Vacuum 86 (2012) 608e613

Contents lists available at ScienceDirect

Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Surface characterization of titanium hydride powder


Irena Paulin a, b, *, Crtomir Donik b, Djordje Mandrino b, Maja Von
cina c, Monika Jenko b
a
TALUM d.d. Kidricevo, Tovarniska cesta 10, 2325 Kidricevo, Slovenia
b
Institute of Metals and Technology, Lepi pot 11, 1000 Ljubljana, Slovenia
c
University of Ljubljana, Faculty of Natural sciences and Engineering, Department of Materials and Metalurgy, Askerceva 12, 1000 Ljubljana, Slovenia

a b s t r a c t
Keywords: Titanium hydride is well known for its stability in air because of formation of thin TiO2 oxide layer on top
TiH2 of TiH2 powder particles. Formation of the oxide layer is directly related to high affinity of Ti to oxygen
TiO2
and it can be formed in few seconds also on top of TiH2 particles in low vacuum. On the other hand,
AES
XPS
thickness of TiO2 layer on the formed TiH2 powder is in the range of 130 nm. Existence of oxide layer on
SEM/EDXS top of powder particles was confirmed with AES, XPS and EDXS cross section line scans. Formation of
DSC/TG thin oxide was confirmed also with calculations based on chemical and TG analyses.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction Due to the exceptionally high affinity of titanium to oxygen, an

Titanium hydride is an excellent catalyst in many chemical
reactions especially in reversible dehydrogenation of carbon nano-
tubes [1] and in preparation of titanium compounds [2,3]. Further it
is used as a source of pure H2 [4] for formation of ceramic and glass
seals using a mixture of active metallic titanium or titanium
hydride in powder form [5] and for titanium coatings [6]. In
powdery form it is also used as foaming agent in production of
metallic foams. It is a highly reactive chemical compound that
needs to be kept away from heat and strong oxidizers, though it is
highly stable in air [7]. It is a dark grey powder with a density of
3.75 kg/dm3 and it decomposes to Ti(s) and H2(g) at 450
C [8].
Titanium hydride is formed by reaction of titanium with
hydrogen, Ti(s) þ H2(g) / TiH2(s). Titanium has high affinity to
hydrogen and high hydrogen concentrations in titanium can cause
formation of various titanium hydrides, such as TiH2, TiH, TiH0.71
and others [9]. Nevertheless, TiH2 is most frequently cited in
references as the product of a chemical equilibrium reaction [10,11].
TiH2 can be rapidly synthesized at room temperature by ball milling
titanium powders in a hydrogen atmosphere. The hydrogenation
process begins with formation of titaniumehydrogen solid solu-
tion, followed by formation of titanium hydride. The hydride that is
formed by the milling process, has lower initial and final temper-
atures of dehydrogenation and a slightly narrower temperature
range of dehydrogenation in comparison with a hydride that is
prepared by standard methods [12].
* Corresponding author. Institute of Metals and Technology, Lepi pot 11, 1000
Ljubljana, Slovenia.
E-mail address: irena.paulin@imt.si (I. Paulin).
oxide layer is formed on the surface of all titanium compounds. The
thickness of this layer depends on the morphology of Ti materials
and on the method of Ti surface preparation [13]. Therefore special
preparation in UHV with noble metal deposition is required when
the surface of titanium and/or titanium compounds is examined. A
thin layer of noble metal sputtered in situ on Ti or TiO2 has been
shown to prevent air interaction with Ti materials, thus enabling
transport of samples to analyzers in order to analyze oxides with
surface-sensitive techniques, such as Auger electron spectroscopy
(AES) and X-ray photoelectron spectroscopy (XPS) [14,15].
Differential scanning calorimetry (DSC) shows that hydrogen is
normally liberated at approximately 495
C [16] and that heat
treatment in air delays hydrogen evolution and shifts it to higher
temperatures. Gas evolution is rapid at relatively high temperatures
(melting point of powdery material). Formation and liberation of H2
takes 3e5 min [16]. When TiH2 powder is pre-treated in air at
a certain temperature, decomposition of hydride is delayed. Liu H.
et al. [9,16] made a study on dehydrogenation of TiH2 powders
which was based on the high-temperature XRD experiment. The
TiH2(s) / TiHx(s) þ H2(g) reaction, 1.5 < x < 2, took place when the
temperature was below 550
C. Bhosle et al. [17] observed dehy-
drogenation of TiH2 that occurred in two steps; TiH2 / TiHx / a-
Ti, where 0.7 < x < 1.1. Kennedy [18] observed dehydrogenation of
TiH2 during heat treatment at various temperatures and he also
discovered a difference in colouration of powders. In this paper we
have focused on the characterization of TiH2 powder at room
temperature and its activity at temperatures up to 720
C. The
selected temperature was approximately the temperature of the
aluminum foaming process because that was our particular interest
in studying TiH2 powders.

