Powder Metallurgy

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Surface chemistry of the titanium powder studied

by XPS using internal standard reference

Ruslan Shvab, Eduard Hryha & Lars Nyborg

To cite this article: Ruslan Shvab, Eduard Hryha & Lars Nyborg (2017) Surface chemistry of the
titanium powder studied by XPS using internal standard reference, Powder Metallurgy, 60:1, 42-48,
DOI: 10.1080/00325899.2016.1271092

To link to this article: http://dx.doi.org/10.1080/00325899.2016.1271092

Published online: 31 Dec 2016.

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POWDER METALLURGY, 2017
VOL. 60, NO. 1, 42–48
http://dx.doi.org/10.1080/00325899.2016.1271092

Surface chemistry of the titanium powder studied by XPS using internal

standard reference
Ruslan Shvab, Eduard Hryha and Lars Nyborg
Department of Materials and Manufacturing Technology, Chalmers University of Technology, Gothenburg, Sweden

ABSTRACT ARTICLE HISTORY

Surface chemistry of the titanium powder has particularly growing interest due to the increasing Received 21 September 2016
application of titanium components prepared by powder metallurgy, in particular metal Accepted 6 December 2016
injection moulding and additive manufacturing. Due to the high chemical activity, number of
KEYWORDS
titanium oxides, calcium and complex Ca–Ti–oxides can be expected on the component/ XPS; titanium oxide
medical implant surface, depending on powder and component manufacturing and post- standards; calcium titanate;
treatment, but are very difficult to analyse due to the lack of the experimental data and calcium oxide; rutile; anatase;
analysis methodology. Therefore, a methodology for the analysis of the surface chemistry of oxide layer thickness; surface
the Ti-powder by XPS utilising internal standard reference was developed. The obtained contaminations
methodology was used for the surface analysis of titanium powder and identification of its
surface oxide composition. The results show that the powder surface is covered by TiO2 layer
in the form of rutile with a thickness of 4.4 nm. Carbon and nitrogen impurities were also
found present on the powder surface.

Introduction spread in published Ti2p3/2, Ca2p3/2 and O1s binding

energy values [3–17]. The absence of unique method-
Titanium and its alloys have become very popular and
ology and connected reliable data concerning different
widely used materials in different structural applications,
titanium oxides makes it difficult to analyse these oxides
aerospace, dentistry and orthopaedics due to their light
and to distinguishing them from one another. The pre-
weight combined with good mechanical properties and
sent study is focused on the analysis of standard peak
corrosion resistance. Powder metallurgy (PM) offers
positions of TiO2, CaTiO3 and CaO powdered oxide
the possibility to produce near-net shape components/
standards by XPS with further application of obtained fit-
implants in one step [1]. However, due to the high surface
ting parameters for the investigation of the surface of tita-
area of the powder, information about surface compo-
nium powder – identification of the type of surface oxide
sition is one of the most important aspects, determining
covering the powder surface and the presence of surface
usability of powder for PM processing and conditions for
impurities.
future consolidation [2]. Calcium is one of the trace
elements, present in Ti-alloys, and hence its effect on sur-
face oxide distribution and chemical state is of vital
Experimental materials and methods
importance. XPS in this case is one of the most powerful
techniques that provides information about the presence TiO2, CaTiO3 and CaO standard powders with the
of Ca-containing oxides, their chemistry and distri- purity better than 99% were acquired from SIGMA-
bution. Titanium and calcium oxides have been widely ALDRICH CHEMIE GmbH (Steinheim, Germany).
studied during the last four decades. Still, there is large Titanium powder was produced by TLS Technik

CONTACT Ruslan Shvab ruslan.shvab@chalmers.se Department of Materials and Manufacturing Technology, Chalmers University of Technology,
Rännvägen 2A, SE-412 96 Gothenburg, Sweden
© 2016 Institute of Materials, Minerals and Mining Published by Taylor & Francis on behalf of the Institute

