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Strengthening of Titanium by Equal Channel Angular Pressing ‐ Impact on

Oxide Layer Properties of Pure Titanium and Ti6Al4V

Article  in  Advanced Materials Interfaces · June 2020

DOI: 10.1002/admi.202000552

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Communication
Strengthening of Titanium by Equal Channel Angular
Pressing - Impact on Oxide Layer Properties of Pure
Titanium and Ti6Al4V
Melanie Franz, Bernhard Mingler, Maciej Krystian, Laszlo Sajti, Darius Pohl,
Bernd Rellinghaus, Cornelia Wolf-Brandstetter, and Dieter Scharnweber*
Equal channel angular pressing (ECAP) as a method applicable to large
samples for strengthening metallic materials via severe plastic deformation
has recently attracted considerable interest. For biomedical applications,
ECAP-treated pure titanium is a promising alternative for implants subjected
to high mechanical loads as it contains no potentially cytotoxic alloying
elements. The consequences of an ECAP treatment for the physico-chemical
properties of the air formed passive layers of pure or alloyed titanium, which
are of the utmost importance for the biological response to these materials,
are studied here for the first time. This includes mechanical, electron
microscopic, and electrochemical investigations in protein containing media
to study the reactions that occur immediately after implantation in the phase
boundary between implant and biological system. The ECAP treatment results
in a positive shift of the flatband potential and a particularly strong increase of
the donor density for the native oxide layers. This is associated with increased
electronic conductivity of the oxide layers under anodic polarization.
Titanium based materials combine very good corrosion stability
with mechanical properties appropriate for many biomedical
applications especially for load bearing implants. However, com-
mercially pure (CP) titanium has mechanical properties inferior
M. Franz, Dr. C. Wolf-Brandstetter, Prof. D. Scharnweber
Technische Universität Dresden
Max Bergmann Center of Biomaterials
Budapester Straße 27, Dresden 01069, Germany
E-mail: Dieter.Scharnweber@tu-dresden.de
Dr. B. Mingler, Dr. M. Krystian, Dr. L. Sajti
AIT Austrian Institute of Technology GmbH
Center for Health and Bioresources
Biomedical Systems
Viktor Kaplan Straße 2, Wiener Neustadt 2700, Austria
Dr. D. Pohl, Dr. B. Rellinghaus
Technische Universität Dresden
Dresden Center for Nanoanalysis (DCN)
Center for Advancing Electronics Dresden (cfaed)
Helmholtzstraße 18, Dresden 01069, Germany
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admi.202000552.
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim. This is an open access article under the terms of the
­Creative Commons Attribution-NonCommercial License, which permits
use, distribution and reproduction in any medium, provided the original
work is properly cited and is not used for commercial purposes.
DOI: 10.1002/admi.202000552
Adv. Mater. Interfaces 2020, 2000552 2000552  (1 of 7)
www.advmatinterfaces.de
to α/β-Ti-alloys such as the widely used
Ti6Al4V. These alloys are in turn critically
discussed because of potential cytotoxic
effects of vanadium and aluminum,[1,2] ele-
ments that can be found in high concentra-
tions on the material surface and are also
released into the surroundings.[3]
It is thus of great interest to improve the
mechanical properties of CP titanium, such
as ultimate tensile and fatigue strength, to
be able to replace the critically discussed tita-
nium alloys in load bearing biomedical appli-
cations.[4,5] The use of severe plastic defor-
mation, multi directional forging,[6,7] and
especially equal channel angular pressing
(ECAP)[5,8–10] to this end offers numerous
advantages. ECAP not only allows for rapid
treatment of large samples[11] which can be
further processed for biomedical applica-
tions, but also results in high dislocation
and grain boundary densities of the metallic
phase[12] in CP titanium. This stabilizes the air-formed passive layer
and thus increases the corrosion stability compared to as received
(AR) coarse grained material.[13,14]
In the biomedical area, multiple in vitro and in vivo investi-
gations have shown that protein adsorption is a very early pro-
cess in the interaction of biomaterial surfaces with biological
systems.[15,16] As specific surface properties, that is, for tita-
nium-based materials the properties of the oxide layers, deter-
mine the adsorption of and interaction with proteins, they play
a key role in the biological response to these materials.