0042-207X/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2011.07.054
 I. Paulin et al. / Vacuum 86 (2012) 608e613 609

However, most researchers claim that hydrogen liberation from

TiH2 commences at approximately 400
C [9,16,19] and they cite
that TiH2 is highly stable in air at room temperature [7]. However,
its stability in air at room temperature is the consequence of the
thin layer of oxide that is formed on the surface of TiH2 powder
particles [20,21].
In this research our intention was to confirm the existence of
a titanium oxide layer as protection on TiH2 powder particles from
premature evolution of hydrogen and to determine the thickness of
the oxide layer on the surface of powder particles. As-received and
AuPd-coated TiH2 powders were characterized by surface-sensitive
techniques, such as Auger electron spectroscopy (AES) and X-ray
photoelectron spectroscopy (XPS). Chemical analysis, SEM imaging
and EDXS line analyses were also made. In order to confirm the
homogeneity of the TiH2 powders, differential scanning calorimetry
(DSC) and thermogravimetric analysis (TG) were also performed.

2. Materials and methods Fig. 2. SE image of EDXS line analysis spots on cross section TiH2 powder particle.

The material used in this study was commercial as-received TiH2

3100RL inductively-coupled plasma-atomic emission spectroscopy
powder, 99.5% pure, with grain size 1e35 mm. It was characterized
system (ICPeAES).
by different surface-sensitive techniques, AES and XPS. Chemical
TiH2 powder was characterized with and without any pre-
analysis, SEM images and DSC/TG analyses were also performed.
treatment by AES/XPS using the VG Scientific Microlab 310F
First of all, scanning electron microscopy images and energy
instrument with Avantage. XPS depth profiles of oxide layers were
dispersion spectroscopy (EDXS) line analysis were performed with
characterized with the VG Microlab 310F AES/XPS. In all the XPS
the FE-SEM JEOL JSM-6500F field emission scanning electron
measurements, Mg K radiation at 1253.6 eV with anode
microscope, and with the Inca Energy 400 EDXS analyzer. TiH2
voltage  emission current ¼ 12.5 kV  16 mA ¼ 200 W was used.
powder was fixed to carbon tape on the SEM holder for SEM
The Arþ energy of 3 keV for 1 mA ion current over the 8  8 mm2 area
imaging. Images were made at 15 kV and various magnifications,
was similar to the ion-beam parameters used in sputter-cleaning of
and they are shown in Figs. 1 and 2. TiH2 powder for the EDXS line
the sample, apart from the raster area being closer to 10  10 mm2 in
analysis was prepared as for standard metallographic specimens:
this case. The thickness of the passive layer was estimated by argon-
hot mounted into Bakelite and then ground and polished.
ion sputtering. The reference-sputtering rate was 0.01 nm/s and it
Differential scanning calorimetry (DSC) and thermogravimetric
was calculated relatively to Ta2O5, as the intensity of oxygen signal
analysis (TG) were performed with the Netzsch STA 445 C Jupiter.
decreased to a half. Casa XPS software [22] was applied to process
As-received TiH2 powder was heated from room temperature up to
the data. The XPS peaks were separated into contribution peaks of
720
C with a heating rate of 10
C/min and then cooled down to
different species that were quantified separately. The Shirley back-
room temperature at the same rate. Analysis was performed in an
ground, the Scoffield cross-sections and the standard peak param-
argon protective atmosphere. The final temperature was selected
eters were used to evaluate and quantify the spectra [22]. Binding
due to our interest of TiH2 powder usage in the production of
energy differences of components were fixed at values given in
aluminum foams.
references and the full widths at half maximum (FWHM) for oxide
An Alcatel CILAS HR 850-B laser grain size analyzer was used for
peaks were fixed to be the same. TiH2 powders were fixed onto
laser granulometry measurements. Ethanol was used as the
sample holders for AES/XPS examinations using UHV compatible
medium in the grain size analysis.
silver double-side sticking tape. Another sample of the as-received
Chemical analysis was made using the standard chemical
TiH2 powder was prepared by gold-palladium screening of the
method for determining elements with the Perkin Elmer OPTIMA
powder surface. The surface of the powder particles was first etched
for 1 h to remove oxides from the surface of powder particles with
the Gatan Model 682 Precision Etching Coating System (PECS) at
500 mA and at approximately 10 keV of beam current. The sample
rotated at 20 rpm during the etching. Afterwards powder particles
were coated with a 7 nm thick layer of AuPd. The precise thickness
was detected by the Gatan Thickness Monitor (Model 681.20000).
The AuPd-coated sample was used for analyzing the TiH2 surface to
avoid the rapid formation of a thin oxide layer on the surface of
powder particles. Screening of the etched powder surface with
noble metal is needed to protect the sample from additional
oxidation during sample transport to analyzer. The as-received and
the AuPd-coated TiH2 powders, were characterized by XPS and AES.

