JABFM

Journal of Applied Biomaterials &

Functional Materials
2018, Vol. 16(1) 3­–13
© The Author(s) 2017
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DOI: 10.5301/jabfm.5000396
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Corrosion of titanium: Part 2: Effects

of surface treatments
Davide Prando1,2, Andrea Brenna1,2, Maria Vittoria Diamanti1,2, Silvia Beretta1,2,
Fabio Bolzoni1,2, Marco Ormellese1,2, MariaPia Pedeferri1,2

 Department of Chemistry, Materials and Chemical Engineering “G. Natta”, Politecnico di Milano, Milan - Italy
1

 National Interuniversity Consortium of Materials Science and Technology, Florence - Italy

2

ABSTRACT
Titanium is well known as one of the most corrosion-resistant metals. However, it can suffer corrosion attacks in
some specific aggressive conditions. To further increase its corrosion resistance, it is possible either to modify its
surface, tuning either thickness, composition, morphology or structure of the oxide that spontaneously forms on
the metal, or to modify its bulk composition. Part 2 of this review is dedicated to the corrosion of titanium and
focuses on possible titanium treatments that can increase corrosion resistance. Both surface treatments, such as
anodization or thermal or chemical oxidation, and bulk treatments, such as alloying, are considered, highlighting
the advantages of each technique.
Keywords: Anodization, Corrosion, Thermal oxidation, TiO2, Titanium

