101, India; J. Jayaraj and
Kumar Babu Surreddi, Materials Technology, Dalarna University,
791 88 Falun, Sweden; Phani S. Karamched, Department of
Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK;
Sokkalingam Rathinavelu, Advanced Materials Processing
Laboratory, Department of Metallurgical and Materials Engineering,
National Institute of Technology, Tiruchirappalli 620015, India;
Neera Singh, Department of Materials Engineering, Indian Institute
of Science, Bangalore 560012, India; K.G. Prashanth, Department of
Mechanical and Industrial Engineering, Tallinn University of
Technology, Ehitajate tee 5, 19086 Tallinn, Estonia; Erich Schmid
Institute of Materials Science, Austrian Academy of Sciences,
Jahnstraße 12, 8700 Leoben, Austria; and CBCMT, School of
Mechanical Engineering, Vellore Institute of Technology, Tamil
Nadu, Vellore 632 014, India. Contact e-mails:
raghu.ummethala@gmail.com and kgprashanth@gmail.com.
the natural bone, albeit lower mechanical strength (Ref 3).
Titanium and its alloys possess high affinity for oxygen and
are known to instantaneously form passive oxide films in
complex physiological environments (Ref 1, 4-8). The passive
film is believed to be composed of non-stoichiometric TiO2
containing anionic vacancies accounting for n-type semicon-
ducting characteristics (Ref 9, 10). The oxide film is highly
stable, adherent and protective against corrosion and has the
ability to repair itself upon mechanical rupture even in most of
the aggressive environments (Ref 6, 11).
Alloys fabricated by SLM show significant anisotropy in the
microstructural features such as grain size, shape, the volume
fraction, size distribution of the secondary phases, texture and
possibly lattice strains due to differential thermal gradients (Ref
12). These differences in turn result in anisotropy in the
mechanical and corrosion behavior of additively manufactured
(AM) Ti- and its alloys. Various studies have established the
anisotropy in mechanical properties of AM titanium with regard
to hardness (Ref 13-16), fracture toughness (Ref 17, 18) and
tensile properties (Ref 19-26). However, understanding the
influence of the microstructural anisotropy on the corrosion
behavior of titanium alloys is more complicated due to the
difficulty in isolating the combined effects of grain size,
distribution, residual stresses and so on, on the rate of corrosion
and polarization resistance. Dai et al., (Ref 27, 28), Chen et al.,
(Ref 29) and Gong et al., (Ref 30) studied the effect of build
direction of AM-Ti6Al4V on the corrosion behavior in
physiological environments. It was observed in their studies
that the planes parallel to the build direction showed poorer
corrosion resistance, while the planes perpendicular to build
direction showed higher corrosion resistance. The lower
corrosion resistance on the parallel planes was attributed to a
weaker passive film and larger, elongated grain structures.
Several authors have investigated the corrosion behavior of
AM-Ti6Al4V in physiological environments such as PBS and
SBF to understand the influence of post-heat treatments (Ref