GmbH & Co. Spezialpulver KG (Bitterfeld, Germany).
As the manufacturing route, electrode induction inert
gas atomisation (EIGA) of Ti rod was used. In the pro-
cess, atomisation of the melt heated by induction is
done by highly pressurised argon (purity 99.9999
vol.-%, oxygen below 0.5 ppm) without contact to
graphite crucible or ceramic nozzle. The chemical com-
position and powder size fraction are summarised in
Table 1.
Specimens were prepared by mounting the powder
on a carbon tape for the XPS analysis of these samples
in their as-received state and after ion etching. In order
to introduce standard reference points for charge com-
pensation and peak positioning for different chemical
states, Au, Ag and Cu standards were applied on the
same sample, see Figure 1. These three standards
were also used for energy calibration using Au 4f7/2
(83.95 eV), Ag 3d5/2 (368.21 eV) and Cu 2p3/2
(932.62 eV) peaks. Energy calibration was carried out
under the same conditions as the high-resolution spec-
tra for the oxide powder standards. Each standard in
the form of plate (2), see Figure 1, was introduced
beside the powder mounted on carbon tape (3) in
such a way that XPS measurement of powder sample
and standard could be performed simultaneously (4).
The analysis area during the XPS analysis was
0.8 mm in diameter and the sample was placed in
such a way that the analysis area covered equal parts
of standard plate and powder sample. Both standard
plate and powder sample were mounted to the sample
holder on the carbon tape to avoid potential difference
in charging. Such measurements were performed in the
as-received state only. The behaviour of powder stan-
dard under ion etching was analysed on the same
Table 1. Powder size fraction and chemical composition of the
Ti powder.
Size fraction, µm O, wt-% C, wt-% N, wt-% Ti, wt-%
−45 0.16 0.003 0.005 bal.
Figure 1. Sample preparation set-up.
POWDER METALLURGY 43
samples, but from the sample site where only powder
was present (5), which prevented the deposition of
Au, Ag or Cu during ion etching. The same approach
was applied for depth profiling analysis of titanium
powder.
For the annealing trials, standard oxide powders
were compacted into thin discs with a thickness of
about 1 mm. The subsequent annealing was conducted
in a vacuum furnace, directly attached to the XPS
instrument, with the pressure from 10–6 to
10–7 mbar. This set-up for standard annealing is
described elsewhere [18]. The annealing was carried
out for 1 h at the temperatures between 500 and 800°
C, depending on the oxide type.
The surface chemical analysis of the oxide standards
and titanium powder was performed by means of a
PHI 5500 (Perkin Elmer, Waltham, MA, U.S.A.) XPS
instrument. The base pressure in the analysis chamber
was ∼10−9 mbar. Photoelectrons were excited by a
monochromatic Al Kα radiation (1486.6 eV). Selected
region spectra were recorded, covering the Ti2p3/2,
Ti2p1/2, Ca2p3/2, Ca2p1/2, O1s, N1s and C1s photo-
electron peaks. The acquisition conditions for such
high-resolution spectra were 23.5 eV pass energy with
the step of 0.1 eV and nominal take-off angle of 45°.
The recorded photoelectron peaks were curve-fitted
utilising the PHI MULTIPAK (Perkin Elmer, Wal-
tham, MA, U.S.A.) software with asymmetric curves
and assuming a Shirley background. The ion etching
was performed in argon gas with an accelerating vol-
tage of 4 kV. The etch rate was calibrated on a flat oxi-
dised tantalum foil with the well-known Ta2O5
thickness (100 nm), thus the oxide thickness refers to
Ta2O5 units. The angle between the ion incidence
and the sample surface was ∼50° [18].
Results and discussion
Taking to account the large spread in published Ti2p3/
2, Ca2p3/2 and O1s binding energy values and the
absence of reliable methodology for XPS investigation
of titanium powders, it was decided to perform the
investigation of powdered oxide standards of TiO2
(both rutile and anatase), CaTiO3 and CaO before
the investigation of the titanium powder. Ag standard
as the internal reference allowed to obtain XPS fitting
parameters necessary for the investigation of titanium
powder surface and identification of the type of the sur-
face oxide.
Investigation of the TiO2, CaTiO3 and CaO oxide
standard powders
Examination of the investigated oxide standards by
means of XPS showed contamination of their surfaces
regardless of their high chemical purity. It was reflected
in the broadening of the O1s peak, indicating the
44 R. SHVAB ET AL.
Figure 2. Detailed XPS spectra of Ti2p peak for TiO2 (rutile)
standard: change in oxide composition during argon etching.
presence of absorbed water/hydroxide and/or complex
oxides due to the chemical reactivity of the powder
samples connected to their large surface area. There-
fore, an accurate evaluation of the standard XPS spec-
tra for investigated oxides was impossible by the direct
acquisition of the XPS spectra without the application
of an additional contaminations removal procedure.
Hence, the most used method in XPS to clean the
sample’s surface by Ar+ sputtering was applied. The
obtained results confirmed the results of some authors
[3,4,7] concerning high sensitivity of titanium oxides to
argon ion etching. The etching damages stoichiometric
TiO2 surface, leads to broadening at the lower binding
energy side due to the reduction of the surface TiO2 to
intermediate oxidation states and even metallic Ti, see
Figure 2. Therefore, ion etching is unacceptable for
obtaining the representative oxide surface. Broadening
of the Ti2p3/2 peak recorded from the CaTiO3 standard
was also observed, while the Ca2p3/2 peak did not
change with ion etching for both CaTiO3 and CaO
cases.
Hence, the special vacuum heat treatment pro-
cedure was employed [18]. A number of annealing
trials at different temperatures followed by the XPS
analysis were performed for each oxide standard to
obtain the suitable annealing conditions. The required
temperatures and times for successful annealing of
the investigated oxide standards are summarised in
Table 2.
Still, obtaining the representative clean oxide surface
with stoichiometric composition, corresponding to the
bulk chemical composition, is not enough for its clear
Table 2. Annealing conditions applied for the investigated
oxide standards (vacuum, ∼10−7 mbar).
Powdered standard Temperature, °C Time, h
TiO2 (rutile) 500 1
TiO2 (anatase) 700 1
CaTiO3 500 1 Figure 3. XPS spectra of Ti2p peak for TiO2 (rutile) calibrated
CaO 800 1
identification due to the proximity of binding energy
peaks’ positions for oxides of interest. Hence, the
reliable XPS analysis always, in such cases, requires
stable internal reference for the interpretation of cor-
rect results. The adventitious C1s, that is the most fre-
quently used internal reference point for investigated
oxides [5,8,10,11,13], cannot be used as an internal
reference due to its very low intensity after annealing
and broad peak. At the same time, it was detected
that adventitious carbon peak position varied depend-
ing on the oxide standard even in as-received state and
hence it could not be a stable and reliable reference.
The Ti2p3/2 oxide peak set to 458.5 eV has also been
taken as the internal reference [3], but this approach
cannot be used in the present case of the identification
of surface compounds. Hence, Au, Ag and Cu stan-
dards as the internal references were applied to mini-
mise the measurement error and give reliable results
of binding energies. Such introduction of the standards
used for XPS calibration to the measured system
allowed us to obtain the peak positions of e.g. Ti2p3/2
in different compounds and easily distinguish them
from each other. Even though different results of bind-
ing energies were obtained using these standards with
the same powder sample, see Figure 3.
The analysis of results indicated that Cu cannot be
used as a stable and reliable internal reference because
it is sensitive to the oxidation. Cleaning of the surface
of Cu standard by ion etching is not applicable in the
current case because it will affect the powder sample
itself. The Au standard shows to be a robust one, but
the Au4f7/2 binding energy is at too low energy in com-
parison with binding energy of the elements of interest.
The Ag standard was chosen as preferable in this case
because the Ag3d5/2 binding energy is closest to the
ones of interest for investigated materials. Hence, this
will minimise instrumental effect on evaluation as e.g.
non-linearity of the binding energy scale. Moreover,
separate analysis of the Ag standard plate in as-received
state and after ion etching did not show shifting of the
according to different standards.
 POWDER METALLURGY 45