Introduction methanol, nitrogen tetroxide, red-fuming nitric acid or solid

Titanium has outstanding corrosion resistance due to a
thin, amorphous, nonstoichiometric TiO2 protective layer
(max. 10-nm thick (1)) that is formed spontaneously on the
surface when exposed to an aerated environment. This pro-
tective layer is very stable and allows the use of titanium in
severe working conditions, such as offshore; in an acid envi-
ronment; in aerospace (2, 3) and automotive industries; in
high-temperature applications; in the chemical and food in-
dustries (4-6); and in marine hydrometallurgical applications
and nuclear fuel waste containment (7-10), where no other
metal can be used.
Nevertheless, commercially pure titanium may suffer dif-
ferent forms of corrosion in very severe environments (11).
­Generalized corrosion is caused by small quantities of fluoride
ions (more than 0.002 M that combine with titanium, form-
ing TiF4, and destroy the passivity film. Hydrogen embrittle-
ment happens mainly on α and α-β titanium, due to the low
hydrogen solubility in α-Ti (12). Stress corrosion cracking can
also happen in very specific environments, such as anhydrous
Accepted: November 1, 2017
Published online: November 21, 2017
Corresponding author:
Prof. MariaPia Pedeferri
Department of Chemistry
Materials and Chemical Engineering “G. Natta”
Politecnico di Milano
Via Mancinelli 7
20131 Milano, Italy
mariapia.pedeferri@polimi.it
cadmium (13). However, the most critical forms of corrosion
of titanium are due to localized breaking of the passive layer,
and this is favored by the presence of concentrated halides,
such hot salty water (above 200°C) or bromide-containing
species (14, 15).
To overcome this weakness, corrosion resistance–­
enhancing treatments can be completed, or proper alloying
elements may be added; the latter is the case with inclusion
of elements that promote cathodic reactions, raising the
cathodic polarization curve above the critical active anodic
curve at higher potentials in the passive region, such as with
palladium (16). A well-know treatment is nitration, which in-
volves introducing nitrogen in the first micrometer of the sur-
face to promote the formation of TiN and increase corrosion
resistance (17, 18). These methods, acting on the titanium
composition, are effective but complicated to perform and
expensive, as are other surface coating techniques, such as
vacuum plasma spray coating, plasma spraying and chemical
vapor deposition (19).
For this reason, treatments that act on the naturally
formed passive layer are preferred. The easiest and cheapest
treatment to tune the oxide layer is anodic oxidation, which
involves applying an anodic polarization of several 10s of
volts to the metal, promoting the growth of the natural oxide
layer with thicknesses from about 40 nm, with an anodizing
potential of 10 V, to about 250 nm at 100 V (20-22). At po-
tentials higher than 100 V, the anodizing begins to cause the
instauration of microarcs in the insulating oxide layer; in this
regime, called anodic spark deposition or plasma electrolytic
oxidation (PEO), the oxide grows much more, reaching the
thickness of several micrometers but switching from a com-
pact to a porous structure (23).
e4
Due to the promising results with increasing corrosion re-
sistance using anodizing treatments, as described in this re-
view the effect of anodizing potential has been investigated,
with values ranging from 10 to 200 V, to define a treatment
procedure able to delay or prevent localized corrosion in very
severe environments.
Surface treatments are greatly influenced by the condition
of the initial surface, in terms of roughness and chemical com-
position. Prior to any anodizing treatment, the surface has to be
degreased, cleaned and have any adsorbed chemicals removed;
for this reason, pretreatments such as etching and mechanical
polishing are required. Moreover, by controlling the conditions
of these pretreatments, it is possible to obtain a similar surface
roughness on all titanium samples prior to oxidation. However,
to perform chemical etching on titanium, a hydrofluoric acid–
containing solution has to be used, and this is reported to cause
fluoride surface enrichment (24, 25). To investigate the effect
of the presence of bromides on anodized titanium corrosion
resistance, the same treatments, in terms of final potential, an-
odizing solution and anodizing current density, are performed
on samples prepared with the 2 different pretreatments. The
samples are then tested for corrosion resistance.
The corrosion resistance of each metal strongly depends
on its surface behavior when exposed to corrosive agents:
The development of a protective passive layer is required, to
reach a passive state in which corrosion is still proceeding but
at such a low rate as to be negligible. For this reason, barrier
layer treatments are very important to increase the corrosion
resistance of metals. The most common and promising treat-
ments to increase titanium corrosion resistance are described
in the next sections.
Anodizing
Anodizing is one of the easiest techniques for modifying
the thickness, composition and morphology of oxides ap-
pearing on valve metals, such as aluminum and titanium. The
treatment involves anodically polarizing a metal to a fixed
voltage in an electrochemical cell containing a counter elec-
trode and an electrolyte providing conduction. Common elec-
trolytes are acids, such as H2SO4 and H3PO4, and salts, such as
(NH4)2SO4, Na2SO4 and NH4BF4.
The main parameters affecting the characteristics of the
resulting oxides are as follows (19, 26, 27):
• Current density of anodization;
• Anodizing voltage;
• Duration;
• Electrolyte composition, pH, concentration and tempera-
ture;
• Agitation of the solution;
• Chemical composition and surface finishing of the
­electrode.
Increasing the current density of anodization accelerates
the oxidation rate and increases the amount of oxide convert-
ed from an amorphous state to anatase or even rutile crystal-
line structure (28), as shown in Figure 1.
Titanium anodized up to 120 V shows the appearance of
a surface color, which is due to interference between light
Ti surface treatment to improve corrosion resistance
Fig. 1 - Relationship between anodization potential and anatase
peak intensity on titanium anodized in 0.5 H2SO4 at different cur-
rent densities (19).
and the oxide layer and is dependent on the oxide thick-
ness, in the range of 10s of 100s of nanometers (29). For
this reason, anodizing techniques are distinguished be-
tween color anodizing, also known as traditional anodizing,
with voltages below 100-120 V, and anodic spark deposi-
tion or PEO anodizing, which will be further described in
the section “Anodic spark deposition or plasma electrolytic
oxidation.”
Traditional anodizing
Oxide thickness is directly related to anodizing voltage
and can be estimated by analysis of the sample reflectance
spectrum, following the equation (6):
nTio2 l = 2d sinq Eq. [1]
where nTiO2 is the refractive index of TiO2, λ is the radiation
wavelength giving constructive or destructive interference
and θ the angle of incidence of light (22).
With increasing anodizing voltage, there is an increase in
film thickness, crystallinity and porosity. In Table I, the anodic
film thickness obtained on Ti anodized at different voltages
in sulfuric acid is reported (30): each anodizing treatment re-
sults in a significant reduction of corrosion rate. As can be
noted, the sample anodized at 10 V shows lowest corrosion
rate. The increase in corrosion rate with anodizing potential
is reported to be due to increasing porosity of the anodized
layer; however, every anodizing treatment increases the cor-
rosion resistance of titanium (30, 31, 32).
Several studies have found correlations between applied
voltage and film thickness. The anodizing ratio is generally
observed to be in the range of 1.5 to 3 nm/V.
The electrolyte used for anodization may vary regarding
the ease of film growth, chemical composition of the oxide
and oxide crystallinity. In sulfuric acid, for example, anodizing
potential was reported to grow faster with a concentration
of 0.5 M, within the range from 0.25 M to 2 M studied (19).
Liu et al (33) reported that oxide growth in H2SO4 compared
with that in H3PO4 had a higher free corrosion potential, but
Prando et al e5

