J Mater Sci (2019) 54:13724–13739

Materials
M A T E R I A L S Ffor
O R Llife
I F E Ssciences
CIENCES

Anodization growth of TiO2 nanotubes on Ti–35Nb–

7Zr–5Ta alloy: effects of anodization time, strain
hardening, and crystallographic texture
Leonardo Fanton1,* , Alessandra Cremasco1 , Mariana G. Mello1 , and Rubens Caram1

1
University of Campinas (UNICAMP), Rua Mendeleyev, 200, Campinas, SP 13083-860, Brazil

Received: 17 June 2019 ABSTRACT

Accepted: 22 July 2019
Published online:
31 July 2019
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2019
Titanium and its alloys are the most suitable metallic materials available for the
fabrication of medical implants. Their biocompatibility can be improved by the
growth of TiO2 nanotubes on their surface by a simple anodization process. This
work involved an investigation into the anodization behavior of Ti–35Nb–7Zr–
5Ta (TNZT) alloy, focusing on the effect of processing conditions (anodization
time and type of electrolyte), previous strain hardening, and crystallographic
texture of the substrate. Studies about the growth of TiO2 nanotubes on b-type
titanium alloys, as the TNZT alloy, are rare in the literature. The TNZT alloy
proved to be an excellent substrate for the growth of TiO2 nanotubes, resulting
in threefold longer nanotubes than those obtained on a commercially pure (CP)
Ti substrate. Moreover, TiO2 nanowires grew after 6 h of anodization in an
organic electrolyte, which could not be achieved using the CP-Ti substrate.
Samples with different crystallographic textures displayed similar nanotube
morphology and only slight differences in grain length, indicating that grain
orientation played only a minor role in the growth kinetics. Lastly, the crys-
tallization of nanotubes at 450 °C did not alter their morphology, but caused
complete detachment of the TiO2 nanotubes at 700 °C.

Introduction temperature, pure titanium (Ti) has a hexagonal

Titanium and its alloys have enhanced corrosion
resistance and high specific strength. Albeit relatively
expensive, they are highly attractive for the aerospace
sector, where weight reduction is decisive, and for
the fabrication of medical implants, due to their good
biocompatibility and corrosion resistance. At room
close-packed (hcp) structure (a-phase). When heated
above 882 °C, it transforms into body-centered cubic
(bcc) allotropic form (b-phase) [1]. The b-phase can be
retained at room temperature in a stable or
metastable form by adding b-stabilizing alloying
elements such as Mo, Nb, Zr, and Ta. Ti alloys based
on the b-phase stand out for their relatively low