Journal of Materials Engineering and Performance

31-35). It was proposed that a higher b fraction and a refined a-
b phase resulted in improved corrosion resistance for the AM-
Ti6Al-4V alloy in comparison with its wrought counterpart.
Zhao et al. performed corrosion tests on both SLM- and EBM-
Ti6Al4V, in comparison with the wrought alloy, and concluded
that the SLM alloy possessed the most stable oxide film and the
best corrosion resistance below 1.2V (Ref 36). These observa-
tions were attributed to the higher grain boundary density and
higher contact angle (>90) of the electrolyte on the SLM
alloy. In most cases, AM-Ti alloys exhibit anisotropic corrosion
behavior, where the plane perpendicular to the build direction
shows better corrosion resistance, compared to the parallel
plane. Hence, the build direction plays a crucial role in
conferring the favorable corrosion attributes to the additively
manufactured alloys. Very few other AM titanium-based alloys
and composites such as Ti6Al4V-Cu, Ti-Mo, Ti-TiB and Ti-TiC
were investigated for their corrosion behavior (Ref 37-41).
Literature studies on the corrosion behavior of additively
manufactured b titanium alloys are extremely rare (Ref 42-44).
It was reported for conventional b alloys that the surface oxides
such as Nb2O5, Ta2O5, and ZrO2 have higher stability and
protective nature than that of TiO2 modified by the oxides of Al
and V (Ref 45). Furthermore, the single b phase was found to
be more corrosion resistant than single a phase (Ref 46).
Hence, the study of passivation tendencies of AM-b alloys
would be very interesting as it provides useful insights into
their in vitro corrosion behavior.
The purpose of this study was to evaluate the in vitro
corrosion characteristics of an additively manufactured b alloy,
Ti-35Nb-7Zr-5Ta (TNZT) and to correlate them with the grain
size, texture and microstrains induced in such non-equilibrium
processing conditions. Since the sample build orientation
during SLM has a significant effect on the texture, grain size
and grain shape of the SLM components, its effect on the
corrosion characteristics was studied in detail. In order to
further compare the influence of the processing route and hence
the resulting microstructural features of the alloy, spark plasma
sintered (SPS) TNZT was also used for this study. Additionally,
the two prominent FDA-approved alloys namely Ti6Al4V and
Ti6Al7Nb alloys, fabricated by SPS, were also used to compare
and correlate the corrosion characteristics with the composition,
phases and microstructural attributes of all the alloys. The
corrosion potential, corrosion current density, passive current
density and resistance to polarization were determined for all
the alloys. Electrochemical impedance spectroscopy and Auger
electron spectroscopy were performed to comprehensively
understand the nature and composition of the passive films
forming on the SLM TNZT alloys under in vitro conditions.
2. Materials and Methods
2.1 Materials
The study broadly involves three titanium alloys, namely Ti-
35wt.% Nb-7wt.% Zr-5wt.% Ta (TNZT), Ti-6wt.% Al-4wt.%
V (Ti6Al4V) and Ti-6wt.% Al-7wt.% Nb (Ti6Al7Nb). Gas-
atomized, pre-alloyed TNZT powder (99.99% purity) was used
to fabricate bulk specimens by means of selective laser melting
(SLM) and spark plasma sintering (SPS). Spherical TNZT
powder particles in the size range of 10-150 lm (d50 = 63.7
lm) were used for SLM, whereas the powder with particle size
150-300 lm was used for SPS. The scanning electron images
demonstrating the particle size, morphology, size distribution
and the diffraction spectrum of the feedstock powder used in
this study are presented elsewhere (Ref 26). The chemical
composition of both the powders was identical. Ti6Al4V ELI
(Grade 23) powder and Ti6Al7Nb powder, each composed of
spherical particles in the size range 20-63 lm, were consoli-
dated by means of SPS.
2.2 Consolidation
2.2.1 SLM of TNZT. Bulk specimens of TNZT produced
by SLM were carried out at room temperature using a Realizer
SLM-50 device, equipped with a fiber laser. The parameters
used for preparing the specimens were: (a) laser power: 100 W;
(b) scanning speed: 167 mm s-1 for the volume and 250 mm s-1
for the contour; (c) layer thickness: 50 lm; (d) hatch spacing:
80 lm; and (e) hatch style rotation: 60. The systematical
approach adopted to arrive at the optimum process parameters
is discussed at length elsewhere (Ref 26). High-purity
(99.999%) argon gas was purged in the SLM chamber during
the entire melting sequence in order to avoid oxygen contam-
ination. Cuboids of dimensions 10 (l) 9 10 (w) 9 5 (t) mm3
were printed on a titanium base plate. Support structures were
built between the specimens and the base plate in order to
ensure good mechanical stability of the SLM parts and to
guarantee adequate heat dissipation during processing. The
effect of texture was investigated by fabricating specimens with
different angles of inclination (c = 0, 45, 90) with respect to
the base plate.
2.2.2 SPS of TNZT, Ti6Al4V and Ti6Al7Nb. Densifica-
tion via SPS for all the three alloys was performed in a vacuum
spark plasma sintering chamber (FCT Systeme GmbH),
enclosed in an argon-filled glovebox (mBraun MB200B), at
1200 C for 5 min under 50 MPa uniaxial pressure.
2.3 Material Characterization
Samples for microstructural characterization were polished
to mirror-finish (0.05 lm colloidal silica suspension) and
etched with KrollÕs reagent. The microstructures of the SPS