3. Results and discussion

3.1. FE-SEM

A secondary electron SEM image of the synthesized titanium

Fig. 1. SEM image of titanium hydride powder particles. hydride powders is shown in Fig. 1. Particle size distribution was in
610 I. Paulin et al. / Vacuum 86 (2012) 608e613
Fig. 3. XPS spectrum of Ti region.
the range from less than 1 mm to over 50 mm in diameter.
Morphology is represented by angular polygonal shapes with many
facets. The distribution of approximately 70 vol% of powder parti-
cles is in the range of 10e20 mm. The particle size distribution of
TiH2 powder was determined by laser granulometry.
The cross section of a TiH2 powder particle was analyzed by
EDXS line analysis. Analyzed spots of EDXS are shown as
a secondary electron image in Fig. 2a. At the beginning and at the
end of the path through the powder particle, in line spectra 1 and
10, oxygen was detected while, in the rest of the line spectra, only Ti
was detected (as shown in Fig. 2b). Results of EDXS line analysis
indicated that not only titanium (hydrate), but also a thin layer of
oxygen (oxide), was on the surface of the TiH2 powder.
It is presumed that hydrogen diffuses from the surrounding
atmosphere into the Ti grain during formation of TiH2, since its size
is very small. It is known that TiH2 is highly stable in air [7] and this
stability can also be the consequence of an oxide layer on the
surface of TiH2 powder particles [23]. The presence of an oxide
layer was also confirmed by surface-sensitive AES and XPS tech-
niques (Figs. 3e7).
3.2. Chemical analysis
The as-received TiH2 powder was analyzed using standard ICP-
AES analysis for determination of chemical elements. TiH2 powder
Fig. 4. XPS spectra of Ti region; spectrum of AuPd shelted TiH2 (S1); spectra S2eS8
each after 10 min of etching time.
Fig. 5. XPS depth profile of TiH2 powder AuPd coated.
should stoichiometrically represent a compound of 95.96 wt% Ti
and 4.04 wt% H. Results of chemical analysis do not support this
theoretically calculated stoichiometric composition and homoge-
neity of the TiH2 powder [9], since 91.0 wt% Ti was determined in
the TiH2 powder. This lower concentration of Ti in powder is
consistent with the existence of a TiO2 layer on the powder parti-
cles surface, since the stoichiometric concentration of Ti is much
lower in TiO2 than in TiH2. If it is assumed that there is just TiO2 on
the surface of TiH2 powder particles, the calculated ratio of TiH2 and
TiO2 is approximately 0.86.
3.3. DSC and TG
DSC and TG analyses were performed in an Ar atmosphere with
heating rate of 10
C/min from room temperature up to 720
C.
Samples were then held there for 10 min and afterwards cooled
down with cooling rate of 10
C/min. The heating trace is shown in
Fig. 8a where the trace up to (3.1) represents the heating period
(10
C/min), from (3.1) to (3.2) is the section of constant tempera-
ture and, from (3.2) to (3.3), there is the cooling section of the
heating trace (10
C/min).
Reduction of mass commenced at 416
C (Figs. 8b and 9) 3.15 wt
% of mass loss occurred up to 720
C (Fig. 8b). The total mass loss
was 3.38 wt% while the calculated value was 4.04 wt% [19]. From
the DSC/TG analysis from the literature [19] of the liberation of
hydrogen up to 920
C the detected total mass loss was 3.78 wt%.
The majority of hydrogen was liberated below 720
C, and mass
Fig. 6. XPS depth profile of the as-received TiH2 powders.
 I. Paulin et al. / Vacuum 86 (2012) 608e613
reduction continued when the sample was held at this tempera-
ture. Our analyzed results confirm the presence of a small amount
of oxide in a layer on the surface of the powder grains. The amounts
of liberated and calculated hydrogen were 3.38 wt% (our results)
and 4.04 wt%, respectively, and their ratio was 0.84, which was
close to the calculated ratio of TiH2 vs. TiO2 from ICP-AES chemical
analyses.