further observation indicated there was oxide rupture due to
oxygen bubbles formed from oxygen evolution during anod-
ization. The oxide rupture appeared to be more severe when
produced in 1 M sulfuric acid than 1 M phosphoric acid, indi-
cating that the oxygen evolution reaction was not favored in
the phosphoric acid.
Anodizing treatment can be modified to achieve better
corrosion resistance; one example of this is the introduc-
tion of nitrogen into a titanium lattice prior to anodization.
This nitridation can be performed by a plasma nitriding unit,
which uses nitrogen plasma in vacuum (34), or through an an-
nealing treatment in a nitrogen environment (35). Nitrogen
is reported to have a beneficial effect on anodization due to
the fact that TiN is overstoichiometric with a weak bond exist-
ing between Ti and N atoms. Thus, while in the conventional
anodization process, anatase TiO2 hardly forms on titanium
surfaces, because of the passive amorphous film that acts as
a barrier to prevent further anodization, the presence of TiN
helps oxide growth and crystallization. It should also be noted
that titanium has a hexagonal close-packed structure, while
TiN has a cubic structure, so oxygen atoms can easily migrate
into the TiN crystal structure due to its low atomic packing
factor (34).
Anodic spark deposition or plasma electrolytic oxidation
Anodization is the common term to refer to the applica-
tion of anodic current to a metal, in order to increase the
thickness of the oxide. When the applied voltage reaches
sufficiently high values – in most cases above 100 V – oxida-
tion of titanium slows down, due to the thick protective and
almost insulating oxide formed on the metal. Yet, oxides are
always defective, therefore if the voltage and current applied
are sufficiently high and a threshold potential is reached, the
electric field will be high enough to break the dielectric, and
sparks will start to appear in the oxide layer, leading to local-
ized heating up to 5000-7000 K (36). In this case, anodization
is referred to, as previously mentioned, as anodic spark de-
position, or PEO or micro-arc oxidation (37, 38). The stages of
PEO are primary anodic oxidation which generates a passive
oxide of growing thickness, then the onset of microarcs at the
oxide surface that are formed when higher voltages are ap-
plied (39). At the point where the arc occurs, the substrate
reacts with the electrolyte, and an oxide layer, thicker than
the one previously formed and with a crystalline structure, is
formed. This oxide layer is an even better insulator than the
passive layer initially formed; the next arc acts on a different
site, until the substrate is fully and homogeneously covered
with the ceramic coating.
PEO usually forms oxides from 10ths to a 100 microme-
ters thick (40), with compared with traditional anodizing that
produces oxides up to 300 nm. This technique is also interest-
ing because of its ability to transfer chemical species from
the electrolyte to the oxide. In fact, local melting and solidi-
fication of the oxide leads particles and ions present in the
electrolyte to be incorporated into the TiO2.
For instance, by executing the treatment in Na2SiO3, it is
possible to enrich the surface layer with Si and Na. At 400 V,
this produces a layer with a complex structure composed of
an inner portion, adjacent to the titanium, which contains

TABLE I - Anodic films grown on titanium anodized in sulfuric acid: refractive index, thickness, free corrosion potential and corrosion rate

Anodizing voltage (V) λmax (nm) Anodic film Anodic film thickness Corrosion potential Corrosion rate
refractive index (nm) (mV vs. SCE) (µ/year)