Table 3. XPS fitting parameters for the Ti2p3/2, Ca2p3/2 and O1s peaks for the investigated samples (Exp.) and values reported in the
literature.
Oxide standard E Ti2p3/2, eV FWHM Ti2p3/2 E O1s, eV FWHM O1s E Ca2p3/2, eV FWHM Ca2p3/2 Ref.
TiO2 (rutile) 459.52 1.09 530.75 1.25 … … Exp.
459.30 … … … … … [4]
458.50 … 530.08 … … … [5]
458.78 … 530.06 … … … [6]
458.80 … 531.40 … … … [8]
459.10 … … … … … [9]
458.46 1.04 529.70 1.03 … … [10]
459.00 … … … … … [11]
TiO2 (anatase) 459.65 1.05 530.87 1.30 … … Exp.
459.10 … … … … … [9]
458.59 1.04 529.87 1.10 … … [10]
459.00 … … … … … [11]
459.00 … 530.40 … … … [12]
CaTiO3 459.09 1.82 530.20 1.68 347.28 1.66 Exp.
458.67 … … … … … [11]
458.40 … 529.70 … 346.50 … [13]
… … … … 346.10 … [14]
458.40 1.70 … … 346.60 1.90 [15]
CaO … … 530.30 1.94 345.65 1.85 Exp.
… … 531.70 … 347.20 … [8]
… … … … 347.20 1.70 [15]
… … 528.90 … 346.00 … [16]
… … 529.90 … 347.10 … [17]