Address correspondence to E-mail: leofanton@gmail.com

https://doi.org/10.1007/s10853-019-03870-5

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J Mater Sci (2019) 54:13724–13739
elastic modulus, which is important to reduce the
stress-shielding effect [2], and their enhanced bio-
corrosion resistance [3]. Ti–35Nb–7Zr–5Ta (TNZT)
alloy is a commercially available metastable b-Ti
alloy designed for use in the manufacture of implants
with an elastic modulus of 60 GPa [3, 4] and a yield
strength of 530 MPa (solution-treated condition) [3].
Despite persistent efforts to render metallic
implants more compatible with the human body,
implant rejection is still an unresolved issue. Implant
surface properties play a major role in the implant’s
biocompatibility; thus, it is understandable that
numerous surface modifications have been proposed
to address this issue. Rougher surfaces enhance the
growth and attachment of bone cells. Therefore,
several treatments to increase the surface roughness
have been investigated, such as anodic oxidation,
grit-blasting, calcium phosphate coatings, plasma
spraying, chemical modifications [5], laser surface
melting [6], and others.
Highly ordered nanotube or nanopore oxide
structures can be grown on the surface of some
metals such as Al, Ti, Zr, Nb, W, Ta, and Hf [7]. In the
case of Ti, the growth of titanium dioxide (titania,
TiO2) nanotube arrays is attracting the attention of
researchers due to their many potential applications,
as in gas sensors, solar cells, photocatalysis, biological
applications, etc. [8]. The presence of TiO2 nanotubes
on the surface of Ti alloys can increase biocompati-
bility and reduce inflammatory processes [9, 10]. The
most common and efficient way to grow TiO2 nan-
otubes is by electrochemical synthesis (anodization),
in which an electric potential is applied between two
electrodes separated by a fluoride-containing elec-
trolyte. This is a simple process that can be applied
even to complex implant geometries [11]. The work-
ing electrode (anode) corresponds to the Ti substrate
on which the TiO2 nanotubes will grow, and the
counter electrode (cathode) is usually made of Pt,
although different materials have been used, includ-
ing stainless steel [12], Ni [13], and others [14]. Two
main types of electrolytes are used to synthesize TiO2
nanotubes, i.e., aqueous and organic. Aqueous elec-
trolytes were the first ones to be studied, and they
generally consist of hydrofluoric acid (HF) [15] or
fluoride salts [16] dissolved in water. Many organic
media can be used as organic electrolytes, including
glycerol and ethylene glycol, with the addition of
fluoride salts, commonly NH4F, and small amounts
of water. A detailed description of the evolution of
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13725
aqueous and organic electrolytes is given in a review
by Regonini et al. [17].
TiO2 nanotubes are formed during anodization due
to a combination of simultaneous processes. Metallic
Ti dissolves continuously, forming Ti4? ions that
react with the O2- ions present in water to form an
oxide (TiO2) layer. The oxide layer continues to grow
by means of field-assisted ion transport (O2- and Ti4?
ions) through the growing oxide [7]. Oxide growth is
self-limited because the electric field is reduced as the
thickness of the oxide layer increases. The use of a
fluoride-containing electrolyte is necessary because it
dissolves the TiO2 layer, creating a porous structure.
The competition between the dissolution of oxide,
which occurs preferentially at the pore/tube base,
and its field-assisted growth enables the synthesis of
TiO2 nanotubes. It has also been reported [18] that
TiO2 nanowires (sometimes called nanofibers) can be
formed on top of nanotubes. Although this phe-
nomenon is not yet fully understood, Lim and Choi
[19] proposed the ‘‘bamboo-splitting’’ model,
whereby nanotubes are vertically split by the longi-
tudinal flow of ions in the channel of nanotubes.
Nanowires have several morphological characteris-
tics that are advantageous for biological applications,
favoring cell activities. They are highly porous, have
high surface-to-volume ratios, and are similar to the
natural extracellular matrix (hydroxyapatite and
collagen fibers). TiO2 nanotubes/nanowires formed
during anodization are generally amorphous,
although they can be crystalline under certain
anodizing conditions [7]. Amorphous TiO2 nanotubes
can be crystallized by means of a subsequent heat
treatment, usually from 300 to 700 °C, and different
allotropic phases can be formed, the most common
one being anatase and rutile [20]. As for implant
applications, several studies [21] indicate that the
anatase form is more effective for the formation of
apatite, which is important for the osseointegration
process. Anatase is also better for photocatalytic
applications [22].
It is well known that nanotube morphology
depends on several factors, such as the electrolyte,
the voltage applied to the system, alloy composition,
temperature, and anodization time [23–26]. In fact,
the condition of the substrate can also affect the
growth of TiO2 nanotubes. Several studies have
shown that mechanically polished or electropolished
surfaces generate more organized nanotubes, since a
smoother surface ensures a uniform electric field
13726
distribution over the substrate surface [27, 28]. Sub-
strate grain orientation may also influence TiO2
nanotube growth, according to Leonardi et al. [29],
who anodized a CP-Ti sample using an organic
electrolyte solution composed of glycerol and 0.25
wt% NH4F and applied a voltage of 20 V to the sys-
tem for 6 h. They found that the strong influence of
grain orientation along the length of the nanotubes
was inversely proportional to the surface atom den-
sity. Crawford and Chawla [30] reached a similar
conclusion. Hence, in principle, the crystallographic
texture (preferred grain orientation) of the substrate
may play an important role in the overall morphol-
ogy of TiO2 nanotubes.
This study evaluates the electrochemical anodiza-
tion growth of self-organized TiO2 nanotubes on a
biomedical TNZT alloy, highlighting the effects of
anodization time, strain hardening, and crystallo-
graphic texture, using aqueous and organic elec-
trolytes. Although TNZT alloy is a commercially
available b-type Ti alloy designed for the fabrication
of medical implants, no reports were found on its use
as a substrate for growing TiO2 nanotubes.
Figure 1 Schematic diagram of the experimental apparatus used
for anodization.
Table 1 Chemical
composition of the TNZT Ti Nb
samples (in wt%)
54.0 ± 0.1 33.8 ± 0.1
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J Mater Sci (2019) 54:13724–13739
Experimental procedure
The Ti–35Nb–7Zr–5Ta (TNZT) alloy was melted in an
electric arc furnace under a high-purity (99.999%)
argon atmosphere. The resulting ingot was encapsu-
lated in a quartz glass tube filled with argon gas,
homogenized in a resistance furnace at 950 °C for
24 h, and water-quenched. The sample was then
cold-rolled (room temperature) using multiple passes
to prevent adiabatic heating, reducing its thickness
by up to 75%. It was then cut in two parts: One of
them was kept in the deformed (strain-hardened)
state, while the other was recrystallized for 30 min at
800 °C in a furnace in an argon atmosphere and
water-quenched. These samples are hereinafter
referred to as ‘‘strain-hardened’’ and ‘‘recrystallized’’
samples.
The composition of alloying elements in the
deformed and recrystallized substrates was exam-
ined by X-ray fluorescence spectroscopy (XRF)
Figure 2 XRD patterns (2h scan) and micrographs (VLM) of:
a strain-hardened and b recrystallized samples.
Zr Ta N (9 10-3) O (9 10-3)
7.0 ± 0.1 5.2 ± 0.1 5.99 ± 0.35 182 ± 5
J Mater Sci (2019) 54:13724–13739
Figure 3 FESEM micrographs showing the top view of the TiO2
nanotubes after 4 min, 8 min, 30 min, and 1 h of anodization in an
aqueous HF (0.3% vol.) electrolyte at a maximum voltage of 20 V,
grown on the a–d strain-hardened TNZT, e–h recrystallized
Figure 4 Side view of TiO2 nanotubes grown on a strain-
hardened TNZT substrate, after 8 min of anodization in the
aqueous electrolyte.
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13727
TNZT, and i–l CP-Ti substrates. The side view (length) of the
nanotubes is depicted in the upper right-hand corner of each
image.
(Shimadzu EDX 7000 spectrometer), while nitrogen
and oxygen gas contents were measured in a LECO
TC400 nitrogen/oxygen analyzer. The samples were
prepared for evaluation by visible-light microscopy
(VLM) by sanding them with SiC abrasive paper up
to 1500 grit, polishing them with diamond paste
(6 lm) and colloidal silica (0.05 lm), and then etching
them with Kroll reagent (6 ml HNO3, 3 ml HF, and
91 ml H2O) to reveal the grain boundaries. Phase
identification was carried out by X-ray diffraction
(XRD) (PANalytical X’Pert Pro).
The crystallographic texture of the strain-hardened
and recrystallized samples was determined by XRD
pole figure measurements (PANalytical X’Pert Pro).
To obtain a quantifiable description of the crystallo-
graphic texture, the orientation distribution functions
(ODFs) were calculated from the experimental pole
figures, using MTEX MATLABÒ toolbox software.
The method used by MTEX to calculate the ODFs is
13728 J Mater Sci (2019) 54:13724–13739