5 259 1.458 44 -399.7 391

10 319 1.454 84 -365.1 2.3
15 348 1.451 59 -339.9 0.96
20 366 1.449 63 -336.9 2.35
25 398 1.446 68 -355.2 1.01
30 452 1.440 78 -293.1 4.38
35 541 1.427 94 -287 5.41
40 519 1.430 90 -338.5 3.51
45 545 1.427 95 -260.3 2.87
50 569 1.423 99 -251.4 7.78
55 643 1.410 114 -236.9 3.16
60 780 1.379 141 -247.2 7.3
65 802 1.374 145 -264.9 12.21
70 826 1.376 150 -261.9 8.67
75 912 1.342 169 -256.2 4.95
80 1000 1.311 190 -295.6 11.48
SCE = saturated calomel electrode.
e6
mainly TiO2, and an outer portion built primarily of silicon, so-
dium and oxygen compounds (41). The outer layer is mostly
porous and does not contribute efficiently to corrosion resis-
tance, which is an effect provided by the inner layer. However,
morphology, chemical composition and phase composition of
the surface are changed, and this finds applications in other
fields, such as biomedical implants. In another study (42),
the formation of titanium silicides above 250 V was report-
ed: TiSix are known as corrosion resistant compounds, and
the electrolyte with the higher amount of Na2SiO3·5H2O and
Na3PO4 produces the most corrosion resistant oxide.
A possible explanation for the enhanced corrosion resis-
tance of samples anodized in silicon containing electrolytes
is given by Hu et al (43). They found that the higher con-
ductivity of Na2SiO3-containing electrolyte gives a denser
microstructure compared with respect electrolytes that do
not contain this additive, leading to a more protective and
insulating layer.
Babaei et al (44) studied the effect of the addition of
Zr-containing species to the anodizing electrolyte: Na2ZrO3
was used for this purpose. They found that ZrOx and ZrTiO4
were formed in the oxide layer during anodization. TiO2 im-
mersed in aggressive media for a long time hydrates to form
Ti(OH)4, dissolving into the solution; as ZrO2 has higher sta-
bility in aqueous solution, its incorporation into the layer
increases the corrosion protection of the metallic substrate,
provided by the anodic oxide. On the other hand, the ad-
dition of Na2ZrO3 usually decreases electrolyte resistivity,
leading to more powerful microdischarges, which create
bigger pores on the surface, with a detrimental effect on
corrosion resistance.
Chlorides can also be used to tune titanium oxide proper-
ties. It is reported that PEO treatment on preanodized ­surfaces
with low-voltage alternating current in a HCl environment
causes the growth of a thick and rough oxide, which can be
suitable for purposes where multiple scale roughnesses are
desired (20) – e.g., in biomedical applications. In contrast, the
use of Cl--containing electrolyte during PEO causes the growth
of a chlorine-rich region on the oxide, with the formation of
TiCl4 species. This phenomenon needs to be avoided, because
it causes oxide cracking (45).
The voltage reached during PEO treatment is reported to
influence not only film thickness and crystallinity, but also
morphology. Galvis et al (23) performed galvanostatic PEO
treatment on titanium at 50 mA/cm2 current density, reach-
ing a voltage up to 260 V. They report a transition poten-
tial between grooved and porous structure that depended
strongly on the composition of electrolyte and weakly on the
current density.
The effect of anodizing duration was studied by Mizuko-
shi et al (46), by anodizing in 1.2 M sulfuric acid for 2, 5, 10,
30 and 60 minutes at 8 mA/cm2 of current density, reach-
ing a maximum voltage of 210 V after 33 minutes. They re-
port an intense dependence of surface structure and oxide
­crystallinity on anodizing duration, as can be seen in ­Figure 2.
In the beginning of the anodization (2-10 minutes), polished
traces on Ti substrate could be observed. With the progres-
sion of anodization, concave curvatures 10s of micrometers
in diameter appeared, suggesting spalling of the formed ox-
ide from the surface during anodization. ­After ­anodization
Ti surface treatment to improve corrosion resistance
progressed for 30 or 60 min, the polished traces were no
longer observed, but concave curvatures were formed all
across the Ti substrate. At high magnification, pores were
visible throughout the course of the anodization. Pores co-
alesced into larger-sized pores, and the surface roughness
of the oxide increased with the progression of the anodiza-
tion (46). The same study reported a conversion of the oxide
from anatase to rutile phase with increasing anodizing time:
the maximum rutile conversion (1%) was reached after 20
minutes. This conversion was low in percentage terms and
much less pronounced than that given by a higher anodizing
voltage (19).
Liu and Thompson (1) have proposed an oxide growth
mechanism for anodic spark deposition in phosphoric acid
(Fig. 3). During oxidation, pores are found to grow prefer-
entially within the outer porous oxide layer. These pores
are formed by localized oxide breakdown and oxidation of
O2- ions, either from the already formed TiO2 matrix or from
migrating oxygen ions, to become molecular oxygen, which
accumulates in O2 bubbles. Here in the porous layer, oxygen
is developed and released through the pore channels, and
the oxidation of O2- is favored by crystallites, and thus, a
high ionic resistivity is offered, which leads to higher elec-
tric fields than the corresponding amorphous oxide (47).
Moreover, the anatase phase has a better electric con-
ductivity than amorphous titanium, and favors the transi-
tion of charges. With increasing anodic voltage and oxide
thickness, the crystalline region extends, nucleates and
develops within the entire oxide film. High temperatures
generated by high anodic voltages promote the growth of
nanocrystals in the region of the barrier film adjacent to
the breakdown sites and the nucleation of crystals in the
amorphous phase. Phosphate ions present in the electro-
lyte diffuse more ­easily in the crystalline phase, migrating
through the oxide and reaching the metal, forming TiPO4
and Ti(HPO4)2. Phosphate ­concentration in the electrolyte
has 2 opposite effects: on the one hand, a more concen-
trated electrolyte promotes field crystallization of the ox-
ide, and on the other, the phosphates incorporated into the
layer inhibit the thermal crystallization induced by sparks
on the surface. For this reason, there is not a linear trend
between phosphate concentration in the electrolyte and
oxide crystallinity (48).
PEO can be carried out in direct current or alternating cur-
rent; in the case of alternating current, a frequency of 50 Hz
or 60 Hz is frequently used. These layers are comparatively
thick and provide an excellent wear resistance, but they
are porous and therefore provide an insufficient protection
against corrosion.
In recent years, PEO at higher frequency has been evalu-
ated. Mann et al (49) studied PEO up to 4 kHz on different
metals. In this range, the corrosion resistance of the PEO
layer can be significantly improved using bipolar pulses. The
higher ­frequencies and bipolar pulses create layers with low-
er roughness than direct current layers. The increased den-
sity and the smoothness of the layers produced with higher
frequencies can be explained by the fact that a ­shorter du-
ration of the discharge results in smaller surface structures
and lower porosity, since pulses with higher frequencies
create arcs with shorter discharge time. A ­smoother surface
Prando et al e7