alloys were determined by a scanning electron microscope,
Zeiss EVO MA15, whereas the grain structure of the SLM
TNZT samples was revealed by band contrast imaging by
means of electron back-scattered diffraction (EBSD). After
fine polishing, the samples were prepared for EBSD by ion
polishing using a Gatan PECS II ion polisher at 8 kV, 5 and
10 min. EBSD was performed on a Zeiss Crossbeam 540
SEM, equipped with an Oxford Instruments detector. Struc-
tural analysis of the samples was carried out by X-ray
diffraction (XRD) using a Rigaku SmartLab X-ray diffrac-
tometer equipped with Cu-Ka radiation (k: 1.5406 Å), with a
step size of 2h = 0.01 in a reflection mode. Auger electron
spectroscopy (AES) was performed on a selected TNZT alloy
to determine the oxide scale thickness and the elemental
distribution in the native condition and post-immersion in
phosphate-buffered saline (PBS). For this purpose, a PHI
700Xi Scanning Auger Nanoprobe with an acceleration
voltage of 10 keV and a beam current of 10 nA was used.
Sputtering was performed with 2 keV Ar+ ion sputtering with
sputter interval of 0.06 min at a rate of 1 min, equivalent to
17.1 nm. PHI Multipak software was used for peak identi-
fication and data analysis.
Journal of Materials Engineering and Performance
2.4 Electrochemical Corrosion Tests
The measurement of open-circuit potentials, followed by
electrochemical impedance spectroscopy (EIS) and polarization
tests, was performed on a PGSTAT302 N electrochemical
workstation (Autolab, The Netherlands). The experimental
conditions were closely conformed to those recommended in
the ASTM standards (F 2129-08). Phosphate-buffered saline,
PBS (8 g NaCl, 0.2 g KCl, 1.15 g Na2HPO4, 0.2 g KH2PO4 in 1
l of water), was used as electrolyte. The pH of the solution was
adjusted to 7.45 by adding HCl/NaOH, and fresh solution was
prepared immediately preceding every test. All the tests were
conducted at 37 C (human body temperature) by placing the
round bottom glass cell on a hot plate during the entire length
of the experiments. The open-circuit potential (OCP) was
measured for 30 min for each sample in PBS. A three-electrode
system, consisting of the Ti alloy (TNZT/Ti6Al4V/Ti6Al7Nb)
as the working electrode, a platinum sheet as the counter
electrode and Ag/AgCl electrode as the reference electrode, was
used. The potentiodynamic polarization tests were conducted in
a potential range of 200 mV below the OCP to an absolute
potential of +1.6 V at a scan rate of 1 mV s-1. The EIS
measurements were performed at open-circuit potential in the
frequency range from 0.01 to 100 kHz. All the electrochemical
experiments were at least triplicated on freshly prepared
samples to verify the repeatability of the results.
3. Results and Discussion
3.1 Microstructure and Phase Constitution of the Ti Alloys
The typical grain structures of the as-SLM and as-SPS
TNZT alloys are represented in Fig. 1. SLM TNZT alloys are
distinguished among themselves based on the build direction
(sample orientation with respect to the base plate: 0º/45º/90º).
As shown in Fig. 1(a), TNZT SLM0 exhibits a typical
combination of large elongated grains along hatches and fine
equiaxed grains along the hatch overlaps, of average size in the
range of 8-100 lm. The TNZT SLM45 sample mostly
constitutes equiaxed grains (majority of the grains in size
range 10-20 lm and a few larger grains in the size range 20-90
lm), along with a small fraction of elongated grains (Fig. 1b).
The TNZT SLM90 exhibits large elongated grains (up to 200
lm in length and 15 lm in width) along the build direction
(Fig. 1c). The TNZT SPS bulk sample, on the other hand,
exhibits a uniform microstructure with equiaxed, large grain
morphology (50 lm to >400 lm) as shown in Fig. 1(d). All
the TNZT alloys exhibit a single-phase microstructure irre-
spective of the fabrication route (Fig. 2a). Both the SPS
Ti6Al4V and SPS Ti6Al7Nb show typical dual phase a+b
lamellae or colony microstructure with prior-b grains, compa-
rable to the colony size, of 500-800 lm, respectively, and a
grain boundary a layer, approximately 3-5 lm thick.
Figure 2(a) presents an overlay of the x-ray diffraction
patterns for all the six samples. The diffraction patterns
collected from the TNZT SLM0/45/90 and SPS TNZT samples
corroborate the presence of a single-phase b (bcc) microstruc-
ture observed in the SEM images shown in Fig. 1(a-d). The
SLM TNZT samples show broader peaks compared to their
SPS counterpart, suggesting the presence of finer grain size in
the former. The lattice parameters of the bcc unit cells in all the
TNZT samples, calculated based on the distance between
adjacent planes in the Miller indices (hkl) (calculated from the
Bragg equation, k = 2dSinh), are found to be in the range of
0.330-0.331 nm, closely matching with that of pure titanium at
900 ºC (Ref 47). The calculated c/a ratios of the hcp unit cells
in SPS Ti6Al4V and SPS Ti6Al7Nb are 1.603 and 1.586,
closely comparable with that of a-Ti (Ref 48). The size-induced
and strain-induced peak broadenings of the xrd patterns are
deconvoluted by employing Williamson-Hall analysis, accord-
ing to the following Eq (Ref 49):
kk
b cos h ¼ Ce sin h þ ðEq 1Þ
L
where b is the full width at half maximum (FWHM), h is the
incident glancing angle, Ce is the lattice strain, k is the form
factor (0.94), k is the wavelength of the incident wave and L
is the crystallite size. The lattice strains in the SLM TNZT
alloys (12.029103, 18.419103 and 13.749103 for 0º, 45º