explained by Hielscher and Schaeben [31]. According Results and discussion

to common practice for rolled samples, the axes of the
external reference frame were defined as the rolling Substrate composition and microstructure
direction (RD), normal direction (ND), and transverse
direction (TD). Table 1 describes the measured chemical composi-
TiO2 nanotubes were grown by anodization on the tion of the TNZT samples. The content of alloying
rolling surface (orthogonal to ND) of the strain- elements Ti, Nb, Zr, and Ta is consistent with the
hardened and recrystallized TNZT samples. For nominal composition, and the levels of oxygen and
comparison, samples of commercially pure (CP) Ti nitrogen contamination can be considered low,
(99.6% pure, according to the supplier) were similarly according to standard specifications for Ti alloy
anodized. Before anodization, the samples were castings (ASTM B367-13-2017).
sanded with abrasive paper (up to 1500 grit) and The XRD patterns of the strain-hardened (Fig. 2a)
chemically polished by immersing them for 10 s in a and recrystallized (Fig. 2b) TNZT samples presented
solution containing equal proportions of nitric acid
and hydrofluoric acid. Chemical polishing was
employed to remove the surface layer deformed by
sanding. An electrolytic cell made of polypropylene
with interior dimensions of 50 mm diameter and
50 mm height was used. The sample to be treated
was placed in contact with the electrolyte through a
round side window, 8 mm in diameter, located at the
midpoint of the cell. A Pt foil with dimensions of
about 40 9 40 mm2 immersed in the electrolyte was
used as the cathode. The process was carried out
using two different electrolytes: (1) an aqueous
solution with 0.3% (vol.%) HF and (2) an organic
(ethylene glycol) solution with 0.5% NH4F and 10%
deionized water (vol.%). The electrolyte was stirred
continuously during the process. Direct current (DC)
was applied to the system by a power supply (BK
Precision 9201), first increasing the voltage from 0 to
20 V at a rate of 2 V min-1 and then keeping this
voltage constant until the end of the process. Samples
were prepared with different anodization times,
depending on the electrolyte employed. When the
aqueous electrolyte was used, the process was stop-
ped after 4 min, 8 min, 30 min, and 1 h, and in the
case of the organic electrolyte, the anodization times
were 8 min, 30 min, 1 h, and 6 h, always counting
from the beginning of the initial ramp. The anodiza-
tion process is schematized in Fig. 1. The morphology
of the nanotubes was examined by field emission
scanning electron microscopy (FESEM, FEI Quanta
650). Nanotube length was measured by scratching
the anodized surface with a scalpel, causing the
nanotubes to break and occasionally fall on their side.
Figure 5 a Top view and b side view of the nanotubes grown on
recrystallized TNZT substrate after 1 h of anodization in the
aqueous electrolyte, showing two groups of nanotubes with
different diameters and lengths.