Furthermore, we have shown earlier that the key parameters
flatband potential (EFB) and donor density (Nd) of the n-type
semiconducting air-formed passive layer[17,18] vary for different
titanium based materials.[19] Additionally, the electronic conduc-
tivity of the oxide layer on Ti6Al4V depends on the underlying
metallic phase.[20,21]
In this work the consequences of an ECAP treatment for the
physico-chemical properties of the air-formed passive layers of
titanium-based materials were investigated for the first time.
The experiments were performed under conditions relevant for
a biomedical use. This included investigations in protein con-
taining media for insight into reactions occurring immediately
after implantation in the phase boundary implant/biological
system. We were able to show that an ECAP treatment of both
CP titanium and Ti6Al4V resulted in a positive shift of the
flatband potential of the native oxide layer, and a particularly
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
strong increase of their donor density. This was accompanied
by an increased electronic conductivity of the oxide layers under
anodic polarization.
Microstructural changes of the materials associated with
the ECAP treatment are illustrated in Figure  1, that compares
Figure 1.  Comparison of the ECAP-induced changes in the microstruc-
ture of Ti and Ti6Al4V. Data of the as received (AR) and ECAP-treated
samples are grouped in the left and right column of the figure, respec-
tively. A,B) SEM images of Ti. C,D) Corresponding EEL spectra (from
cross-sectioned samples) of the surface oxide layer (blue) and the bulk
area of the samples (red). E,F): SEM images of Ti6Al4V. G,H) STEM
images and EDX-derived elemental mappings of Ti, O, Al, and V from
the regions marked in the STEM images. I,J) Corresponding EEL spectra.
The absorption peaks at the L3 and L2 edges are due to excitations from
the Ti 2p3/2 and 2p1/2 core level states into the unoccupied 3d t2g and eg
states, respectively.
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Table 1.  Grain size (determined from SEM images) and hardness data
for titanium and Ti6Al4V in the states AR and ECAP.
Material Grain size ± SD [µm] Hardness ± SD [HV10]
Ti AR 11.1 ± 0.3 177 ± 1
Ti ECAP 1.55 ± 0.02 236 ± 2
Ti6Al4V AR α phase 0.19 ± 0.005 300 ± 3
β phase 1.46 ± 0.02
Ti6Al4V ECAP α phase 0.19 ± 0.003 373 ± 3
β phase n.d.
SEM images of both materials and STEM images of Ti6Al4V
in the AR and ECAP state. Additionally, scanning transmission
electron microscope (STEM) energy dispersive X-ray analyses
(EDX) distribution images and electron energy loss spectro­
scopy (EEL) spectra are presented. The grain size of the four
materials as derived from the analysis of scanning electron
microscope (SEM) images is summarized together with the
HV10 hardness data in Table 1.
For titanium the SEM data reveal a strong ECAP-induced
reduction of the grain size by a factor of about 7 (11.1  ±  0.3 to
1.55  ±  0.02  µm). This decrease is associated with a significant
increase of the hardness by almost 50%. These data are in good
agreement with the literature for similar ECAP conditions both
in the grain size reduction[22] and hardness increase.[10,23–25] For
Ti6Al4V the SEM images indicate no effect of the ECAP treat-
ment on the grain size of the α phase. For the β phase, how-
ever, no separate detectable grains are present after the ECAP
treatment, a drastic reduction compared to Ti6Al4V AR (grain
size 1.46  ±  0.02  µm) that is in agreement with the findings of
Semenova et al.[26] It is also possible that the observed effect is
at least partially due to a decrease in the amount of β phase as
described by Valiev et al.[8]
In contrast, STEM images show a much finer overall micro-
structure for ECAP-treated Ti6Al4V as compared to the AR
sample, indicating that small angle grain boundaries are not
resolved by the etching process in this material. This finding
is similar to the grain size differences between SEM and trans-
mission electron microscope (TEM) reported for Ti.[22,24,25] The
ECAP effect on the hardness of Ti6Al4V amounts to 25% and
is thus smaller than for titanium but still significant, which is
in good agreement with ref. [27]. A detailed analysis of SEM
images from sample center and edge in both the horizontal and
vertical direction showed no significant microstructural differ-
ences for any of the four investigated materials (Table S2, Sup-
porting Information).