Fig. 1 Band contrast images showing the grain structures of TNZT alloys fabricated by SLM at (a) 0, (b) 45 and (c) 90 orientations with
respect to the base plate; SEM images of spark plasma sintered (d) TNZT, (e) Ti6Al4V and (f) Ti6Al7Nb alloys

Journal of Materials Engineering and Performance

Fig. 2 (a) X-ray diffraction patterns for the SLM TNZT alloys fabricated at 0, 45, 90 orientations with respect to the base plate and SPS
TNZT, Ti6Al4V and Ti6Al7Nb alloys, (b) Texture coefficients of the b (110) and (002) planes for the samples TNZT SLM0, TNZT SLM45 and
TNZT SLM90, quantified based on Eq (2)
and 90º orientations, respectively) are approximately 5 times
higher than that in the SPS TNZT (2.01910-3), Ti6Al4V
(3.799103) and Ti6Al7Nb (2.959103) owing to the reten-
tion of thermal stresses in the rapidly cooled alloys in the
former case (Ref 50, 51). Such non-equilibrium processing also
leads to finer crystallite sizes in the SLM alloys: 30.94 nm,
82.04 nm and 44.97 nm for TNZT SLM 0/45/90, respectively,
compared to 132.85 nm, 109.71 nm and 130.46 nm for the SPS
TNZT, Ti6Al4V and Ti6Al7Nb alloys, respectively. The
variation in crystallite sizes among the six samples calculated
using Williamson-Hall method closely matches with the trend
in the variation of their respective grain sizes observed with
SEM. These factors contribute to higher strength and hardness
in the SLM alloys, compared to the alloys processed by SPS.
Additionally, mild texture is observed within the SLM
TNZT alloys suggested by the differences in the peak
intensities, especially for the planes [110] and [002] at 2h
values 38.45º and 55.5º, respectively, in Fig. 2(a). The
extent of texture of the b [110] and [002] planes was quantified
by means of texture coefficient, which is given by Eq. (2) (Ref
52)
I ðhklÞ=Io ðhklÞ
Tc ðhklÞ ¼  hP i ðEq 2Þ
1 I ðhkl Þ=
N N Io ðhkl Þ
where Tc ðhkl Þ is the texture coefficient of the ðhklÞ plane, I is
the measured intensity, Io is the standard intensity from
reference (gas-atomized TNZT powder) and N is the number
of diffraction peaks. Figure 2b indicates that with change in the
build orientation (from 0º to 90º), the texture coefficient of
[110] increases, while that of [002] planes decreases. TNZT
SLM45 and TNZT SLM90 exhibit preferential orientation
along the closely packed [110] of the bcc crystal lattice. The
microstructural attributes of all the alloys are compared in
Table 1.
3.2 In vitro Corrosion Behavior
The in vitro corrosion behavior of the alloys was studied by
conducting potentiodynamic polarization tests, linear polariza-
tion, electrochemical impedance spectroscopy and potentio-
static measurements in PBS solution of pH 7.45 at 37 ºC. The
pH of the solution was found to be the same before and after
every test. Corrosion current density (jcorr) and corrosion
potential (Ecorr) were calculated by Tafel extrapolation method
from the Tafel regions as indicated in Fig. 3(a). The corrosion
potential (Ecorr) and corrosion current density (jcorr) values
derived from Tafel extrapolation are presented in Table 2. The
Ecorr values of all the alloys nearly coincide with one another in
the close range of  0.04 to  0.004 V vs. Ag/AgCl probably
due to the same base metal (Ti), identical electrolyte/testing
conditions and similar surface finish for all the alloys. The
disparities in the microstructural features among different
samples did not significantly alter their corrosion potential.
However, interestingly, the rate of corrosion differs consider-
ably among the alloys. The jcorr for the four TNZT samples,
namely TNZT SLM0/45/90 and TNZT SPS, is measured as
0.18, 0.23, 1.75 and 3.15 lA cm2, respectively, whereas that
for SPS Ti6Al4V and SPS Ti6Al7Nb are 2.38 and 3.40 lA
cm2, respectively. It is worthwhile to note that all the alloying
elements in TNZT, namely Nb, Zr and Ta, are capable of
forming protective passive films unlike in the case of alloying
elements such as Al or V (Ref 53). The trend in the variation of
jcorr of all the SPS alloys, irrespective of the alloy composition,
suggests that the values vary in a rather narrow range.
However, when the variation of jcorr is correlated with the
processing route for the TNZT alloy, it is apparent that the jcorr
of the SLM samples is lower than that of the SPS sample. It
may be recalled that all the SLM TNZT samples constitute finer
grains compared to their SPS counterpart. The finer grains, and
consequently a higher grain boundary density, provide a larger
flux of metal ions aiding in the formation of a protective oxide
film, thus reducing the jcorr. Besides the grain size, the degree of
lattice strains also plays a significant role in determining the
ease of passive layer formation. The SLM TNZT samples show
approximately 6-9 times higher degree of microstrains (12.02-
18.49103) compared to the SPS TNZT alloys (2.019103).
The higher strains in the SLM TNZT samples suggest a higher
driving force for the formation of the passive film. It is
speculated that these lattice strains instigate a rapid formation
and retention of passive oxide layer due to some sort of
mechano-oxidation reaction (Ref 54, 55). The microstrains
within the crystals promote the rate of additional non-sponta-
neous reactions exponentially leading to the formation of sub-
oxidations states that were originally thermodynamically unfa-
Journal of Materials Engineering and Performance
Table 1 Comparison of microstructural and compositional attributes of the SLM- and SPS-processed TNZT alloy and
the SPS-processed Ti6Al4V and Ti-6Al7Nb alloys.
S. Grain size, Lattice strain, 3 Crystallite size, [110] texture Alloying elements and Phases
No. Sample lm 10-3 nm coefficient present

1 TNZT SLM0 8-100 12.02 30.94 0.6 Nb, Zr, Ta (single phase b)
2 TNZT SLM45 10-90 18.41 82.04 1.6
3 TNZT SLM90 50-200 13.74 44.97 1.7
4 SPS TNZT 50-400 2.01 132.85 …
5 SPS Ti6Al4V 500-800 3.79 109.71 … Al, V (dual phase a and b)
6 SPS Ti6Al7Nb 500-800 2.95 130.46 … Al, Nb (dual phase a and b)

Fig. 3 Potentiodynamic polarization plots for the SLM TNZT alloys fabricated at 0, 45, 90 orientations with respect to the base plate and
SPS-fabricated TNZT, Ti6Al4V and Ti6Al7Nb alloys in PBS of pH 7.45 at 37 C: Current densities in (a) log scale and (b) linear scale

Table 2 Summary of various polarization parameters as well as corrosion rates for the SLM TNZT alloys fabricated at
0°, 45°, 90° with respect to the base plate and SPS-fabricated TNZT, Ti6Al4V and Ti6Al7Nb alloys in PBS of pH 7.45 at
37 °C.
Sample Ecorr (V vs. Ag/AgCl) jcorr lA cm22 Epass (V vs. Ag/AgCl) jpass lA cm22 Etrans (V vs. Ag/AgCl)