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J Mater Sci (2019) 54:13724–13739
only reflections of the cubic b-phase, as was expected
for this alloy. The VLM micrograph of the strain-
hardened sample (inset in Fig. 2a) shows a typical
microstructure obtained after cold-rolling, with
highly elongated grains, while the recrystallized
sample (inset in Fig. 2b) shows well-defined equiax-
ial grains, indicating complete recrystallization. The
strain-hardened sample showed a measured hard-
ness of 246 ± 6 HV, which decreased to 198 ± 6 HV
after recrystallization.
TiO2 nanotube morphology
Figure 3 depicts the general morphology of TiO2
nanotubes grown in aqueous electrolyte after 4 min,
8 min, 30 min, and 1 h of anodization on strain-
hardened (a–d) and recrystallized (e–h) TNZT sub-
strates, and on the CP-Ti substrate (i–l) used as ref-
erence. A comparison of equal anodization times
indicates that the nanotubes grown on strain-
Figure 6 FESEM micrographs showing the top view of TiO2
nanotubes after 8 min, 30 min, 1 h, and 6 h of anodization in an
organic electrolyte (ethylene glycol ? 0.5 vol.% NH4F ? 10
vol.% deionized water) at a maximum voltage of 20 V, grown
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13729
hardened and recrystallized TNZT substrates pre-
sented similar length, diameter, and general appear-
ance, confirming that the strain-hardened condition
did not significantly affect nanotube growth. The
nanotubes grown on TNZT alloy were much longer,
reaching approximately 1500 nm after 1 h of
anodization, compared to a length of only 490 nm on
the CP-Ti substrate. The diameter of nanotubes
grown on the CP-Ti substrate was larger at the
beginning of anodization (4 and 8 min), but became
similar on the two alloys after longer anodization
times (30 min and 1 h), reaching about 90 nm. After
30 min and 60 min of anodization, the morphology of
the nanotubes was similar on all the alloys, indicating
that the maximum length and diameter had already
been attained in the first 30 min of anodization.
TiO2 nanotubes in the early stages of growth of up
to 8 min of anodization appear to be less organized,
and their diameter is about three times smaller than
the nanotubes obtained after longer anodization
on the a–d strain-hardened TNZT, e–h recrystallized TNZT, and
i–l CP-Ti substrates. The side view (length) of the nanotubes is
depicted in the upper right-hand corner of each image.
13730
times. To exemplify, the nanotubes produced after
8 min of anodization on strain-hardened TNZT sub-
strate (Fig. 3) have an apparent diameter of only
about 22 nm at their top opening. However, a side
view of the nanotubes, as in the example shown in
Fig. 4, reveals that their base is thicker, with a
diameter of approximately 65 nm. A nanoporous
layer of TiO2 is initially formed at the beginning of
the anodization process. After some time, nanotubes
begin to grow and their diameter increases as the
process continues. This initial porous structure is still
present during the first 8 min of anodization as a
remnant layer on top of the nanotubes, as seen in
Fig. 4, resulting in nanotubes of poor quality. This
initial nanopore/nanotube layer is consumed during
the process, and the diameter at the top of nanotubes
is considerably larger after longer anodization times.
After 30 min and 1 h of anodization, the TiO2
nanotubes grown on TNZT substrates (both strain-
hardened and recrystallized) (Fig. 3c, d, g, h) can be
divided into two groups of different sizes. The nan-
otubes grown on the CP-Ti substrate did not exhibit
this behavior. Figure 5a clearly shows a group of
Figure 7 Cross sections of TiO2 nanotubes from their base (near
the substrate) to their tip (top opening), grown in the organic
electrolyte on a–c the TNZT substrate after 30 min of anodization,
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J Mater Sci (2019) 54:13724–13739
nanotubes with larger diameters (about 85 nm),
spaced apart from each other, surrounded by a sec-
ond group of nanotubes whose diameter is approxi-
mately half that of the first group. The narrower
nanotubes also appear to be slightly shorter, which
can be confirmed by a side view (Fig. 5b). TiO2 nan-
otubes ordered on two different scales have already
been reported by Ozkan et al. [32, 33], but with a very
different morphology. Their SEM images show that
the longer nanotubes of the first group were about
2 lm in length, while the shorter nanotubes in the
second group were only about 0.1 lm in length and
were morphologically thinner. They also found that
the shorter nanotubes split after a short growth,
forming a stack of small nanotubes. The size of this
stack of nanotubes was very limited, since it was
easily dissolved by etching after some time during
anodization. However, none of the characteristics
reported by Ozkan et al. was observed in our study.
Figure 6 shows the general morphology of the
nanotubes grown in the organic electrolyte after
8 min, 30 min, 1 h, and 6 h of anodization on strain-
hardened TNZT (a–d), recrystallized TNZT (e–h),
showing different perspectives of the initial growth process, and on
d–f the CP-Ti substrate, after different anodization times.
J Mater Sci (2019) 54:13724–13739
and CP-Ti (i–l) substrates. The morphologies of the
nanotubes grown on strain-hardened and recrystal-
lized TNZT substrates were similar. The maximum
length of the nanotubes grown on the TNZT alloy
was about 5000 nm, which was reached during the
first hour of anodization. However, after 6 h of
anodization, TiO2 nanowire structures were found to
grow on top of the nanotubes. This growth, which
will be discussed later, was not considered in the
measurement of nanotube length. After 1 h of
anodization, the nanotubes grown on the CP-Ti
substrate reached a length of about 1200 nm, which
more than doubled after 6 h of anodization, reaching
about 3300 nm. However, the surface of the nan-
otubes after 6 h of anodization showed an irregular
aspect, called ‘‘nanograss’’ [34], which is characteristic
of longer anodization times, leading to excessive
etching in the electrolyte. In general, the diameter of
Figure 8 a Length and
b diameter of nanotubes
grown in aqueous (0.3% vol.
HF) and organic (ethylene
glycol ? 0.5 vol.%
NH4F ? 10 vol.% deionized
water) electrolytes after
different anodization times at a
maximum voltage of 20 V.
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13731
the nanotubes grown in organic electrolyte was sig-
nificantly smaller than those of the nanotubes grown
in aqueous electrolyte. The maximum nanotube
diameter reached on the TNZT alloy was 39 nm (after
1 h), and on the CP-Ti substrate, it was about 68 nm
(after 6 h).
As explained in the ‘‘Experimental procedure’’
section, the surface of TiO2 nanotubes was scratched
with a scalpel in order to separate the nanotubes from
the substrate, enabling them to be viewed from the
side. In the case of nanotubes grown in organic
electrolyte, this procedure also caused some nan-
otubes to break in several sections along their length,
enabling the nanotube growth process to be exam-
ined in greater detail. Figure 7 shows some examples
of nanotubes grown on the CP-Ti and TNZT sub-
strates. In each case, note that the nanotubes are
considerably thicker close to their base, which can be
13732 J Mater Sci (2019) 54:13724–13739