EDX elemental mapping of AR Ti6Al4V and the ECAP-treated
samples show large differences in the elemental distribution of
V and Al. Ti and O are homogeneously distributed in both AR
and ECAP-treated samples, and while Al and V distribution in
the ECAP-treated sample are also mostly homogeneous, they
are phase-separated in the AR state. In both samples, oxygen is
mainly present at the surface and not diffused into the bulk.
Local EEL spectra of the surface oxide layer and the bulk area
are obtained from cross-sectionally prepared samples and are
used to quantify the native sample oxide surface layer thick-
ness. For this, the intensity of the O–K edge was plotted as a
function from the surface to the depth of the metallic phase (for
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 2.  Flatband potentials A,B) EFB ± SE and donor densities C,D) Nd ± SE of air-formed passive layers on titanium (Ti) and the bi-phasic alloy
Ti6Al4V both in the AR and ECAP-treated state. Diagrams (A) and (C) present data in 0.133 m phosphate buffers (pH 4.4, 7.4, and 9.2), diagrams (B)
and (D) compare data from phosphate buffer 7.4 (phosphate) with 0.2 m NaClO4 electrolyte (perchlorate) and cell medium. The gray line in diagram
(A) with the assigned text “60 mV per pH” indicates the theoretical slope of EFB per pH curves; ⁎, ⁎⁎, ⁎⁎⁎ for p < 0.05, 0.01, 0.001.

details see Figures S1–S4, Supporting Information). Fitting the
resulting intensity at the surface by a Gaussian resulted in oxide
layer thickness data of 7 ± 1 and 23 ± 2 nm for Ti in the AR and
ECAP state, respectively; for Ti6Al4V these values are 6 ± 1 nm
for AR and 21  ±  1  nm for ECAP. These more than threefold
thicker oxide layers for ECAP-treated materials are contrary to
Garbacz et al.[28,29] who did not find an effect of ECAP treatment
of oxide layer thickness. In addition, a strong modification of the
Ti-L fine structure was visible due to the altered oxidation state
in the surface area (Figure  1). To increase the signal-to-noise
ratio, spectra are averaged parallel to the surface. Figure 1 shows
the Ti-L edge spectra for the individual samples of the oxide sur-
face layer as well as of the bulk. The absorption peaks at the L3
and L2 edges are due to excitations from the Ti 2p3/2 and 2p1/2
core level states into the unoccupied 3d t2g and eg states, respec-
tively. A strong chemical shift between the two spectra (red and
blue curves in Figure  1) reveals a strong oxidation of Ti in the
surface layer. This also manifests in the fine structures (i.e., the
“sharpening”) of the L3 and L2 peaks.
Flatband potentials and donor densities were derived from
a Mott-Schottky analysis of the impedance data in analogy to
ref. [19]. The relative dielectric constant was set to 50 based on
literature[30,31] and in agreement with earlier work.[19] As no lit-
erature data are available for oxide layers on Ti6Al4V, a relative
dielectric constant of 50 was also used here.
With the exception of Ti6Al4V ECAP in cell medium,
the EFB values as a function of the pH for phosphate buffers
(Figure 2A) and the media composition for pH 7.4 (Figure 2B)
are in a range between −100 and −900 mVAgCl with the trend in
diagram (Figure 2A) following the theoretical slope of −60 mV
per pH.[32] In phosphate buffers the values for ECAP-treated
materials are more positive by 300–400 mV compared to the AR
state (exception Ti6Al4V ECAP). Additionally, the values for tita-
nium are significantly more positive compared to Ti6Al4V for
both treatments in all investigated media.
Comparing the effects on AR and ECAP materials of per-
chlorate electrolyte and cell culture medium to phosphate
buffer in Figure 2B, opposing results are found for the different
materials. While for AR cell culture medium results in more
positive flatband potentials compared to phosphate buffer, for
both ECAP materials a ranking in the order of phosphate > per-
chlorate > cell medium is observed. These differences are all
significant for Ti, for Ti6Al4V this is true only for phosphate
buffer compared to the two other electrolytes.
The data for the donor densities in Figure  2C,D show
an extremely significant effect of the ECAP treatment.
