Applied Surface Science 426 (2017) 987–994

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Applied Surface Science

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Full Length Article

Corrosion anisotropy of titanium deformed by the hydrostatic

extrusion
A. Chojnacka a,b , J. Kawalko a , H. Koscielny a , J. Guspiel a , A. Drewienkiewicz c , M. Bieda a ,
W. Pachla d , M. Kulczyk d , K. Sztwiertnia a , E. Beltowska-Lehman a,∗
a Institute of Metallurgy and Materials Science, Polish Academy of Sciences 25 Reymonta St., 30-059 Krakow, Poland
b Faculty of Chemistry, Jagiellonian University, 3 Ingardena St., 30-060 Krakow, Poland
c Faculty of Metals Engineering and Industrial Computer Science, AGH University of Science and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland
d
Institute of High Pressure Physics, Polish Academy of Sciences, Sokolowska 29/37, 01-142 Warsaw, Poland

a r t ic l e in f o a b s t r a ct

Article history: The corrosion behaviour of titanium rods deformed by hydrostatic extrusion (HE) in artificial saliva
Received 4 April 2017 (Carter-Brugirard’ssolution of pH 7.6) was investigatedusing open-circuit potentials (OCPs), (DC) poten-
Received in revised form 3 July 2017 tiodynamic polarisation curves and (AC) electrochemical impedance spectroscopy (EIS) techniques.
Accepted 24 July 2017
Various electrochemical parameters (corrosion potential Ecorr , corrosion current (icorr ), polarisation resis-
Available online 29 July 2017
tance Rp , chargetransfer resistance Rct and oxidefilm resistance Rf ) were analysed. Significant coherence
was observed between results achieved from these procedures, i.e., all applied techniques showed
Keywords:
the same trend for corrosion resistance. The obtained electrochemical data were then related to the
Hydrostatic extrusion
microstructure parameters (crystallographic texture, grain size, grain boundary distribution and den-
Titanium
Corrosion sity) determined using the EBSD/SEM technique. It was found that the corrosion behaviour of titanium
Crystallographic texture processed by the HE method was superior compared to the unprocessed Ti, and this was clearly depen-
Dental implants dent on the extrusion direction. The highest corrosion resistance was revealed for the HE-deformed Ti
rod of the surface oriented longitudinal (parallel) to the extrusion direction.
© 2017 Published by Elsevier B.V.

1. Introduction tant since considerable differences between the elastic modulus

For many years, scientists have devoted much attention to the
search for materials suitable for use as dental implants. These
materials must be biocompatible and resistant to corrosion in the
physiological fluid environment. Initially ivory, pearls, shells, ani-
mal bones, ceramics and precious metals were applied as tooth
replacements [1]. Currently, stainless steel and Co-Cr alloys are
the most commonly used, due to excellent mechanical properties
allowing the easyformation of components of complex shapessuch
as tooth crowns, bridges, and fixed or moveable prosthesis parts
[2]. However, titanium and titanium alloys remain the most inter-
esting materials for dental applications. A significant advantage of
unalloyed titanium is the relatively low Young’s modulus (of about
105–120GPa), the most similar to bone stiffness among all metallic
biomaterials presently applied in implantology [3]. This parameter
(a measure of the stiffness of solid material) is extremely impor-
∗ Corresponding author.
E-mail addresses: e.beltowska@imim.pl, beltowska@gmail.com
(E. Beltowska-Lehman).
of human bone and the implant can lead to bone resorption and
implant loosening. Titanium is also inert and resistant to corro-
sion due to the formation of the stable surface oxide film, which
consists mainly of titanium oxide TiO2 of a rutile-type tetragonal
structure. This feature is very important, since the environment of
saliva in the oral cavity (pH change from 2 to 11) is highly corrosive
to many noble metals [3,4]. Nevertheless, the relatively poor tribo-
logical properties (due to low hardness and high friction coefficient)
such as low strength, wear and abrasion resistances are the main
disadvantages of titanium. Therefore, many studies today focus on
improving titanium’s mechanical properties.
One of the common methods is to replace the pure titanium
with alloys, for instance Ti6Al4V [4]. However, this alloy has unde-
sirable properties due to the strong cytotoxic reactions induced by
vanadium and the negative impact of aluminium on nerve cells.
Thus, unfavourable components oftitanium alloys (e.g. Al andV) are
replaced by biocompatible elements including tantalum, niobium,
and zirconium. At the same time, various procedures for improving
the mechanical properties of pure titanium, including microstruc-
ture refinement, have been suggested [5]. It was observed that,
in accordance with the Hall-Petch relationship, the mechanical