explained by the fact that the upper portion of the
nanotubes is older and was therefore etched by the
electrolyte solution for a longer time.
Similarly to the anodization process in aqueous
electrolyte (Fig. 4), a residual porous layer was visi-
ble on the nanotubes in the initial stages of anodiza-
tion. In the case of nanotubes grown on TNZT
substrate, this layer was still present after 30 min of
anodization (Fig. 7a, b, c), but on those grown on CP-
Ti substrate it was only visible after 8 min (Fig. 7d),
having disappeared after longer anodization times
(Fig. 7e, f). The porous layer took longer to consume
in both aqueous and organic electrolytes when
anodization was performed on TNZT substrate. The
nanotubes grown on TNZT substrate appeared to be
more resistant to etching during anodization, which
may also explain why they were able to grow longer.
The graph shown in Fig. 8 depicts the length and
diameter of TiO2 nanotubes grown on CP-Ti and
TNZT substrates after different anodization times in
aqueous and organic electrolytes.
As a reference, Table 2 shows the percentage of
grains whose {100}, {110}, and {111} planes are ori-
ented parallel to the rolling surface, considering a
misorientation tolerance angle of 15°.
Considering a0 as the lattice parameter of the bcc
unity cell, the relative atomic densities of the {100},
{110}, and {111} planes are, respectively, 1.00, 1.41,
and 0.58 atoms per a20. Given that atomic planes of
lower density favor TiO2 nanotube growth [29, 30],
the crystallographic texture of the recrystallized
TNZT sample should, in principle, result in a higher
average length of TiO2 nanotubes. However, the
length of both strain-hardened and recrystallized
nanotube samples is similar. In addition, only minor
changes in length from grain to grain are visible in