TNZT SLM0  0.03 0.18 0.39 80.6 1.13

TNZT SLM45  0.04 0.23 0.39 59.3 1.25
TNZT SLM90  0.03 1.75 0.42 94.8 1.14
SPS TNZT  0.02 3.15 0.40 136.7 1.14
SPS Ti6Al4V 0.00 2.38 0.42 147.2 1.21
SPS Ti6Al7Nb  0.01 3.40 0.43 434.5 1.11

vorable (Ref 54, 55). Hence, the jcorr for the SLM alloys is
lower than that of the SPS alloy. Furthermore, when we draw
comparisons among all the three SLM TNZT samples built at
0, 45 and 90 orientations, the TNZT SLM90 sample shows
the highest jcorr compared to the other two, owing to its larger
grain size as evident from Fig. 1(c). TNZT SLM0 and TNZT
SLM45 exhibit nearly the same and the least jcorr values of 0.18
and 0.23 lA cm-2 (about 9.7 and 7.5 times lower, as compared
to TNZT SLM90), respectively. The higher grain boundary area
in the TNZT SLM0 and TNZT SLM45 alloys results in a lower
rate of corrosion due to a more rapid formation of passive layer,
as also confirmed by a low jpass. The jpass values were
determined by extrapolating the linear passive region and
identifying the corresponding current density for the alloys.
Larger grain sizes exceeding 180 lm and up to 400 lm in case
of TNZT SLM 90 and TNZT SPS alloys, respectively, display a
higher jcorr and a delayed passivation, i.e., higher jpass. On a
comparative note, all the six samples tested showed superior
corrosion resistance compared to stainless steels 304 and 316 in
PBS, whose jcorr values were reported as 24.1 lA cm2 and 5.8
lA cm2, respectively (Ref 56).
The passivation behavior of the alloys was studied by
extending the anodic polarization regime beyond the Tafel
region and up to 1.6 V vs. Ag/AgCl. Figure 3(a,b) shows an
overlay of the potentiodynamic polarization plots for the alloys
in semi-logarithmic and linear scales, respectively. All the
alloys showed stable passivity below the transpassive potential
(Etrans). Various parameters such as the passivation potential