http://dx.doi.org/10.1016/j.apsusc.2017.07.231
0169-4332/© 2017 Published by Elsevier B.V.
988 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994
strength of pure titanium increases considerably as a result of grain
size reduction [5–9]. There are many different methods of obtain-
ing ultrafine-grained or nanocrystalline microstructures in metallic
materials, including titanium. With the emergence of new pos-
sibilities in material engineering, titanium with ultrafine-grained
microstructure can be obtained using Severe Plastic Deformation
(SPD) methods [10–12]. The best known SPD techniques include
Equal Channel Angular Pressing (ECAP), Accumulative Roll Bonding
(ARB), High Pressure Torsion (HPT) and Cyclic Extrusion Compres-
sion (CEC) [13].
Regarding corrosion behaviour, the majority of data available in
the literature concern titanium processed byECAP, as themost pop-
ular SPD method. These studies have shown that ultrafine- grained
titanium (after ECAP) shows better corrosion resistance in NaCl,
HCl and H2 SO4 environments than the coarse-grained counter-
part [5,6]. The effect was related to the higher density of defects
in the crystal lattice of the surface layer in which the passivation
process is initiated. Furthermore, it has been demonstrated that
titanium transformed by ECAP reveals (inaddition to excellent cor-
rosion properties) higher adhesion, and fibroblast proliferation in
an environment simulating human body fluid (SBF) compared to
the unprocessed material [14].
Recently, the hydrostatic extrusion (HE) technique [15] and the
KoBo method, e.g. [16], have been proposed as means of modifying
titaniummicrostructure leading to the improvementof its mechan-
ical properties. In contrast to other Severe Plastic Deformation
(SPD) techniques, the product dimension change accompanies both
extrusion methods, and the final strain is determined by cumu-
lative cross section area reduction of processed billets. Based on
literature and the authors’ own studies, it was possible to con-
clude that titanium deformed by the HE method showed better
mechanical properties compared to the unprocessed material, due
to strengthening by grain refinement. The significant improve-
ment was observed in yield strength (about two and a half times
higher) and microhardness (about one and a half times higher)
values [17]. The hydrostatic extrusion (HE) method seems to be
particularly effective for the development of nano and ultrafine
microstructures, and for the enhancement of biomaterial proper-
ties for medical applications.
There are little data available in the literature on the corrosion
of titanium after the hydrostatic extrusion (HE) process, and none
relate to corrosive properties depending on the extrusion direction
(ED). This work presents the first study on the corrosion anisotropy
of commercially pure CP (grade 2) titanium deformed by the HE
method. The corrosion behaviour was investigated in an artificial
saliva solution. The resulting data were analysed in relation to the
microstructure,and will provide basis for the development of a den-
tal implant-distractor (ID) designed to be embedded in the bone.
TheID is an innovative treatment for bone tissue atrophyafter tooth
loss, and combines the function of vertical bone osteogenesis with
implantation [18].
2. Experimental details
The material selected for testing was commercially pure
titanium grade 2 supplied by Wolften, Poland. The nominal com-
position (wt.%) of samples was C 0.02, Fe 0.12, O 0.10, N 0.02, H
0.003, with the balance being titanium. Initial titanium samples
were subjected to severe plastic deformation using the hydrostatic
extrusion technique in the Institute of High Pressure Physics of
the Polish Academy of Sciences. The deformation was performed
at room temperature (20 ◦ C), in five passes from a diameter of
25 mm to a diameter of 6.07mm. The process was carried out with-
out intermediate annealing. Extrusion pressures were in the range
between 550 and 950 MPa. The final deformation was performed
Fig 1. Schematic drawing of titanium samples (a), trans cross-section (b), and long
cross-section (c).
by means of rotary swaging,which further reduced the diameter of
the product to 4.74 mm. Combined deformation steps performed
after annealing resulted in equivalent strain accumulation equal to
␧: 3.32. Samples from extruded and initial titanium were prepared,
with surfaces oriented parallel (long cross-section) and perpendic-
ular (trans cross-section) to the extrusion direction (ED). The two
types of samples are presented schematically in Fig. 1.
Samples for corrosion testing and metallographic samples for
microstructure and texture investigations were prepared using SiC
sandpaper grinding up to 7000grit, followed by mechanical polish-
ing with a 1:1 solution of colloidal silica suspension and hydrogen
peroxide (30%) resulting in highly polished, mirror like surfaces.
The samples for SEM EBSD (electron backscattered diffraction)
microstructure characterisation were additionally polished elec-
trochemically for 15 s in Struers A3 electrolyte at 5 ◦ C and 35 V.
The EBSD microstructure investigations of the titanium sam-
ples in the initial state and after HE deformation were carried out