Fig. 2 - Scanning electron micros-

copy (SEM) images of TiO2 surfaces
with the progression of anodization
(46).

Fig. 3 - Scanning electron microscopy (SEM) images of anodic oxide film formed on titanium after 100 V (A), 150 V (B) and 200 V (C) anodiza-
tion in 1 M phosphoric acid for 900 seconds (1).

created with high-frequency bipolar pulses leads at least a few studies have been conducted on titanium or Ti alloy
to a better corrosion protection because of a sealing effect anodized with high-frequency plasma electrolytic oxidation
where cathodic pulses follow anodic ones. Up to now, only (37, 44, 49-53).
e8
Fig. 4 - Potentiodynamic polarization curves of untreated and ther-
mally treated Ti samples with temperatures between 500°C and
800°C (53).
Thermal oxidation
Another method to grow titanium oxides is to thermally
treat titanium in an oxygen-containing atmosphere. The pas-
sive layer formed on titanium with exposure to air is some
nanometers thick and composed of amorphous or poorly
crystallized nonstoichiometric TiO2. This layer is highly stable
and provides protection against aggressive environments but
can be disrupted at very low shear stresses, even by rubbing
against soft tissue (54). The structure of thermally grown
titanium oxides can be either anatase or rutile, depending on
treatment temperatures (55).
Such oxides show higher chemical resistance than those
grown anodically, as well as those produced through chemi-
cal oxidation: In fact, the latter can be removed by an acid
pickle, while the removal of thermally grown oxides often re-
quires sandblasting or a caustic descaling bath (55).
With thermal oxidation, surface morphology changes
from a thin adherent surface layer at 500°C to the forma-
tion of a small grain structure at 650°C, until there is a com-
plete coverage with grains oriented perpendicular to the
substrate, at 800°C. Corrosion resistance increases with
increasing treatment temperature, with lower anodic cur-
rent densities at higher temperature (Fig. 4) (54). This trend
is explained by the increase in oxide thickness with tem-
perature, passing from 10s of nanometers at 500°C-600°C
to hundreds of nanometers at around 700°C (55, 56). Tem-
peratures higher than 800°C and longer times are reported
to cause spallation of the oxide layer and worsening of the
properties (54).
Concerning treatment time, Kumar et al (57) performed
thermal treatment at 650°C with a duration of from 8 to
48 hours. Their results showed the presence of oxide scales
throughout the surface without any spalling, irrespective
of treatment time. At 800°C longer treatment caused oxide
spallation. X-ray diffraction (XRD) on oxidized samples with
different durations reveals the formation of rutile, TiO and
α-Ti phase, as reported in Figure 5.
Ti surface treatment to improve corrosion resistance
Fig. 5 - X-ray diffraction (XRD) patterns of untreated and ­thermally
treated Ti samples with different treatment durations (57). R =
­rutile phase.
The advantages of thermal oxidation compared with an-
odic oxidation are well reported in the literature (55, 58).
Birch and Burleigh report the effect of anodization at low
voltages (up to a few volts), and of thermal treatment at dif-
ferent temperatures with different durations, on free corro-
sion potential (55). They performed potentiodynamic tests and
electrochemical impedance spectroscopy (EIS) tests, measur-
ing anodic current densities in the passive range and free corro-
sion potentials of all samples prepared with those treatments.
Higher-temperature oxides show progressively lower pas-
sive current density and higher corrosion potential, which im-
plies that the films are more protective and inert. The oxide
formed at 700°C for 30 minutes shows the highest free corro-
sion potential and the lowest current density. Both anodiza-
tion and thermal oxidation provide better corrosion resistance
compared with nontreated metal. The difference in corrosion
behaviors of the tested oxidizing techniques is due to the crys-
tal structure of the oxide: In Figure  6, a summary of oxides
formed according to the difference techniques is shown.
Chemical oxidation
Thermal oxidation is simple, but its reproducibility is poor
and should be preceded by acid pickling to remove embed-
ded surface contamination, such as iron. In addition, the tem-
perature has to be higher than 500°C to build a film with good
corrosion resistance. It is not practical to heat a large vessel at
500°C. Anodic oxidation, instead, is more consistent and can
be effective as a single step if it is applied for a sufficient time
to dissolve surface contamination. However, sometimes an-
odizing at high voltage is time consuming and laborious with
potential safety problems, and applying current to a large
vessel is not practical. In these cases, another technique can
be used – that is, chemical oxidation (8).
Heating up titanium in a H2O2 or NaOH environment at
temperatures of 60°C-90°C results in oxidation of the surface
with no external contamination. Acids like H2SO4 and HCl can
Prando et al e9