The DSC curve in Fig. 4 indicates the starting point of TiH2
powder decomposition at 416
C. The double negative maximum
on the DSC curve indicates two endothermic reactions, where the
first negative maximum is at approximately 500
C and the second
one at approximately 585
C. A third small endothermic shoulder-
like peak can be seen at elevated temperatures above 620
C. This
was in good agreement with Refs. [9,18]. Our first endothermic
Fig. 7. Differentiated AES spectra of Ti region; (a) after short sputtering time; (b) after
sputtering time of 2400 s; (c) after sputtering time of 6000 s.
611
reaction started at 416
C and the second one at 538
C, while the
third one could not be precisely determined, but it was around
620
C. These three endothermic reactions can be explained by
slight modification of the 4-step TiH2 dehydrogenation theory
described in Ref. [9]. The proposed 4-step TiH2 dehydrogenation [9]
is: TiH2 / TiH1.5, as step 1, Ti1.5 / TiH, as step 2, TiH / TiH0.2 as
step 3, and TiH0.2 / Ti as step 4. We propose an explanation of our
DSC peaks by modifying the 4-step TiH2 dehydrogenation. The
steps 1 and 2 occurred simultaneously and could be combined into
one larger endothermic peak with negative maximum at 500
C.
The second DCS negative maximum could be assigned to e.g. step 3
(TiH / TiH0.2), and the last broad shoulder could be explained as
the last step of the 4-step TiH2 dehydrogenation theory that
consumed the least amount of energy. Total consumed energy for
this reaction was determined to be 1431 J/g, and it was obtained
from the area between the ‘zero line’ and negative peaks on the DSC
curve.
3.4. X-ray photoelectron spectroscopy and Auger electron
spectroscopy
Fig. 3 shows high-resolution XPS scans of the Ti 2p1/2 and Ti 2p3/
2 transitions for corresponding metallic and oxide species. Typical
binding energies (2p3/2) for different Ti species are at approxi-
mately 453 eV, for TiH2, at 454.5 eV for Ti (metal), and at 459.5 eV
for TiO2. Different references give various binding energy values for
Ti species [11,24e27]. Nevertheless, the peaks of TiO2 have binding
energy of approximately 5 eV or 6 eV higher than the peaks of Ti
and TiH2, from which the thickness and composition of the oxide
layer on the top TiH2 powder can be determined.
Fig. 4 shows both the oxide and the metallic components for the
specific region of Ti 2p transitions of the Ti species. These types of
spectra sets were used for assembling the presented XPS depth
profiles in Figs. 5 and 6 [28e30].
XPS depth profiles of TiH2 powders prepared by AuPd screening
and without any pre-treatment are shown in Figs. 5 and 6. The
AuPd screening was applied on the surface after the ion sputtering
in the Gatan PECS to protect pure TiH2 bulk material inside the
powder particle for the purpose of analyzing non-contaminated
samples with surface-sensitive analyses (AES/XPS). Although the
TiH2 powder was sputtered for an hour in the Gatan PECS and then
coated with goldepalladium to prevent oxidation during transport
to the XPS/AES chamber, TiO2 was still seen to be present on the
surface of the powder in the XPS and AES spectra even after pro-
longed sputtering at 10 kV, 400 mA over an area of 1 cm2 with Arþ
ions in the Gatan PECS.
Fig. 5 shows the XPS depth profile of Ti where a TiO2 layer covers
Ti hydride powder particles. The oxide was partially removed only
after prolonged Ar-ion sputtering inside the VG Microlab 310F in
a vacuum of order 109 mbar. The TiO2 concentration was reduced
by 60% only after 1200 s of sputtering. This is probably due to the
high titanium affinity to oxygen. A certain amount of TiO2 was
deposited on the surface of powder particles even after treatment
with Ar-ions for an hour at 10 keV, since the vacuum in the PECS
preparation chamber was approximately of order 105 mbar. After
this prolonged sputtering the AuPd layer was applied on the