Whereas the values for both materials in the AR state are
between 2.3  ×  1020 cm−3 (for titanium in cell medium) and
6.1  ×  1020 cm−3 (for Ti6Al4V in phosphate buffer 7.4), donor
densities increase by more than two orders of magnitude to
1.8 × 1021 – 1.1 × 1022 cm−3 and 3.6 × 1022 – 2.8 × 1023 cm−3 for
Ti ECAP and Ti6Al4V ECAP, respectively.
The donor densities for ECAP-treated Ti6Al4V are at least one
order of magnitude higher than the corresponding values for Ti

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ECAP over all studied media. Further, for both materials the same
ranking of perchlorate > cell medium≈phosphate (7.4) is observed.
No other groups have so far compared the semiconductor
properties of air-formed oxide layers on ECAP-treated and
AR titanium based materials. Although the flatband poten-
tials in Figure 2A,B, are shifted to more positive values due to
the ECAP processing, the values remain negative to the body
potential given with 400 to 500 mVAgCl by Velten et  al.[33] and
thus in the “biologically safe region”. Other groups, how-
ever, report redox potentials measured in plasma as being in
the range of −334  ±  9 mVAgCl for healthy patients aged below
60 years.[34] These values increase to with age and/or diseases
such as diabetes type 2 or atherosclerosis to values above
−280 mVAgCl.[35,36] Given these data, the EFB-values measured for
both ECAP-treated materials in phosphate buffer pH 7.4 come
close the redox potential and indicate potentially increased
electronic conductivity of the oxide layers under these condi-
tions. Interestingly, the flatband potentials determined in cell
medium become more negative after ECAP treatment, which
might be related to the cysteine/cysteine and glutathione/glu-
tathione disulfide redox systems present in this medium[34] in
combination with the increased electronic conductivity of the
oxide layers at potentials positive to the flatband potential.
Although a general increase in the dislocation and grain
boundary density is expected as a consequence of an ECAP
treatment,[37] little is known about specific values for either
CP titanium or Ti6Al4V as a function of the ECAP treatment
parameters.[12] For the strong increase in the donor densities of
the air-formed oxide layers shown in Figure  2C,D, we hypoth-
esize a correlation with the dislocation densities in the metallic
phase that forms the substrate for the oxides layers. Zhilyaev
et  al.,[23] have reported an increase in the dislocation density
from ≈0.03 × 1015 m−2 for the AR material to above 0.4 × 1015 m−2
depending on the location within the ECAP-treated titanium
sample, with an oxygen content corresponding to grade 1 for
ECAP conditions similar to those used in our work. Schafler
et al.[38] report even higher dislocation densities of 2 × 1015 m−2
for titanium grade 2 after an ECAP treatment with 8 passes BC
in the same temperature range as used here. For Ti6Al4V an
increase in the dislocation density by almost an order of mag-
nitude (0.8 and 7.5 × 1015 m−2) is reported for AR and ECAP
states for six ECAP passes at 650 °C under conditions identical
to those applied in this work.[26]
Galvanostatic anodic polarization in phosphate buffer 7.4 and
perchlorate electrolyte was applied as an independent method
to study the effect of ECAP treatment on the electronic conduc-
tivity of oxide layers on the different materials (Figure 3).
Possible (electrochemical) reactions during polarization can
be described with:
Ti → Ti4+ + 4 e− for the formation of titanium ions in the interface
metal/oxide
Ti4+ + 2 O2−→ TiO2 and their reaction with oxygen ions formed in the
interface oxide/electrolyte via dissociation of water for
the oxide formation
and with:
2 H2O → O2 + 4 H+ + 4 e− for the formation of oxygen by oxidation of water in
the interface oxide/electrolyte due to the electronic
conductivity of the oxide layer as side reaction.