Fig. 7 - Potentiodynamic test results for thermally treated chemi-

cally oxidized titanium, carried out in sea water solution (60).

Fig. 6 - Titanium oxide structures with different surface treat-

ments.

be added to the treatment solution to remove surface con-

taminants (59).
Oxide thickness increases almost linearly with treatment
duration. Oxide growth with this technique is comparable to
that produced with anodization or thermal oxidation.
Films obtained in solutions containing HCl are thicker. XRD
analyses of the same samples show that the addition of SO4-
ions promotes the formation of pure anatase, while the addi-
tion of Cl- ions favors the formation of pure rutile phase.
An evolution of this oxide growing method has involved
annealing a chemically oxidized surface. Wang et al (60)
studied the effect of thermally treating the sample at 350°C,
400°C, 500°C and 600°C after chemical oxidation at 80°C for
6 hours in H2O2. They found large differences in surface wet-
tability: with average water contact angles of 29.5°, 130.5°,
115.6° and 30.6°, respectively. This effect influences corro-
sion resistance, as can be seen from the potentiodynamic Fig. 8 - Scanning electron microscopy (SEM) images of TiO2 film pre-
tests reported in Figure 7, due to the great changes of sur- pared at different temperatures, 350°C (A), 400°C (B), 500°C (C) and
600°C (D) (60).
face structure of the film after thermal treatment; scanning
electron microscopy (SEM) images of samples treated at the
same 4 temperatures are shown in Figure 8. 500°C compared with that measured on samples heated at
A different trend is reported by Krupa et al (61) for chemi- 600°C may result from the better structural homogeneity of
cal oxidation carried out in a 10 M NaOH solution at 60°C for the former samples. The structure of samples heated at 600°C
24 hours and then heated at 500°C, 600°C and 700°C. In this is partially amorphous and partially crystalline, and this mor-
case, the last sample, calcined at 700°C, showed the best cor- phology negatively affects corrosion ­resistance (61).
rosion resistance according to the polarization resistance of
the oxide and the potentiodynamic behavior. Corrosion resis- Ion implantation
tance follows the order: 700°C > 500° > 600° > untreated. The
explanation proposed is related to the sodium titanate hydro- The ion implantation technique has been exploited to en-
gel present in the oxide. At 500°C, the sodium titanate hydro- rich the surface of titanium with certain amounts of selected
gel surface layer is dehydrated and transformed into amor- elements; this permits the production of surfaces that are
phous sodium titanate. At 600°C, the hydrogel layer is partially more biocompatible (62). Thus, the majority of the studies
transformed into crystalline sodium titanate and rutile, but reported in the literature available regarding this technique
remains amorphous. From 600°C, a densification process be- refer to attempts to enhance biocompatibility. Another re-
gins, resulting in the pores being closed. The transformation quirement for devices in the human body is the resistance to
of the amorphous structure into crystalline is observed to oc- corrosion, and ion implanted samples are usually tested for
cur above 700°C. The higher corrosion ­resistance achieved at this purpose in simulated body fluid (SBF).
e10
According to EIS analyses, implantation of calcium at a
dose of 1017 Ca+/cm2 with ion energy 25 keV produces an in-
crement in uniform corrosion resistance of titanium in an SBF
environment. However, the formation of pits is reported in
corrosion tests after this treatment. The mechanism of the
initiation of the pits on the surface of implanted titanium has
not yet been explained, though it is suggested that the altera-
tion of chemical composition of the oxide layer results in a
weakening of the oxide toward localized corrosion (63).
The same test performed on samples implanted with 1015-
3 × 1017 P+/cm2 shows that for doses higher than 106, a new
TiP phase appears in the oxide (64). Phosphorous implanta-
tion causes an increase in corrosion resistance performance
– a conclusion derived from both potentiodynamic and EIS
analyses – and the resistance to polarization of the implant-
ed layer is 2.5 times larger than that of the untreated oxide,
which is due to the amorphous structure of the TiO2 surface
during the implantation. Phosphorous is known to stabilize
amorphous structures (28, 65). The authors claim that the
amorphous layer made up of the native titanium oxide does