powder particles to protect TiH2 powder for transportation to the
XPS chamber. Profiles in Figs. 5 and 6 indicate that this oxide layer is
ill defined, with slowly changing concentrations of oxidized and
non-oxidized Ti from the surface of the oxide layer towards the
sample interior consisting of Ti and TiH2. The last section of the Ti
XPS depth profile shows total removal of TiO2 and increase of TiH2
and Ti concentrations. Higher Ti concentration can also be present
due to an Ar-ion sputtering effect of possible reduction/oxidation,
and it partially belongs to TiH2 and TiO2.
612 I. Paulin et al. / Vacuum 86 (2012) 608e613
Fig. 8. TG trace of heating TiH2 up to 720
C and cooling down in Ar flow at 10
C/min; (a) heating trace, (b) TG curve.
Fig. 6 shows the Ti XPS depth profile of TiH2 powder without any
pre-treatment. The results of the XPS depth profile are similar to
the measured differences of layer thicknesses in Fig. 5. The
concentration of TiO2 here was reduced after 5000 s of sputtering
time to approximately 50 at%. This indicated a much thicker TiO2
oxide layer that was still approximately 130 nm thick. Differences
in obtained results between the not pre-treated and the AuPd
screened TiH2 powders were observed just after longer sputtering
time, and this led to the conclusion that TiO2 was present on the
whole TiH2 powdery material when this material was exposed to
oxygen. After much longer sputtering, TiO2 concentration was
reduced, and that resulted in an increase of TiH2 and Ti concen-
trations on the TiH2 powder. The conclusion can be made that the
thickness of the TiO2 layer on the as-received TiH2 powder particles
was approximately 130 nm.
Also AES analyses were performed on the surface of TiH2
powders prepared by AuPd surface screening. In the VG Scientific
Microlab 310F instrument the Argon ion sputtered AuPd screened
layer was first removed and then the powder was analyzed. The
AES spectrum had, according to Ref. [26], typical differentiated
characteristic peaks of Ti at approximately 385 eV and a small
hydrogen-induced peak around 443 eV of kinetic energy [14,31].
However, the AES characteristic peak for TiH2 has also a different
peak shape (Fig. 5). This indicated possible application of AES also
for chemical characterization and not just for elemental
Fig. 9. DSC trace of heating TiH2 in Ar flow at 10
C/min up to 720
C.
composition as commonly used because the shapes of peaks
differentiate Ti, TiO2 and TiH2 species.
Fig. 7a shows the differentiated AES spectrum of the AuPd-coated
TiH2 powder, where the oxygen peak present at approximately
510 eV is large, while the Ti peak is at approximately 385 eV. This
indicates the presence of TiO2 on the surface of the TiH2 powder.
After sputtering for 2400 s, the peak at 510 eV was reduced with the
time of sputtering (Fig. 7b), but the peak at 385 eV became bigger,
which also confirms the thickness of the titanium oxide layer on top
of TiH2 powder particles. After sputtering, a different peak shape
appeared at approximately 385 eV, which is the characteristic peak
for Ti metal. The oxygen peak disappeared with continued sputter-
ing, and the characteristic Ti metal peak changed its shape and
intensity. The characteristic Ti metal peak was no longer observed
after 6000 s sputtering (Fig. 7c), while additional hydrogen-induced
lines, characteristic of Ti, start to appear at approximately 411 eV.
Another specific feature for TiH2 powders was at approximately
411 eV, where the peak intensity was much lower than the one that
existed at 385 eV, when spectra in Fig. 9(b) and (c) were compared.
This was in good agreement with other published results [14,26].
However, the differentiated AES spectra show that characteristic
oxygen peak has the highest intensity at the beginning of sputter-
ing and that it is slowly attenuating with sputtering time, though it
still looks high in comparison to titanium peaks. The characteristic