Effect of crystallographic texture

An XRD crystallographic texture analysis was made

of the strain-hardened and recrystallized TNZT
samples. The ODF calculated from the experimental
pole figures provides a complete description of the
texture, but the most important information to be
extracted from this result is the planes that are pref-
erentially exposed on the substrate surface, since
their density may influence the growth of TiO2 nan-
otubes to some degree [29, 30]. The most practical
way to display this information is through inverse
pole figures (IPFs). Figure 9 illustrates the IPFs of the
strain-hardened and recrystallized substrates, show- Figure 9 Inverse pole figures (IPFs) of the a strain-hardened and
ing the crystals planes that are most frequently par- b recrystallized samples, showing the crystal planes that are
allel to the rolling direction (orthogonal to the ND). preferentially parallel to the rolling surface (orthogonal to ND).
The intensity of the IPFs is indicated in multiples of The intensity of the IPFs is indicated in multiples of uniform
uniform density, i.e., in the number of times a certain density (MUD).
plane is more frequently aligned to the rolling surface
compared to a non-textured (uniform orientation Table 2 Fraction of grains with their {hkl} plane oriented parallel
density) material. The IPF of the strain-hardened to the substrate surface, considering a misorientation tolerance
sample shows a strong intensity on the {100} plane angle of 15°
(Fig. 9a), which means that the {100} plane of most of
Crystal plane Strain-hardened TNZT Recrystallized TNZT
the grains is parallel to the rolling surface. The
{hkl} (%) (%)
intensities of the IPFs of the recrystallized sample
(Fig. 9b) are significantly weaker, indicating a more {100} 52.4 13.6
varied distribution of orientations, with a maximum {110} 2.1 9.8
intensity on the {111} plane. {111} 18.0 22.6

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J Mater Sci (2019) 54:13724–13739
the recrystallized TNZT and CP-Ti samples. After
4 min of anodization in the aqueous electrolyte,
nanotube growth on the CP-Ti sample was found to
be inhomogeneous. As can be seen in the low-mag-
nification SEM image in Fig. 10a, some grains are
brighter than others. A closer look at Fig. 10b, c
reveals that the nanotubes with brighter grains have a
well-defined porous/tubular structure, while the
darker grains appear to indicate an earlier stage of
the anodization process. After 1 h of anodization,
some grains, albeit only a few, still showed slight
differences in length (Fig. 10d). A reasonable expla-
nation for the differences in grain length is that their
orientation affected the TiO2 nanotube growth rate,
since this was the only characteristic that varied from
one grain to another. However, these variations in
length were not as significant as those reported by
Leonardi et al. [29]. Differences in the surface
preparation employed in our study and in that of
Leonardi et al. may have been the cause of this
Figure 10 SEM micrographs illustrating the difference in TiO2
nanotube morphology between different grains after anodization.
a Low-magnification image of the CP-Ti sample after 4 min of
anodization in aqueous solution, showing grains with (light
regions) and without (dark regions) nanotubes. b, c High-
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13733
contradictory finding. Those authors used electrolytic
polishing to remove the layer deformed during the
preceding mechanical polishing, while we employed
chemical polishing in our study. The sample grown
on recrystallized TNZT showed slight differences in
nanotube length between grains after 8 min of
anodization in organic solution, as illustrated in
Fig. 10e. However, this behavior was not observed
after longer periods of anodization in either the
aqueous or the organic electrolyte solutions. No
information was found in the literature about the
effect of grain orientation on the growth of TiO2
nanotubes on b-Ti alloys. The degree of anisotropy of
the cubic structure of b-Ti phase is lower than that of
the hexagonal a-phase present in CP-Ti alloy, which
in principle should reduce the influence of grain
orientation on nanotube growth. Moreover, the fact
that the nanotubes grown on the recrystallized sam-
ple presented the same morphology as those grown
on the strain-hardened sample is another indication
magnification images of the same sample shown in (a).
d Surface of nanotubes grown on the CP-Ti sample after 1 h of
anodization in aqueous solution. e Surface of nanotubes on the
recrystallized TNZT sample after 8 min of anodization in organic
solution.
13734
Figure 11 SEM micrographs of the nanowires formed on TNZT
samples after anodization in the organic electrolyte. a Onset of
nanowire formation after 1 h of anodization, with the sample tilted
at an angle of 45° to facilitate viewing. b Top-view image of
nanowires after 6 h of anodization. c High-magnification image of
that grain orientation does not play a significant role
in the anodization process.
TiO2 nanowires
As already shown in Fig. 6, TiO2 nanowires were
found to grow on nanotubes during the anodization
of TNZT substrates in the organic electrolyte solu-
tion. The formation of nanowires began after 1 h of
anodization. Albeit not clearly visible in the top view
images (Fig. 6g, k), nanowire clusters were detected
upon tilting the sample at an angle of 45° (Fig. 11a).
After 6 h of anodization, the nanowires were much
longer, well developed, and still grouped in clusters
(Fig. 11b). Individual nanowires were visible under
higher magnification (Fig. 11c), evidently growing
from the borders of the nanotubes underneath them.
This finding is consistent with the ‘‘bamboo-splitting’’
model proposed by Lim and Choi [19] to explain the
formation of TiO2 nanowires. A side view of the TiO2
nanostructures (Fig. 11d, e) reveals the nanotube and
nanowire sizes. Measuring the actual length of
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J Mater Sci (2019) 54:13724–13739
the same sample shown in (b). d, e Side views of the nanotubes
covered with nanowires after 6 h of anodization. f Image of a
region where the nanowires were broken, providing a view of the
underlying nanotubes.
nanowires is difficult because of their flexibility and
hair-like appearance. However, it is reasonable to
assume that they are more than 5 lm long, and
longer than the underlying nanotubes. Figure 11f
shows a region where the nanowires were acciden-
tally broken, providing a clear view of the nanotubes
underneath them.
It has been already reported [19] that nanowires
can be grown through the anodization of CP-Ti in
ethylene glycol ? NH4F electrolytes. However, they
were only formed upon applying voltages above
80 V. The formation of TiO2 nanowires on TNZT
substrates using a voltage of only 20 V indicates that
this alloy is an excellent substrate for nanowire
growth.
Crystallization of TiO2 nanotubes
Heat treatments were applied at 450 and 700 °C for
1 h to evaluate the crystallization behavior of TiO2
nanostructures. The samples chosen for this analysis
were the ones anodized for 6 h in organic electrolyte,
J Mater Sci (2019) 54:13724–13739 13735