not contain defects, such as grain boundaries and contami-
nant segregation, which are characteristic of the crystalline
state; this fact can be considered the reason for the increased
corrosion resistance of amorphous oxides compared with
crystalline oxide with the same thickness. The formation of
the TiP phase, which itself has a high corrosion resistance,
probably helps the increase in resistance (64).
The effect of both calcium and phosphorous ion implan-
tation is to avoid the pitting corrosion observed in the case
of implantation of Ca alone (66). The corrosion resistance of
the treatments can be classified as follows: Ca + P implanted
titanium > P implanted titanium > Ca implanted titanium >
untreated titanium (67).
Oxygen implantation in concentrations from 1013 to 1015
ions/cm2 has been exploited by Ningshen et al (68). Unfortu-
nately, this treatment was found to be detrimental for tita-
nium corrosion resistance in highly aggressive environments.
Carbon implantation was found to have a much greater
effect on titanium corrosion resistance. Table II reports the
free corrosion potential Ecorr and resistance of the oxide layers
of samples implanted with carbon at doses from 5 × 1015 to
2 × 1017 ions/cm2 (69). The best improvement was obtained
with an implantation dose of 2 × 1017 ions/cm2. The effect of
carbon in the oxide is based on the formation of a continu-
ous, solid and nanocrystalline TiC layer.
TABLE II - F ree corrosion potential and polarization resistance on
titanium samples implanted with different amounts of C
C implanted dose Ecorr (mV) Rp (MΩ cm2)
Not implanted -95 2.5
5 × 1015 ions/cm2 34 6 1 × 10 ions/cm
1 × 1016 ions/cm2 65 12
1 × 10 ions/cm
17 2
220 50
2 × 10 ions/cm
17 2
330 54
Ecorr = free corrosion potential; Rp = polarization resistance.
Ti surface treatment to improve corrosion resistance
A similar study was conducted on nitrogen implantation,
with doses from 1016 to 1018 ions/cm2. Table III reports the free
corrosion potential and polarization resistance for all of the
tested implantation conditions (70). The maximum increase in
corrosion resistance was found in the correspondence of a dose
of 1 × 1017 ions/cm2. Nitrogen in the lattice formed nanocrystal-
line TiN precipitates that were coherent with the basic titanium
lattice and uniformly distributed throughout the surface layer.
Grain refinement
In recent years, a variety of techniques to obtain ultrafine
grain (UFG) size on metals were developed (71). A comparison
between corrosion resistance of UFG titanium with that of
coarse grain titanium was proposed from Balyanov et al (72).
UFGs were obtained using the equal channel angular pressing
(ECAP) technique, reaching an average grain size of 300 nm.
Table IV reports the difference in free corrosion potential and
corrosion rate of coarse grain and UFG titanium, for HCl and
H2SO4 solutions at 1 M, 3 M and 5 M concentrations. Lower
corrosion rates and more positive free corrosion potentials
were associated with UFG titanium.
Kim et al (73) carried out a similar study on UFG titanium
produced using 3 different methods. The first 2 methods in-
volved rolling with a single pass at different speed ratios of 3
and 5, and producing a thickness reduction of 61% and 77%
(W3 and W5), respectively. The third method involved cold
rolling to produce a thickness reduction of 63% by a single
rolling pass (C3). Table V reports the current density and
corrosion potential for treated titanium that was immersed
in 1 M HCl and 1 M H2SO4.
The treatment C3 produced the best result, with the corro-
sion rate decreasing by 40.6% and 48.2% in HCl and H2SO4 solu-
tions, respectively. The corrosion rate decreased linearly with
the inverse square root of grain size. This effect was due to the
higher energy of the grain boundaries. Corrosion tends to take
place in grain-boundary regions, and a large extent of grain
boundaries in nanocrystalline materials enhances passivation
kinetics, leading to rapid formation of a stable passive layer.
Alloying with palladium
Among the variety of titanium alloys, 3 of them were de-
veloped to enhance titanium corrosion resistance: titanium
grade 7, grade 12 and grade 16. The best alloying elements to
TABLE III - Free corrosion potential and polarization resistance on
titanium samples implanted with different amounts of N
N implanted dose Ecorr (mV) Rp (MΩ cm2)
Nonimplanted -95 2.5
16 2
85 6.6
1 × 10 ions/cm
17 2
233 62.9
6 × 10 ions/cm
17 2
230 40.3
1 × 1018 ions/cm2 160 4.8
Ecorr = free corrosion potential; Rp = polarization resistance.
Prando et al e11