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After 300 s at the open circuit potential (EOCP), galvano-
static polarization with increasing current densities from 0.5 to
5 mA cm−2 for 120 s each was applied until a maximum poten-
tial of 10 VAgCl was reached (Figure  3A–D). The dotted lines
with a slope of 2.5 mC V−1 cm−2 in these diagrams, assigned to
100% Faraday efficiency (FarEff), indicate the theoretical gain of
the potential given the case that all charge transferred through
the system is used for oxide formation.[39] Thus, higher poten-
tials at comparable time points of polarization can be assigned
to higher Faraday efficiencies for the oxide formation for a given
material, corresponding to a lower amount of oxygen formation
as a side reaction due to the lower electronic conductivity of the
oxide layer. Further, for galvanostatic polarization the time axis
in the diagrams can also be considered as a charge density axis.
For phosphate buffer 7.4 (Figure  3A,B) the AR state of both
materials results in different shapes of the potential/time (charge
density) curves. Whereas a continuously rising curve for current
densities ≥ 1 mA cm−2 is observed for Ti AR, after a similar start
a voltage maximum is detected for Ti6Al4V AR at the end of the
1.5 mA cm−2 polarization interval between 600 and 650 s. This
corresponds to a transferred charge density of ≈350 mC cm−2.
Irrespective of these differences, the Faraday efficiency for the
formation of anodic oxide of both AR materials is substan-
tially above the corresponding ECAP materials throughout
the whole experiment. These materials show flatter curves
that start to rise at higher current densities (≥1.5  mA cm−2),
indicative of a higher inherent electronic conductivity of the
oxide layers.
For perchlorate electrolyte (Figure  3C,D) the potential/time
(charge density) curves for Ti AR and Ti ECAP are in general
comparable to those for phosphate buffer. However, the current
density at which potentials start to rise continuously (the point
where the electronic conductivity of the oxide layer requires the
formation of additional oxide to be able to transport all charge)
is shifted toward higher values. This shift is to 1.5 instead of
1  mA cm−2 for Ti AR and to 2 instead of 1.5  mA cm−2 for Ti
ECAP, with the slopes for higher current densities being steeper
for both materials compared to those in phosphate buffer.
For both Ti6Al4V states a very limited increase of the poten-
tial is observed for polarization in perchlorate electrolyte. A
voltage maximum similar to the one in phosphate buffer occurs
for Ti6Al4V AR at current densities ranging from 2.5 to 4 mA
cm−2 between individual samples. For Ti6Al4V ECAP potentials
stay below 3.5 VAgCl even for the highest current density, inter-
secting the 2 VAgCl line for current densities between 2.5 and
3 mA cm−2. Whereas for titanium the Faraday efficiency for the
oxide formation of the AR state is clearly above the ECAP state,
no such conclusion can be drawn for Ti6Al4V.
Figure 3E shows a quantification of the required charge den-
sities to reach potentials of 5, 8, and 10  VAgCl as a function of
the material treatment (AR or ECAP) and the electrolyte for all
investigated samples. A value of 2500 mC cm−2 with no error
bars in the diagram indicates that the target voltage was not
reached for the given combination of material and electrolyte.
For Ti AR the charge densities required to reach potentials
of 5, 8, and 10 VAgCl increase continuously in both electrolytes,
with the values in phosphate buffer being above those of per-
chlorate electrolyte. All data stay well below 1000 mC cm−2 even
for 10 VAgCl. Controversially, the required charge densities for
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Figure 3.  Galvanostatic anodic polarization: Typical potential/time (charge density) curves for stepwise galvanostatic polarization with current densi-
ties increasing from 0.5 to 5 mA cm−2 for A,C) titanium and B,D) Ti6Al4V in the AR and ECAP state in phosphate buffer 7.4 (A,B) and perchlorate elec-
trolyte (C,D). The dotted lines correspond to a theoretical curve for 100% Faraday efficiency for oxide formation. Diagram (E) quantifies the potential/
time (charge/density) curves presenting charge density data required to reach different potentials. Columns with a charge density of 2500 mC cm−2
without error bars indicate that this potential was not reached for the given combination of material and electrolyte; ⁎, ⁎⁎, ⁎⁎⁎ for p < 0.05, 0.01, 0.001.