using the FEI Quanta 3D FEG microscope, with integrated EDAX TSL
system using a Hikari camera, and OIM Data Collection software
for the acquisition and indexing of electron backscattered diffrac-
tion patterns. The EBSD maps were collected using electron beam
energy of 20 keV. The step sizes used for EBSD measurement of
severely deformed Ti samples were 55 and 75 nm, and the sizes
of the maps collected were 63 ␮m × 63 ␮m and 86 ␮m ×86 ␮m.
The EBSD map from the titanium sample in as received state was
collected over an area of 1 mm2 with a 1 ␮m step size. The col-
lected EBSD data were post-processed and analysed using the TSL
OIM Analysis 7 software. Post-processing consisted of a single iter-
ation of the “grain dilation” procedure with a grain tolerance angle
of 2◦ and minimum grain size of 2 points. Using the OIM Analy-
sis software, microstructure parameters based on EBSD data were
calculated, including distribution of grain size, and density of low
angle grain boundaries (LAGB) and high angle grain boundaries
(HAGB). A grain was defined a as set of at least five properly indexed
points enclosed completely by boundary segments with misorien-
tation between neighbour points of at least 2◦ . Points that did not
meet this criterionwere excluded from analysis (for example,about
4% of points were excluded from analysis in the case of titanium
after hydrostatic extrusion HE). The size of grains was calculated
as a diameter of circles with equivalent surface area, and as a sec-
ond method by using maximum and minimum feret size function.
Feret size function calculates the maximum and minimum distance
between two parallel lines tangential to the boundaries of a grain,
which essentially is the measurement of each grain’s long and short
axis respectively. LAGB (low angle grain boundaries) was defined
as boundary segment with a misorientation angle between neigh-
bours from 2 ◦ to 15 ◦ , and HAGB (high angle grain boundaries) was
defined as boundary segment with a misorientation angle of 15◦
and above. Grain boundary density was reported as a measure of
total grainboundary length divided by the surfacearea of measured
EBSD map (1/␮m). Thecrystallographic EBSD data were also used in
local texture analysis to calculate inverse pole figures. The texture
from discreet EBSD data was calculated in TSL OIM Analysis soft-
ware using the method of spherical harmonicseries expansion. The
 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994
structure ofthe titanium in the initialstate and after the hydrostatic
extrusion(HE) process was also examined by transmissionelectron
microscope TEM (FEI TECNAI G20). Thin foils for TEM observations
were electropolished using a twin jet electro polisher.
Electrochemical experiments were carried out in a conven-
tional three-electrode electrochemical cell using an AUTOLAB
PGSTAT302N potentiostat/galvanostat with NOVA 1.11 software
to control the experiment, and to collect and analyse the data
obtained. Titanium rods (unprocessed and after the HE process,
respectively) were used as working electrodes. The counter elec-
trode was platinum sheet located at a distance of 50 mm from the Ti
working electrode. The saturated calomel electrode (SCE) placed in
a Luggin capillary was used as areference electrode. The corrosion
resistance of the titanium samples was investigated in an aerated
Carter-Brugirard synthetic saliva solution, prepared according to
the PN-EN ISO 10993-15 standard. All reagents were of analytical
grade purity. The reagents NaCl (0.7 g L −1), Na2 HPO4 (0.26 g L −1 ),
KSCN (0.33 g L −1), KH2 PO4 (0.2 gL −1 ), NaHCO3 (1.5 g L−1 ), KCl
(1.2 g L−1 ) were dissolved in distilled water. The pH of 6.7 was
adjusted by addition of HCl or NaOH. Electrochemical measure-
ments were conducted at a temperature of 37.0 ± 0.3 ◦ C. After
metallographic preparation, specimens were washed in distilled
water in the presence of an ultrasonic field. The surface area of
titanium samples exposed to the electrolyte was 0.24 cm 2. The cor-
rosion behaviour was estimated both in parallel and perpendicular
cross-sections to the extrusion direction, using the potentiody-
namic polarisation and electrochemical impedance spectroscopy
(EIS) techniques:
• Potentiodynamic polarisation technique: titanium rod samples
were immersed in the corrosive solution and the open circuit
potential (OCP) was measured for two hours. The anodic and
cathodic polarisation curves were recorded using a sweep poten-
tial test in the range of ±150mV with respect to OCP, with a
scanning rate of 1 mV/s. Three polarisation measurements were
repeated for each sample. The corrosion current (icorr ) and corro-
sion potential (E corr) were determined based on the Tafel relation:
log i= f (E). The polarisation resistance (Rp ) was calculated using
b ·b
the Stern-Geary equation: Rp = 2,3·(b c+ba )i , where b a, bc are the
a c corr
slope of anodic and cathodic polarisation curves.
• Electrochemical impedance spectroscopy (EIS): the impedance
measurements (single sine alternating current AC) were carried
out at open circuit potential with a voltage amplitude of 10 mV
and a frequency range from 0.1 Hz to 100 kHz (50 points for each
frequency decade were acquired). The impedance data were ana-