Journal of Materials Engineering and Performance

(Epass), passive current density (jpass) and transpassive potential
(Etrans) are deduced from the potentiodynamic plots and
compared in Table 2.
Broadly, among the three alloy systems, namely TNZT,
Ti6Al4V and Ti6Al7Nb, the passivation current density (jpass)
is the least for TNZT, probably owing to the strong oxidizing
ability of the alloying elements viz. Nb, Zr and Ta. Additionally,
the presence of a single phase in the TNZT alloy minimizes the
possibility of heterogeneous corrosion reactions or formation of
localized galvanic cells. The disparity in the jpass values for the
alloys is more apparent in the linear plots shown in Fig. 3(b).
Ti6Al7Nb exhibits the highest jpass (434.5 lA cm-2), while
TNZT SLM45 shows the least (59.3 lA cm2). A higher jpass
for Ti6Al4V may be ascribed to the formation and diffusion of
vacancies in the oxide layer resulting due to the dissolution of
vanadium oxide from the passive film. Furthermore, the higher
jpass for both Ti6Al4V (147.2 lA cm2) and Ti6Al7Nb (434.5
lA cm2) may be a result of their heterogeneity with respect to
chemical composition (uneven distribution of the alloying
elements) and dual phase microstructure, unlike TNZT, and
their selective dissolution (Ref 57). It has been further reported
that Al tends to dissolve in similar simulated body fluids such
as HankÕs solution (Ref 58). On the other hand, a high
concentration of Nb (24 at%) in TNZT alloys, compared to a
mere 3.6 at% in Ti6Al7Nb, aids in stabilizing the surface films
(Ref 59). Nb cations further improve the structural integrity of
the surface film by occupying the anion vacancies generated by
the presence of lower oxidation states of titanium (Ref 60, 61).
Yu et al. have further reported that the modification of TiO2
layer by niobium oxide (Nb2O5) or zirconium oxide (ZrO2)
reduces the Cl- ingress into the oxide layer, thereby improving
the passivation properties of the surface film such that pitting
tendency was reduced (Ref 60).
It can be further noted from Table 2 that the TNZT alloys
fabricated by SLM show a lower jpass compared to their SPS
counterpart, despite bearing identical composition and phases.
The finer grain size, typical cellular structure arising from the
SLM fabrication and a higher extent of thermally induced
microstrains, as evident from Table 1, in the SLM TNZT
samples contribute to an easier and quicker formation of the
passive film, and hence a lower jpass. Moreover, when
distinction is made only among the three SLM TNZT samples
with respect to the jpass values, it can be observed from
Table 2 that jpass [TNZT SLM45] (59.3 lA cm2) < jpass [TNZT
2 2
SLM0] (80.6 lA cm ) < jpass [TNZT SLM90] (94.8 lA cm ).
The effect of build orientation of TNZT SLM samples on
their corrosion rate is significant. It may be recalled that the
jcorr values for these samples follow a similar trend, which
reiterates the influence of the grain size and the degree of
lattice strains on their corrosion and passive current densities.
TNZT SLM45 exhibits the least jpass, indicating that the
passive film forms more instantly than on the other SLM-
fabricated samples. Enhanced passivity of TNZT SLM45
samples may be also be attributed to their preferential
orientation along the close-packed [110] plane of the bcc
crystal. Although TNZT SLM90 exhibits similar degree of
preferred texture, other factors such as the large grain size
negate the effect of the preferred texture. Overall, among all
the samples tested, TNZT SLM45 undergoes easiest or
quickest passivation under in vitro conditions. The lowest
passive current density for the TNZT SLM45 sample indicates
that the passive film has a highly protective nature, probably
due to its very low ionic/electronic conductivity.
Figure 3(b) clearly indicates that all the alloys display a
transpassive potential (Etrans), beyond which the current
densities have again increased exponentially. This phenomenon
may occur likely due to the rupture of the passive film or due to
oxygen evolution. TNZT SLM45 exhibits the highest Etrans
(1.25 V vs. Ag/AgCl), while Ti6Al7Nb records the least (1.11
V vs. Ag/AgCl). The ETrans for TNZT SLM0, TNZT SLM90
and SPS TNZT samples match very closely with one another
(1.13-1.14 V vs. Ag/AgCl). An ideal combination of lower jcorr,
lowest jpass and highest Etrans obtained from the potentiody-
namic polarization of the TNZT SLM45 sample makes it the
best candidate among rest of the samples.
For additional electrochemical analyses hereafter, TNZT
SLM0 and TNZT SLM90 samples have been left out of the
discussion in order to compare only the best SLM alloy, namely
TNZT SLM45, with the rest of the samples. The variation of
polarization resistance (Rp) of the samples is illustrated by the
slopes of their linear polarization plots, as shown in Fig. 4(a).
The tests were carried out in a potential window of 20 mV
above and below the free corrosion potentials (FCP) of the
alloy samples, and the respective current densities (j) were
measured. The slope of the curve at j = 0 indicates the Rp of the
respective material, which is mentioned in Table 3 for all
samples. It may be noticed that the trend in the variation of Rp
among the samples matches perfectly with the variation of jcorr,
confirming an inverse relationship between these two param-
eters. It has been revealed that Ti6Al7Nb exhibits the least Rp
of 10.98 kX cm2, followed by Ti6Al4V and TNZT SPS, while
TNZT SLM45 demonstrates the highest Rp of 24.49 kX cm2.
Superior Rp for the TNZT alloys may be ascribed to the quick
formation of TiO2, Nb2O5 and ZrO2 passive layers.The
electrochemical impedance spectroscopy results for the samples
TNZT SLM45, TNZT SPS, Ti6Al4V and Ti6Al7Nb are
compared in Fig. 4(b-d). In the Nyquist plots shown in
Fig. 4(b), the experimental data are represented by discrete
points, while the simulated data are projected in the form of
curves. The nature of the Nyquist plots is similar for all the
alloys. The capacitance loops appear like incompletely resolved
arcs indicating that Rp is large. This response is a characteristic
of passive materials like Ti-based alloys in neutral electrolytes
at body temperature (Ref 62). The diameter of the arcs, when
extended to a semicircle, represents the resistance to polariza-
tion (Rp) of the respective alloy in PBS. Among all the alloys,
TNZT SLM samples showed the highest Rp, whereas Ti6Al7Nb
showed the least under identical conditions. The Rp values
obtained by two independent methods, namely linear polariza-
tion and ac impedance spectroscopy, show excellent agreement
in both trend and magnitude as indicated in Table 3.
In order to acquire deeper insights into the nature of the
passive films, Bode phase and Bode |Z| impedance magnitude
plots have been obtained and the results have been fitted with
simulated data using appropriate circuit model. Electrochemical
impedance spectroscopy was carried out at the corresponding
open-circuit potentials (OCP) of the alloys in PBS at 37 ºC. The
Bode phase and Bode magnitude plots shown in Fig. 5(b,c),
respectively, indicate a similar pattern for all the samples. In
Fig. 4(c), the phase angle drops toward zero at high frequen-
cies, which is a typical response of the solution resistance (Rs).
Similarly, the solution resistance, Rs, is also manifested in the
Bode |Z| impedance magnitude plots (Fig. 4c) at high frequency
range (> 103 Hz), where log |z| remains constant as a function
of log (frequency). At the mid-frequency range, the phase angle
(Fig. 4c) reaches maximum and remains constant for one
Journal of Materials Engineering and Performance
Fig. 4 (a) Linear polarization (b) Nyquist plots, (c) Bode phase plots and (d) Bode magnitude plots obtained at the respective open-circuit
potentials of TNZT SLM 45, TNZT SPS, Ti6Al4V and Ti6Al7Nb alloys immersed in PBS of pH 7.45 at 37 ºC

Table 3 Various electrical parameters obtained after equivalent circuit fitting to the EIS data obtained at the respective
open-circuit potentials of TNZT SLM 0/45/90, TNZT SPS, Ti6Al4V and Ti6Al7Nb alloys immersed in PBS of pH 7.45 at
37 ºC.
Constant Phase Element
Rp, kX cm2 (CPE)

Rs, X cm2 Based on equivalent circuit Based on linear polarization Y0, lX-1 Sn n Capacitance, lF cm22