peak position. Hence, using Ag-standard as internal
reference, the accurate binding energy peak positions
(E) and width of the peak at half maximum
(FWHM) of Ti2p3/2, O1s and Ca2p3/2 were obtained
for the oxides of interest, see Table 3. The comparison
of such experimentally obtained peak characteristics
with the literature data shows high scatter of the pre-
sent data, as discussed above.
Narrow scans over the binding energies of the Ti2p
and Ca2p peaks for the annealed oxide standards, pre-
sented in Figures 4 and 5, clearly indicate a shift in the
peak positions and thus the possibility for easy identi-
fication of the type of Ti and Ca oxide present on the
surface of the powder.
Titanium powder surface investigation
Titanium powder surface characterisation was per-
formed by utilising fitting parameters obtained from
the oxide standards investigation to check the possi-
bility of usage and identification of the type of surface
oxide. Ag standard plate was co-mounted with powder
sample on the carbon tape as described above. The sur-
vey spectrum of such sample shows strong peaks of
titanium (Ti2p), silver (Ag3d), oxygen (O1s) and car-
bon (C1s), see Figure 6.
Ag standard as the internal reference allowed to
identify successfully the type of the powder surface
oxide. The exact match of Ti peak positions between
titanium powder and TiO2 rutile standard powder at
459.5 eV indicates the presence of rutile on the surface
of titanium powder, see Figure 7.
Wider Ti2p peak of titanium powder, in comparison
with rutile standard, is caused by metallic titanium and
some amount of oxides corresponding to lower oxi-
dation states (Ti2+ and Ti3+) present under the layer
of rutile covering the surface of the powder. Fitting of
Ti2p peak of titanium powder in as-received state

Figure 4. XPS spectra of Ti2p peak for TiO2 and CaTiO3 oxides. Figure 5. XPS spectra of Ca2p peak for CaO and CaTiO3 oxides.
46 R. SHVAB ET AL.

Figure 6. XPS survey spectrum of titanium powder co- Figure 8. XPS Ti2p spectrum of titanium powder in as-received
mounted with Ag standard plate. state, fitted using fitting parameters obtained from standards
analysis.