lysed based on the Boukamp model. Impedance spectra were
reported by Nyquist diagram.
• Immersion test: measurements were conducted according to the
ISO 10993-15:2000 standard. Tested samples (initial Ti and Ti
after hydrostatic extrusion HE) were dipped in an artificial saliva
solution (80 ml) and placed in an incubator at 37 ◦ C for three
months. The pH and weightof the samples were measured every
seven days.
3. Results and discussion
3.1. Microstructure of titanium after hydrostatic extrusion
Titanium microstructure in the as received condition is mod-
erately deformed, which is the result of the production process.
Grains are slightly elongated in the extrusion direction, grain size
ranges from 5␮m to about 140 ␮m and overall mean grain diame-
ter is 47.2 ␮m. Larger grains show often sub-grain microstructure
defined by developed mesh of LAGB’s. Some tension 101̄2 101̄ 1̄
twins are present in the microstructure. Grain boundary density is
989
low and equal to 0.01 1/␮m for both LAGB and HAGB (low and high
angle grain boundaries).
The titanium samples after hydrostatic extrusion have a
microstructure consisting of two distinct types of grains: rela-
tively coarse ones, which are severely elongated in the direction
of extrusion, and clusters of strongly refined grains, with much less
elongated shapes. The elongation of the microstructure results in
very different shapes and sizes of grains observed on transversal
(Trans) and longitudinal (Long) cross-sections. The two types of
microstructures are presented in Fig. 2 by means of EBSD grain
orientation spread (GOS) maps. Observations in TEM (bright field
(BF) images presented in Fig. 3a, b) also revealed equiaxed grains in
transversal cross section and elongated in extrusion direction (ED)
grains in longitudinal cross section. Moreover, analysis of selected
area diffraction patterns obtained from transversal cross section
confirms the microstructure’s ultra-fine grain character.
The grain sizes vary greatly between the two cross-sections. In
the trans cross-section, grain sizes range from 70 nm(short axis) to
6.5 ␮m (long axis), and overall mean grain diameter (diameter of
equivalent circles) is equal to 0.57␮m. On the other hand, sizes of
the grains observed in the long cross-section range from 140 nm to
44.63 ␮mfor shortand long grainaxis, respectively, and the average
diameter of grains in this cross-section is equal to 2.00 ␮m. The
histograms of grain sizes (short and long axes) are presented in
Fig. 4. Such very large discrepancies between sizes of grains points
to the substantial heterogeneity of the microstructure. Since grain
size is a parameter determining macroscopic properties such as
hardness or tensile strength, and can affect corrosion resistance, it
is important to investigate parts of the microstructure with such
different grain sizes separately.
Based on the criterion of grain diameter below 1 ␮m, the ultra-
fine grained fraction of microstructure can be distinguished and
analysed separately from the coarse-grained fraction, consisting
of grains with diameter equal to or greater than 1 ␮m. The main
difference between the two fractions can be observed in the con-
tent (density) of HAGB (Table 1). For instance, HAGB density in
the fine-grained fraction is equal to 5.60 1/␮m in the trans cross-
section, while in the coarse-grained fraction HAGB (high angle grain
boundaries) density is much lower (0.15 1/␮m). On the other hand,
differences in LAGB (lowangle grain boundaries) content are not
that great, but similarly the density is higher in the fine-grained
fraction. Such great differences in HAGB content between the two
fractions results in the uneven spatial distribution of crystal lattice
defects. Additionally, heterogeneity differs between both cross-
sections, due to different ratios of surface area occupied by the two
fractions. In the trans cross-section, the fine-grained fraction with
high HAGB density occupies 84% of the microstructure, while in the
long cross-section only 48% of the microstructure is occupied by
the high-density HAGB fraction. The additional difference in over-
all HAGB density between the trans and long cross-sections results
from severe elongation and the overall bigger grains observed in
long cross-section.
Titanium in the as received state (before hydrostatic extrusion)
has almost random crystallographic texture, with a very weak max-
imum atthe [0001 ] direction oninverse pole figurefor the extrusion
direction (Fig. 5a). After hydrostatic extrusion, titanium samples
have a sharp, 101̄0fibre texture typical for extruded hexagonal
materials. The texture is characterised with the main maximum
on the 101̄0 pole figure in the position of extrusion direction,
and the (0001) pole distributed in the surface perpendicular to this
direction. Such texture results in very different crystallographic
planes observed on transversal and longitudinal cross-sections.
On the transversal cross-section 101̄0 , planes of grains are
almost exclusively observed (Fig. 5b), while on the longitudi-
nal cross-section the grain orientation is distributed between the
(0001) and 112̄0} planes, with the maximum shifted towards the
990 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994