Ti ECAP increase from about 700 mC cm−2 for 5 VAgCl to ≈1500
and 2000 mC cm−2 for 8 and 10 VAgCl, respectively, and are com-
parable between the two media. A similar situation is observed
for Ti6Al4V AR in both media, but with a parallel shift to higher
required charge densities for the perchlorate electrolyte and a
strong increase in the required charge densities between 8 and
10 VAgCl. While charge densities required for 5 and 8 VAgCl are
comparable between Ti AR and Ti6Al4V AR this is no longer
the case for 10 VAgCl. This potential is reached for Ti6Al4V AR
in phosphate buffer only at a charge density twice as high as
the one for Ti AR and not reached at all in perchlorate electro-
lyte. For the two ECAP-treated materials, higher charge densi-
ties are required in both electrolytes to reach given potentials, a
difference that is already pronounced for 5 VAgCl.
We thus can rank the electronic conductivities of the
forming anodic oxide layers in the initial phase of polariza-
tion in the order of Ti6Al4V ECAP > titanium ECAP > Ti6Al4V
AR≈titanium AR, which is in perfect agreement with the Nd
data presented in Figure 2C,D.
The increasing slope of the potential/time (charge density)
curves for ECAP-treated titanium at potentials > 6 VAg/AgCl indi-
cates an increasing Faraday efficiency. Anodic oxide formation on

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titanium based materials in neutral electrolytes results in oxide
layers from two sub-layers.[40] While the inner part is formed via
solid state reaction between titanium ions and oxygen ions in the
metal/oxide interface, the outer part is formed via “precipitation”
by transferred titanium ions with electrolyte components in the
interface oxide/electrolyte.[39] Here we postulate that the growing
outer part of these oxide layers is mainly responsible for the
increased Faraday efficiency, as its properties will not be affected
by the dislocation density in the metallic phase.
In conclusion, we present the first physico-chemical data
on the properties of air-formed and anodically prepared oxide
layers on ECAP-treated titanium materials. Studying changes
in the flatband potentials, donor densities, and electronic con-
ductivities of the oxide layers, we conclude that these properties
potentially influence the biological response to such materials
via increased redox interactions with adsorbed proteins.
Experimental Section
Cylindrical samples from CP titanium grade 2 (Ti/titanium) and
Ti6Al4V-ELI (Ti6Al4V) (for the chemical analysis of both materials
see Table S1, Supporting Information) were ECAP-treated under the
following conditions:
Ti 6 passes, route B120 at 400 °C (channel angle Φ 105°)
Ti6Al4V 4 passes, route BC at 500 °C (channel angle Φ 120°)
Afterward samples were metallographically prepared and contacted
with a wire made of CP titanium. For TEM investigations, thin lamellas
were prepared using a focus ion beam (Dual Beam FIB, FEI Helios 660).
The lamellas were further polished using slight Ar ion milling utilizing
a Fishione Nanomill model 1040 to remove surface damage stemming
from the Ga FIB.
The electrolytes used were 0.133 m phosphate buffer (phosphate) (pH
4.4, 7.4, and 9.2), 0.2 m NaClO4 (pH 7.4, adjusted with diluted NH4OH
solution) and cell culture medium (cell medium). Cell medium was
based on Dulbecco’s modified Eagle medium (DMEM) and contained
10% fetal calf serum.
Microscopic investigations were conducted using a Zeiss DSM
982 Gemini SEM and a JEOL JEM F200 STEM. EELS applied a GATAN
ContinuumER spectroscopic image filter, and EDX were obtained from a
window-less JEOL dual detector EDX system. Spatially resolved hardness
was measured with a testing machine KB-250BVZ.
EFB and Nd data were derived from electrochemical impedance
spectroscopy (EIS) measurements in a potential range from −0.5 to +1
VAgCl and a frequency range from 10 kHz to 1 Hz. Stepwise galvanostatic
polarization (GP) with increasing current densities (0.5 to 5  mA cm−2)
was run with 120 s polarization at each current density.
An electrochemical work station VMP3 (software package EC-Lab V
10.34) was used for all EIS and GP measurements. All electrochemical
measurements were performed at a temperature of 25 °C.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research did not receive any specific grant from funding agencies in
the public, commercial, or not-for-profit sectors.
Adv. Mater. Interfaces 2020, 2000552 2000552  (6 of 7)
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Conflict of Interest
The authors declare no conflict of interest.
Keywords
donor density, equal channel angular pressing, flatband potential, oxide
layer properties, titanium
Received: March 27, 2020
Revised: May 8, 2020
Published online:
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