TNZT SLM45 8.10 24.80 24.49 390 0.823 113

TNZT SPS 9.71 19.90 18.99 624 0.815 196
Ti6Al4V 5.35 11.85 15.89 828 0.838 218
Ti6Al7Nb 5.66 9.98 10.99 1013 0.847 300

decade in all the samples: TNZT SLM45 (73.36º), TNZT SPS
(71.8º), Ti6Al4V (73.62º) and Ti6Al7Nb (74.27º). This is a
characteristic response of a protective passive film (Ref 63).
The Bode phase plots (Fig. 4c) also reveal an inflection in the
lower frequency range of 0.01-1Hz, which suggests that at least
two time constants are involved, probably reflecting a layered
oxide film. At frequencies less than 103 Hz, a pure capacitive
response is obtained, indicated by a large negative phase shift
in the Bode phase plot (Fig. 4c), corroborated by a straight line
with slope   1 in the Bode magnitude plot (Fig. 4d). Such a
typical capacitive response of the passive film demonstrates its
high corrosion resistance. Based on the Bode plots, as well as
the negligible v2 (error) values, an equivalent electrical circuit,
[Rs (Rp CPE)] has been fit, where CPE represents constant
phase element. The model circuit is shown in the inset of
Fig. 4(d). As can be seen from the Bode plots (Fig. 4c,d), the
fitted data (colored lines) matches perfectly with the experi-
mental data points. Hence, the above circuit model has been
employed to deduce the resistive and capacitive parameters
displayed in Table 3.
The impedance of CPE with the value of n is often
associated with a non-uniform current distribution due to a
defective passive film. CPE describes an ideal capacitor for n =
1, an ideal resistor for n = 0, and a pure inductor for n =  1.