Fig. 2. Grain orientation spread (GOS) maps of titanium after hydrostatic extrusion a) transversal, b) longitudinal cross-section. HAGBs are indicated by black lines, LAGBs
are indicated by bright grey lines.

Fig. 3. TEM BF images of titanium after hydrostatic extrusion a) transversal, b)longitudinal cross-section and c)selected area diffraction patternfrom transverse cross section
indexed as Ti ␣.

Table 1
Statistical microstructure parameters.

Trans HE Long HE

Overall Fine-grained Coarse-grained Overall Fine-grained Coarse-grained

fraction fraction fraction fraction

Structure fraction – 84% 12% – 48% 48%

Avg. grain size (diameter) [␮m] 0.57 (SD 0.47) 0.42 (SD 0.20) 1.59 (SD 0.53) 2.00 (SD 2.21) 0.57 (SD 0.21) 3.42 (SD 2.38)
LAGB density [1/␮m] 3.30 3.11 2.78 3.51 3.15 2.77
HAGB density [1/␮m] 5.26 5.60 0.15 2.50 2.95 0.46

(0001) position (Fig. 5c and d). Using the discrete crystallographic
data from EBSD (electronbackscattered diffraction) measurements,
textures were calculated separately for ultra-fine grained and
coarse-grained componentsof the microstructure.Inverse pole fig-
ures presented in Fig. 5c and d indicate that the texture is similar in
both fractions of the microstructure; however, the non-basal com-
ponents oftexture are slightly weaker inthe caseof the fine-grained
fraction.
3.2. Corrosion behaviour
Titanium rod samples were prepared for corrosion tests in an
artificial saliva solution according to the diagram shown in Fig. 1
(see the Experimental details section). Fig. 6 presents changes of
the open circuit potentials (OCP) against time for tested Ti samples
in anaerated Carter-Brugirard solution at 37 ◦ C. It is known that the
OCP value varies with time of immersion in a corrosive medium due
to changes in the surface nature of the electrode, and indicates the
 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994 991

Fig. 4. Histograms showing distribution of crystallite sizes in titanium samples after hydrostatic extrusion, a) short axes in trans cross-section, b) short axes in long cross-
section, c) long axes in trans cross-section, d) long axes in long cross-section.