Figure 13 XRD analysis of nanotubes grown on a CP-Ti

Figure 12 XRD analysis of nanotubes grown on a TNZT
substrate after 1 h of anodization in organic solution (ethylene
substrate after 1 h of anodization in organic solution, a as-
glycol ? 0.5 vol.% NH4F ? 10 vol.% deionized water). a As-
anodized and heat-treated at b 450 °C and c 700 °C for 1 h. The
anodized, b heat-treated at 450 °C for 1 h, and c heat-treated at
insets in (b) and (c) are SEM (backscatter detector) cross-sectional
700 °C for 1 h. The inset in (c) is a visible-light microscopy image
images of the region near the surface.
(real colors) of the nanotube surface.
which was the condition that produced the longer
Fig. 12c). This result was similar to that of the ano-
nanotubes. Figure 12 shows the XRD patterns of TiO2
dized specimens; hence, the TiO2 nanotube layer was
nanotubes/nanowires grown on the TNZT sample.
not related to a-phase precipitation. The cross sec-
The as-anodized nanotubes did not present peaks
tions of the substrates were investigated by SEM.
corresponding to any crystalline phase other than the
While the sample treated at 450 °C showed only
substrate (b-Ti), indicating their amorphous nature
equiaxed b-phase grains (inset in Fig. 12b), the sam-
(Fig. 12a). After a heat treatment at 450 °C, several
ple treated at 700 °C presented a-precipitates close to
anatase peaks and one rutile peak were detected
the surface, which was revealed by their darker shade
(Fig. 12b). When treated at 700 °C, the XRD patterns
(inset in Fig. 12c). An XRD analysis of the cross sec-
showed anatase and rutile peaks similar to those of
tion of the surface of the sample treated at 700 °C
the sample heat-treated at 450 °C. However, peaks of
(third XRD pattern in Fig. 12c) showed only b-peaks,
metallic a-Ti phase were also observed, which was
which is explained by the fact that a-precipitates are
not expected. To determine the source of the a-phase,
present only in a very thin layer near the surface. The
non-anodized TNZT samples were also heat-treated
precipitation of a-phase close to the surface of b-Ti
at 450 and 700 °C for 1 h and their surfaces were
alloys after heat treatments is a common phe-
analyzed by XRD. The sample treated at 450 °C
nomenon [35]. This precipitation is attributed to the
showed only b-peaks (second XRD pattern in
high affinity of Ti to absorb oxygen from the atmo-
Fig. 12b), while the sample treated at 700 °C showed
sphere, which is an element known to stabilize the a-
peaks of a- and b-phases (second XRD pattern in