Journal of Materials Engineering and Performance


Fig. 5 Potentiostatic polarization plots for SPS-fabricated TNZT
and SLM TNZT alloy fabricated at 45orientation with respect to the
base plate, measured in PBS of pH 7.45 at 37 C at +0.75 V with
respect to their respective open-circuit potentials
The power index values (n) for all the alloys lie in the range
0.82-0.85, which also indicates that CPE is better choice than
C for fitting the data. The conversion of Y0 (CPE) to
capacitance values is calculated by applying the following
Brug et al., equation, as described elsewhere (Ref 64):
h  i1=n
C ¼ Y0 R1 þ R 1 n1
ðEq 3Þ
S P
The Rs for TNZT alloys fall in the range 8.1-9.7 X cm2,
while that for Ti6Al4V and Ti6Al7Nb are recorded as 5.35 and
5.66 X cm2, respectively. A slightly lower Rs for the latter
alloys is probably due to the change in solution conductivity
due to mild leaching of alloying elements into the electrolyte or
active corrosion of the selective elements before passivation.
However, the values of Rs seem negligible compared to the Rp
values of the alloys. The Rp, derived from equivalent circuit
fitting, is the highest for TNZT SLM45 (24.8 kX cm2), while
the least is observed for Ti6Al7Nb (9.98 kX cm2). High Rp
values for TNZT SLM samples indicate that the charge transfer
at the solution-film interface is very low and hence the
corrosion resistance is high. Minor disparities are evident in the
Rp values derived from circuit fitting and from the linear
polarization plots, but in summary, most values agree well with
other and the overall trend in the variation is corroborated
perfectly. Furthermore, TNZT SLM samples demonstrate the
least capacitance, while the Ti6Al4V and Ti6Al7Nb alloys
show nearly double the values. Smaller capacitance values
indicate that the overall reactive area of the alloy surface is
lowered due to effective passivation. The TNZT SLM alloys
show a high Rp and a low capacitance, which confirms their
excellent corrosion resistant properties compared to the rest of
the samples.
In order to gain more information on the kinetics of passive
film formation and its effectiveness, potentiostatic current
density-time transients are recorded in the passive region, i.e.,
at +0.75 V (vs. Ag/AgCl) with respect to the open-circuit
potentials of SPS TNZT and TNZT SLM45 samples. Only the
two variants of TNZT samples have been focused in order to
obtain the influence of the processing route on the current
density-time transients of identical alloys. Figure 5 shows that
at the onset of polarization, an anodic current density of 500
lA cm2 flowed due to the charging of the double layer and
subsequent active dissolution of Ti and the alloying elements
into PBS (Ref 65). As evident from Fig. 5, a drastic decrease in
the current density with time is observed for both SPS TNZT
and TNZT SLM45 in the initial 180-200 seconds, after which
the decrease is mild. This is a typical behavior of continuous
and protective oxide film formation on passive metallic surfaces
(Ref 66). The duration required for the initial current density
(500 lA cm-2) to reduce to half (250 lA cm2) for the SPS
TNZT and TNZT SLM45 is 150 s and 70 s, respectively.
This indicates that the kinetics of passive film formation for the
TNZT SLM45 sample is more than double that of SPS TNZT
alloy. Subsequently, a steady-state value of current densities is
achieved for both alloys, where the SPS alloy displayed 79
lA cm-2, while the SLM45 alloy demonstrated 46 lA cm2.
The area under the curves indicates the amount of charge
transfer at the surface-electrolyte interface. The calculated areas
(charge densities) for SPS TNZT and TNZT SLM45 are 0.426
and 0.298 C cm2, respectively, which suggests that the charge
transfer for the SLM alloy is significantly lower. These findings
consolidate that the passive film formed on the SLM alloy is
more protective in nature. The faster film formation kinetics
and enhanced protection of the passive film on the SLM alloy
may be attributed to the fine grain size in the base material and
consequently, a larger flux of ions participating in the formation
of the oxide layer. These results strengthen the validity of the
conclusions drawn from the potentiodynamic behavior of both
the alloys at the same applied potential. The log-log plot of the
current density and time transient curves shown in the inset of
Fig. 5 indicates that each alloy demonstrates two linear portions
with slopes changing at 1 s. The negative slopes (-d log j / d
log t) for the SPS TNZT (0.40) and TNZT SLM45 (0.48)
indicate that the decrease in the current density is caused by the
commencement of oxide layer formation on the alloy surface.
The slopes, approaching a value of 0.5, indicate that the
formation of the passive film is diffusion controlled. The
continuous thickening of the passive film results in a steady
decrease in the current density. However, it competes with
substrate dissolution (of the Ti, Nb, Zr, Ta elements) into/
through the film (Ref 67) since the slope is not unity (Ref 68).
3.3 Auger Electron Spectroscopy (AES) Studies
Auger electron spectroscopy was limited to only the primary
sample of interest, viz. SLM TNZT. AES was employed to
assess the thickness of the oxide film forming on the TNZT
SLM0 alloy under normal implantation conditions. A depth
profile and variation in stoichiometry of the oxides have been
obtained on the alloy before and after 36h of immersion in PBS
of pH 7.45 at 37 ºC. Figure 6(a) shows the position on the
sample surface with a rectangular box that indicates the precise
location from which the profiles have been obtained on the as-
SLM alloy. The corresponding film thickness profiles of the
native oxide film are shown in Fig. 6(c). Similarly, Fig. 6(b,d)
represents the same location on the sample after 36 h of
immersion in PBS and its corresponding oxide layer depth
profile, respectively. Figure 6(c,d) shows that Ti and Nb are
present in the outermost surface layer, suggesting that both
participate actively in the passive film formation. No evidence
of any enrichment of Zr or Ta in the surface layer is seen. A
small amount of carbon as an impurity is also visible in the
Journal of Materials Engineering and Performance
Fig. 6 Auger images of the (a) as-polished TNZT SLM0 and (c) TNZT SLM0 after 36h immersion in PBS at 37 C. The blue boxes indicate
the specific sites selected for spectroscopic study; Auger spectra collected from the (b) as-polished TNZT SLM0 and (d) TNZT SLM0 after 36h
immersion in PBS at 37 C
spectra. The profiles suggest that the oxide-alloy interface in
both cases is not sharp, but rather graded. The average
thicknesses of the oxide layer on TNZT SLM0 before and after
immersion are 10 nm and 25 nm, respectively. These results
suggest that the immersion of SLM TNZT alloy in PBS results
in the formation of a thick, highly protective oxide layer rich in
Ti and Nb.
In general, the outstanding corrosion resistance of the TNZT
alloy has been reported as mainly due to the presence of a high
concentration (24 at%) of niobium, besides a low amount of
zirconium (4.8 at%) and tantalum (1.7 at%). NbxOy is
known to form much more quickly than TiOx due to the high
enthalpy of Nb with oxygen and both the oxides possess the
ability to self-repair in the case when passive film ruptures.
Moreover, niobium oxide is more stable than TiOx and
improves the passive nature of the film by reducing the
concentration of anions in the oxide layer (Ref 69, 70).
Ultimately, TNZT is the most favorable choice compared to the
existing commercial implant alloys, namely Ti6Al4V and
Ti6Al7Nb, due to its superior biocompatibility. The passive
layer formed on the SLM-processed TNZT samples is per-
ceived to be an n-type semiconducting film, wherein the
diffusivity of oxygen along the grain boundaries becomes more
rapid as the grain boundary area increases. Consequently, a
larger flux of metallic oxides is generated that quickly enters the
surface oxide lattice, instantly forming a highly protective
passive film.
Journal of Materials Engineering and Performance
4. Conclusions
The present study investigated the in vitro corrosion
behavior of selective laser-melted (SLM) Ti-35 wt% Nb-7
wt% Zr-5 wt% Ta (TNZT), a b alloy in correlation with its
microstructural attributes, aiming for application as a potential
biomaterial for hard tissue replacements. TNZT specimens built
at an orientation of 45 with respect to the base plate showed
the lowest corrosion current density (0.23 lA cm-2), lowest
passivation current density (59.3 lA cm-2) and highest
transpassive potential (1.25 V vs. Ag/AgCl) compared to the
TNZT samples at other orientations, spark plasma sintered
(SPS) TNZT, SPS Ti6Al4V and SPS Ti6Al7Nb samples. The
better corrosion resistance for the TNZT specimens built at 45
is attributed to their fine and equiaxed grain structure, preferred
orientation along [110] and a higher degree of lattice strains.
Electrochemical impedance spectra and potentiostatic measure-
ments confirmed that the passive film formed on the SLM
TNZT alloy was dense, defect free and protective in nature.
AES analyses confirmed that the origin of passivity of SLM
TNZT alloy in PBS was due to the formation of thick and
protective passive layer predominantly rich in Ti and Nb. The
electrochemical data suggest that the build orientation of the
SLM TNZT alloy has a significant influence on its in vitro
corrosion characteristics and the alloy outperforms the com-
mercial titanium alloys produced by SPS. Further biomedical
potential of the SLM TNZT alloy shall be investigated through
in vitro tests with osteoblast/fibroblast cells under de-aerated
conditions as a closer simulation of human physiological
environment.
Acknowledgments
Authors would like to thank the financial support from
European Regional Development fund through the projects
ASTRA 6-6 and ASTRA 35-6.
Data Availability
The datasets generated during and/or analyzed during the
current study are not publicly available as the results belong to an
ongoing research, but are available from the corresponding author
on reasonable request.
Conflict of interest
On behalf of all authors, the corresponding author states that
there is no conflict of interest.
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