Fig.5. Inverse pole figures (normal direction) calculated for titanium samples from discreteEBSD crystallographic data: a) transversal cross-section – before HE, b) transversal
cross-section – after HE, c) longitudinal cross-section – after HE – coarse-grained fraction, d) longitudinal cross-section – after HE – fine-grained fraction.

thermodynamic tendency of a material to electrochemical oxida-
tion. Thus, the open circuit potential can be a criterion for corrosion
behaviour [19].
As can be seenin Fig. 6, a substantial shift of the open circuit (OC)
potential towards less negative values was observed for all tested
samples. Then, the open circuit potential (OCP) increases slowly
and eventually stabilises at a certain stationary value. The effect is
mainly related to the formation and growth of the oxide films at
the Ti sample surface in the artificial saliva medium. These results
clearly indicate that unprocessed titanium rods behave worse than
Ti deformed by hydrostatic extrusion (HE), after which the open
circuit potential is less negative, about 0.15 mV −0.22 mV (depend-
ing on the sample surface orientation to the extrusion direction)
(Table 2). Thus, hydrostatic extrusion treatment improves the cor-
rosion resistance of titanium, which reveals a more noble character
and then less chemical activity. Open circuit potential variations
are very similar for all unprocessed Ti samples regardless of the
examined surfaces (sample code: Trans Init and Long Init) (Fig. 6).
However, for Ti deformed byHE, it should be highlighted that OCP is
influenced by the extrusiondirections, showing a progressive shift
towards noble values for surface parallel oriented (Long HE).
The cathodic and the anodic polarisation curves of all inves-
tigated Ti samples after two hours of immersion in an aerated
Carter-Brugirard solution are reported in Fig. 7. The electrochemi-
cal parameters derived from the Tafel plots, including the corrosion
current density (icorr ), corrosion potential (Ecorr), polarisation resis-
tance(Rp ), and theslope of anodic(b a) and cathodic(bc ) polarisation
curves are summarised in Table 2.
As seen from the data in Table 2, all investigated Ti samples
were characterised by verygood corrosionresistance in an artificial
saliva solution, as evidenced by the low corrosion currentsand high
values of corrosion potential and polarisation resistance. More-
over, the corrosion parameters of unprocessed titanium samples
(Trans Init and Long Init) are very similar in both directions.In turn,
for titanium deformed by hydrostatic extrusion (HE) the corro-
sion properties (especially corrosion potential E corr and polarisation
resistance Rp ) differ significantly for the surface perpendicular and
parallel to the extrusion direction (Trans HE and Long HE). It is
clearly shown that the Long HE surface (oriented parallel to the
extrusion direction ED) reveals the highest corrosion resistance in
the artificial salivasolution of pH 7.6. Those results suggest that the
sharp texture and different orientation of grain planes observed on
Trans HE and Long HE samples is more important than the crys-
tal lattice defect density in determining corrosion behaviour. The
basal (0001) planes in titanium have the highest atom density in
this hcp structure. It has been reported previously that high atom
992 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994

Table 2
Corrosion parameters of titanium samples determined in a solution of artificial saliva.

Ti specimen code OCP mV/SCE Ecorr , mV/SCE icorr , nA/cm 2 b a mV/dec b c mV/dec Rp ·cm2

Trans Init −373 −383 156 132 119 134674

Long Init −384 −394 149 125 120 123455
Trans HE −230 −248 147 116 112 126644
Long HE −146 −168 130 124 106 237975

Fig. 8. Comparison of the impedance response of Ti grade 2 samples Trans HE and

Long HE.
Fig. 6. Open circuit potential evolution in the first two hours, for tested Ti samples
in a solution of artificial saliva of pH 7.6.

Fig. 9. Equivalent circuits fitted to the EIS data.