using fitting parameters obtained from standard analy-

to the significant decrease in the oxygen peak intensity.
sis, see Figure 8, showed that powder surface is predo-
Nitrogen has almost constant concentration of around
minantly (85.9%) covered by TiO2 oxide in the form of
2 at.-% at all etching depths. This indicates the pres-
rutile. Ti2O3 (5.7%), TiO (3.9%) and metallic Ti (4.5%)
ence of particulate nitrides, the size of which is larger
present under TiO2 layer were also detected in small
than the etching depth applied in this study.
amount indicating small layer thickness.
The thickness of the surface titanium oxide layer
The XPS analysis combined with Ar+ etching was
was evaluated using representative narrow scans of
further performed on the powder surface (analysing
titanium utilising the methodology developed in
area 2, Figure 1). It revealed very clean powder surface,
[19,20]. This methodology uses the relationship
containing titanium, oxygen, carbon and nitrogen.
between the normalised intensity of the titanium
Change in the chemical composition of the surface
metal peak and etch depth. Intensity of the metallic
with etching depth, see Figure 9, indicates a steep
peak of titanium at every etch depth was obtained by
decrease in oxygen concentration up to about 5 nm
the extraction of the metal intensity peak from the
etch depth after which slope of the decrease in oxygen
intensity of superimposed Ti peaks from high-energy
content becomes weaker. Removal of the surface con-
resolution narrow scans. Evaluation indicates the
taminants – etching of 1 nm – results in significant
thickness of the homogeneous titanium oxide layer to
decrease in the carbon peak that results in the increase
be 4.4 nm, Figure 10. Such small oxide layer thickness
in intensity of the titanium peak. Further etching leads
correlates very well with the presence of small Ti-metal
shoulder on the Ti2p peak in as-received state and with
Ti powders’ investigations in [21].
Taking to account that electron mean free path for
titanium oxide is λ = 1.7 nm, the XPS sampling depth

Figure 7. XPS Ti2p spectra of titanium powder, TiO2 rutile and

anatase standard powders, showing exact match in peak pos-
ition at 459.5 eV with rutile standard. Figure 9. XPS analysis of titanium powder vs. etch depth.

Figure 10. The normalised intensity of Ti-metal (Ti2p3/2-peak)
and oxygen (O1s–peak) vs. etch depth, indicating surface oxide
layer thickness of ∼4.4 nm.
is not more than 5.1 nm (3λ), according to the Beer–
Lambert law. In this case, 4.4 nm TiO2 layer thickness
corresponds to ∼86% of as-received signal intensity
what was also obtained by fitting of Ti2p peak in as-
received state, see Figure 8.
Conclusions
Ag standard as the internal reference for XPS analysis
of the TiO2 (rutile and anatase), CaTiO3 and CaO
oxide standards in powder form was utilised. The
values of the binding energy and width of the peak at
half maximum of Ti2p3/2, Ca2p3/2 and O1s for investi-
gated oxide standards were hence obtained. The con-
ditions for the heat treatment, required for obtaining
representative surfaces of the oxide standards, were
developed and peak positioning referencing was estab-
lished using internal standard sample like Ag plate co-
mounted with the oxide powder sample. The argon ion
etching is not recommended for obtaining a represen-
tative surface of titanium oxide standards because of
high sensitivity of Ti oxides to the ion bombardment.
Fitting parameters obtained from oxide standards
analysis were successfully applied for the titanium
powder. The examination of titanium powder showed
that its surface is covered by TiO2 oxide in the form
of rutile. The thickness of such oxide layer was
4.4 nm. Carbon and nitrogen impurities were also
detected on the powder surface.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
Support from the Chalmers Areas of Advance in Production
and Materials Science and funding from the strategic
POWDER METALLURGY 47
innovation programme LIGHTer provided by Vinnova are
gratefully acknowledged.
Notes on contributors
Ruslan Shvab is a postdoctoral researcher at the department
of Materials and Manufacturing Technology of Chalmers
University of Technology. The main research focuses are
powder surface characterisation, modelling of oxides in pow-
der for PM steels and recyclability of powders for additive
manufacturing. Ruslan Shvab obtained PhD in Materials
Science and Materials Engineering in 2014.
Eduard Hryha is an Associate Professor at the department of
Materials and Manufacturing Technology of Chalmers Uni-
versity of Technology. The main focuses of the research are
powder metallurgy, surface analysis using advanced surface-
sensitive techniques, thermal analysis, thermodynamic and
kinetic simulations. Eduard Hryha obtained PhD in
Materials Science and Materials Engineering in 2008.
Lars Nyborg is a Professor of Surface Technology in the
Department of Materials and Manufacturing Technology,
Chalmers University of Technology. He is the leader of pow-
der metallurgy and surface technology research within the
Surface and Microstructure Engineering Group. He is a fel-
low of Royal Swedish Academy of Engineering Sciences
and he has taken strong interest in developing scientific
co-operation with industry in the area of powder metallurgy,
but also in other areas integrating materials and manufactur-
ing engineering research, such as metal cutting and high
strength materials. Lars Nyborg was educated in Gothenburg
and received his PhD in 1987.
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