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13736 J Mater Sci (2019) 54:13724–13739

Figure 14 SEM micrographs

of TiO2 nanotubes/nanowires
grown on the CP-Ti and TNZT
substrates, after 6 h of
anodization in organic
electrolyte and heat-treated at
a, b 450 °C and c, d 700 °C
for 1 h. The insets in (b), (c),
and (d) show high-
magnification images of the
regions marked in a black
rectangle.

phase. Although the heat treatments were performed
in a protective argon atmosphere, the relatively high
temperature (700 °C) may have facilitated the
absorption of some residual oxygen.
Figure 13 shows XRD patterns of nanotubes grown
on the CP-Ti substrate. As expected, only peaks of the
substrate (a-Ti) were visible before the heat treatment
(Fig. 13a). After the heat treatment at 450 °C, crys-
tallization occurred and anatase peaks became visible
(Fig. 13b), but no rutile phase was detected. When
treated at 700 °C, three titanium oxide allotropes
were detected: anatase, rutile, and Ti2O3 (Fig. 13c).
The anatase peaks were more intense than those of
the sample treated at 450 °C, indicating that the
amount of this phase was higher. The nanotube and
substrate surfaces acquired a strong blue coloration
(see inset in Fig. 13c), which is the characteristic color
of Ti2O3 phase [36].
The morphology of the TiO2 nanostructures was
examined after applying crystallization heat treat-
ments. After the heat treatment at 450 °C, the nan-
otubes grown on the CP-Ti substrate (Fig. 14a) and
the nanotubes/nanowires grown on the TNZT sub-
strate (Fig. 14b) showed a similar appearance to those
observed before the treatments (Fig. 6d, h). However,
when heat-treated at 700 °C, the TiO2 nanotubes
grown on the CP-Ti sample cracked (Fig. 14c) and
became detached from the substrate, as can be seen
by the elevation of the nanotubes near the cracks
(inset in Fig. 14c). This effect was even worse on the
TNZT substrate, where the nanotubes became com-
pletely detached from the substrate, forming small
‘‘blocks’’ of nanotubes that were visible all over the
surface (Fig. 14d). No nanotubes remained on the
substrate surface, indicating that the nanotubes broke
at their base, as illustrated by several detached blocks
that were turned upside down (inset in Fig. 14d).
Losertová et al. [37] also reported the collapse of TiO2
nanotubes after heat treatments, showing that it is an
important issue to be taken into consideration when
choosing the crystallization treatment temperature.
Conclusions
(a) The TNZT substrate proved to be suitable for
growing TiO2 nanotubes, enabling the

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J Mater Sci (2019) 54:13724–13739
formation of threefold longer nanotubes than
those grown on the CP-Ti substrate.
(b) The nanotubes grown on the recrystallized and
strain-hardened TNZT substrates showed no
significant morphological difference. Moreover,
the crystallographic texture also did not play an
important role.
(c) TiO2 nanotubes grown on the TNZT samples
presented two groups of different scales, with
characteristics that have never before been
reported in the literature.
(d) Upon anodizing the TNZT sample in organic
electrolyte for 6 h, long nanowires grew on top
of the nanotubes, in conditions that would not
be possible using a CP-Ti substrate.
(e) Crystallization of the nanotubes grown on the
TNZT substrate was successful after 1 h of heat
treatment at 450 °C, forming anatase and rutile
phases with no noticeable change in the nan-
otube morphology. However, crystallization at
700 °C for 1 h caused detachment of the
nanotubes from the substrate and a-phase
precipitation.
Acknowledgements
The authors gratefully acknowledge LNNano/
CNPEM (National Nanotechnology Laboratory of
the National Center for Research on Energy and
Materials) for providing access to its SEM facilities.
This work was supported by the Brazilian research
funding agency FAPESP (São Paulo Research Foun-
dation) [Grant #2017/16715-0].
Authors’ contributions
LF is the main author, performed the experiments,
and took the lead in writing the paper. MGM and AC
contributed to the implementation of the research
and to the interpretation of the results. RC designed
and supervised the study and revised the
manuscript.
Compliance with ethical standards
Conflict of interest All authors declare that they
have no conflict of interest.
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
13737
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