lected results are presented in the form of Nyquistplots. To explain

Fig. 7. Polarisation curves in semi-logarithmic coordinates for tested Ti samples in
a solution of artificial saliva of pH 7.6.
density planes offer higher corrosion resistance than lower density
ones [20]. In the HE titanium (0001), orientations are observed on
long cross-sections, which, in synergy with increased grain bound-
ary density after hydrostatic extrusion (HE), results in the highest
corrosion resistance among tested samples. On the other hand,
Trans HE cross-section crystal lattice defect density is higher than
in Long HE, but 101̄0 crystal planes observed on Trans HE are
less corrosionresistant, thus this cross-section has effectively lower
corrosion resistance.
The EIS (electrochemical impedance spectroscopy) measure-
ments support the results of open circuit potential (OCP) and
potentiodynamic polarisation methods. Fig. 8 shows EIS spectra
for the processed titanium samples Trans HE and Long HE. Col-
the corrosion behaviour of the system, experimental EIS data were
fitted to an appropriate electrical equivalent circuit (EEC) model,
presented in Fig. 9.
The Nyquist plots show a depressed semi-circle, indicating
that there is more than one time constant that describes the
impedance response of the system [20,21]. Based on the compo-
sition of testing system and other studies concerning EIS analysis
of titanium [20–24], the respective parts of the circuits were
analysed. Rs is related to resistance resulting from all electrical
contacts in the measuring system. The first parallel connection
of the resistance-constant phase element (R ct -CPE dl ) in the high
frequency range corresponds to the charge transfer processes, rep-
resented by the double layer constant phase element (CPEdl) and
charge transfer resistance (R ct ), respectively. Thesecond parallel of
the resistance-constant phase element (R f -CPEf ) can be associated
with slower mass transport processes in the oxide phase, namely
the diffusion of electroactive species [20,21]. CPE elements are
introduced to replace the capacitors due to the non-ideal behaviour
of capacitive elements resulting in inhomogeneities present at the
micro or nano (atomic/molecular) levels, such as surface rough-
ness/porosity, adsorption, or diffusion [25]. Calculated values of all
parameters are collected in Table 3. The additional parameter is
polarisation resistance (Rp ) which is given by the sum of charge
transfer resistance (Rct ) and film resistance (R f ). It should be noted
that the Rp values calculated from EIS are consistent with the Rp
values obtained using the potentiodynamic polarisation technique.
 A. Chojnacka et al. / Applied Surface Science 426 (2017) 987–994
Table 3
The parameters of specific elements of equivalent circuits fitted to EIS spectra.
Ti sample code Rs  cm 2 Rct  cm 2 CPE dl  s N cm−2
−5
Trans HE 17 9997 3·10
Long HE 17 10490 6·10−5
Fig. 10. The pH values of artificial saliva containing titanium samples (initial and
HE processed), and blank solution for 90 days.
For both samples, film resistance Rf is higher than charge trans-
fer resistanceR ct and Ndl is higher than Nf . This suggests that passive
film exercises more resistance than the charge transfer in the dou-
ble layer, and that the behaviour of the film is not ideal, which is
consistent with earlier studies [24]. Rf (film resistance) values are
at a similar level for both materials, so it can be assumed that the
passive film formed on samples is of comparable quality. However,
all parameters related to charge transfer and the formation of pas-
sive film for the sample in longitudinal direction to the hydrostatic
extrusion (HE) process are slightly higher, which means that this
material is expected to demonstrate better corrosion properties.
Corrosion immersion tests for the initial and HE processed tita-
nium samples were carried out in a Carter-Brugirard solution at
37 ◦ C, for 90 days. Every seven days the pH changes of the blank
solution and solutions with the samples immersed were measured
(Fig. 10). The corrosion of titanium in artificial saliva resulted in
a slight decrease in the pH value in relation to the blank solu-
tion. However, measurements carried out in the incubator showed
no significant differences for either type of Ti sample up to about
60 days. After exceeding this period, changes in pHfor unprocessed
titanium became more apparent. It is also important that the sur-
faces of all samples tested revealed a well protective surface free of
any corrosion attack after 90 days.
4. Conclusions
Based on the results obtained in the present study on the cor-
rosion anisotropy of titanium deformed by hydrostatic extrusion
(HE) in artificial saliva, the following conclusions have been drawn.
• The open-circuit potential measurements showed that hydro-
static extrusion treatment improves the corrosion resistance of
titanium. Polarisation measurements and EIS (electrochemical
impedance spectroscopy) analysis were in good agreement and
revealed the same trend in corrosion properties. In general, this
effect is related to the fast formation and growth of oxide films at
993
N dl R f  cm 2 CPEf  sN cm −2 Nf ␹2 Rp  cm2
−5
0.93 102432 3·10 0.92 0.004 112429
0.98 116864 4·10 −5 0.93 0.003 127354
the titanium surfaces of very high lattice defect density (in par-
ticular the high density of high angle grain boundaries HAGBs).
• The corrosion resistance of titanium processed by HE was dis-
tinctly affected by the extrusion direction, due to sharp 101̄0fibre
texture and different crystal orientations observed on Trans HE
and Long HE samples.
• The best corrosion behaviour in an artificial saliva solution was
exhibited by titanium samples of the longitudinal cross-sections
(Long HE). This effect is due to synergy between the high density
of crystallographic lattice defects and the crystallographic tex-
ture, where the corrosion resistant, close-packed crystallographic
planes (0001) are mainly oriented parallel to the extrusion direc-
tion ED.
Acknowledgement
This work was supported by the National Centre for Research
and Development in Poland through Project No PBS2/A6/18/2014.
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