TABLE IV - Free corrosion potential (OCP, V SCE) and mass loss rate (g/m2h) for coarse grain (CG) and ultrafine grain (UFG) titanium,
measured in HCl and H2SO4 acids

Solution

1 M HCl 3 M HCl 5 M HCl 1 M H2SO4 3 M H2SO4 5 M H2SO4

CG Ti OCP, V 0.193 -0.252 -0.362 0.237 -0.235 -0.352
UFG Ti OCP, V 0.210 -0.242 -0.358 0.256 -0.223 -0.345
OCP difference, % 8.8 4.7 1.1 8.0 5.1 2.0
CG Ti corr. rate (g/m2h) 0.62 1.37 1.98 0.76 1.46 1.87
UFG Ti corr. rate (g/m2h) 0.42 0.90 1.38 0.58 0.78 1.09
Corr. rate difference, % 32 34 30 24 47 43

Corr. = corrosion; OCP = open circuit potential; SCE = saturated calomel electrode.

TABLE V - Corrosion current density and corrosion potential

measured on untreated titanium and that treated with
procedures W3, W5 and C3

Corrosion current Corrosion potential

density (µA/cm2) (V SCE)

1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4

Untreated 186 257 -0.635 -0.677
W3 165 235 -0.623 -0.653
W5 148 206 -0.612 -0.639
C3 124 178 -0.597 -0.621

C3 = cold rolling to produce a thickness reduction of 63% by a single rolling

pass; SCE = saturated calomel electrode; W3 = rolling with a single pass at
speed ratio of 3, producing a thickness reduction of 61%; W5 = rolling with a
single pass at speed ratio of 5, producing a thickness reduction of 77%.
enhance corrosion resistance are palladium, molybdenum and
nickel (12, 74). Palladium and nickel have the effect of acceler-
ating cathodic hydrogen evolution reactions (HERs) on titani-
um, due to their higher exchange current density for HER, while
molybdenum is used to enhance the stability of the oxide.
Among the 3 elements, palladium is the one that gives
higher corrosion resistance to titanium to the point that
Ti-Pd alloy has been proposed for the manufacture of high-
level nuclear waste containers (75). Nakagawa et al (76)
showed that alloying with palladium altered the cathodic
process and resulted in lower overvoltages for HER: This may
shift the working potential in the passive region of the alloy.
They also found that palladium adsorbs hydrogen to form a
protective layer of titanium hydride.
Brossia and Cragnolino (77) report a comparison between
Ti grade 2 and 7 pitting resistance, in a 1 M solution of Cl-
at 95°C. Pitting potential increases from 1.08 V vs. saturated
calomel reference electrode (SCE) to 7.69 V vs. SCE, in passing
from Ti grade 2 to Ti grade 7 (with 0.2% of palladium). They
also pointed out the effect of palladium alloying on the ca-
thodic polarization curve, as visible in Figure 9, where the re-
duced overvoltage of HER is shown together with the higher
free corrosion potential of grade 7.
Fig. 9 - Cathodic polarization curves for Ti grades 2 and 7 in deaer-
ated 5 M chloride + 0.1 M HCl at 95°C (77). SCE = saturated calomel
electrode.
Conclusions
The excellent corrosion resistance of titanium in many
aggressive environments can be further enhanced by tuning
its surface properties and/or bulk composition. In the sec-
ond part of this review concerning the corrosion of titanium,
some of the most important treatments to increase corrosion
resistance are described, in relation to the forms of corrosion
described in Part 1. The effects of the variation of treatment
parameters have been described, with particular attention to
those techniques that enable the modification of natural tita-
nium oxide in terms of thickness and morphology.
However, knowledge of even these kinds of treatment is
far from being exhaustive, and further research will likely be
conducted into this important topic.
Disclosures
Financial support: No grants or funding have been received for this
review.
Conflict of interest: None of the authors has any financial interest
related to this review to disclose.
e12
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