Ti metal peak that appears at certain kinetic energy (385 eV) is
present only after a defined sputtering time, which means that
there are titanium metal and titanium compounds present.
4. Conclusions
TiH2 powder is highly stable in air and all the results of this
study were applied to characterize the surface of the powder
particles. XPS depth profiles, AES and SEM EDXS line scans yield
similar results. All the surface-sensitive techniques confirm the
existence of an oxide layer on top of powder particles. The calcu-
lated thickness based on sputtering time and sputtering ratio from
AES and XPS depth profiles analysis was approximately 130 nm.
The DSC curve indicates that hydrogen is liberated from tita-
nium hydride above 416
C according to the 4-step TiH2 dehydro-
genation theory. Heating up to 720
C and holding at this
 I. Paulin et al. / Vacuum 86 (2012) 608e613
temperature yields a mass reduction of 3.38%, as a result of
hydrogen evolution.
Chemical analysis corroborated that the actual concentration of
titanium in TiH2 is lower than the calculated value due to the
presence of a TiO2 layer on top of TiH2 powder particles. The
calculated ratio of TiH2 vs. TiO2 obtained from chemical analysis is
in good correlation with the same ratio obtained by the TG analysis,
with values 0.86 and 0.84, respectively.
Characteristic peaks of TiH2 were determined using AES analysis
and confirmed by XPS spectra and XPS depth profiles.
Acknowledgements
This work has been supported by the “Physics and Chemistry of
Porous aluminum for Al panels capable of highly efficiently energy
absorption” project L2-2410 (D), funded by the Slovenian Research
Agency. Views expressed in this publication reflect only the views
of the authors and the SR Agency is not liable for any use that may
be made of information contained therein. The authors also
acknowledge Dr Borivoj Su starsi
c who provided the TiH2 powder.
References
[1] Kumar RS, Cornelius AL, Pravica MG, Nicol MF, Hu MY, Chow PC. Bonding
changes in single wall carbon nanotubes (SWCNT) on Ti and TiH2 addition
probed by X-ray Raman scattering, vol. 16. SA: Elsevier Science; 2007. p.1136.
[2] Reilly JJ, Wiswall RH. Formation and properties of iron titanium hydride.
Inorganic Chemistry 1974;13:218.
[3] Jia FQ, Chi TS. Tin and tinetitanium as catalyst components for reversible
hydrogen storage of sodium aluminium hydride. Fuel 2006;85:2141.
[4] Antonov VE, Bashkin IO, Fedotov VK, Khasanov SS, Hansen T, Ivanov AS, et al.
Crystal structure and lattice dynamics of high-pressure scandium trihydride.
Physical Review B 2006;73:6.
[5] Bankuti, Laszlo, Gyorgy, Miklos, Nagy, Barnabas. Discharge lamp with end of
life arc extinguishing structure, vol. 6380676. United States.
[6] Beeferman, Dennis, Lucas, William. Titanium hydride coated brazing product,
vol. 5186380. United States Patent.
[7] Vennila RS, Durygin A, Merlini M, Wang Z, Saxena SK. Phase stability of TiH2
under high pressure and temperatures. International Journal of Hydrogen
Energy 2008;33:6667.
[8] Lide DR, Lide BB. Critical data in physics and chemistry. In: Robert AM, editor.
Encyclopedia of physical science and technology. New York: Academic Press;
2001. p. p.1.
[9] Liu H, He P, Feng JC, Cao J. Kinetic study on nonisothermal dehydrogenation of
TiH2 powders. International Journal of Hydrogen Energy 2009;34:3018.
613
[10] Mackay KM. Hydrogen compounds of the metallic elements. London: Spon;
1965.
[11] Hayashi K, Nakagawa ST, Mizuno Y, Tanaka A, Homma T. Ab initio molecular
orbital calculation for hydrogen-induced states of titanium (III). Surface and
Interface Analysis 2003;35:104.
[12] Zhang H, Kisi EH. Formation of titanium hydride at room temperature by ball
milling. Journal of Physics-Condensed Matter 1997;9:L185.
[13] van den Berg AHJ, Lisowski W, Smithers M. SEM and AES depth profile studies
of thin titanium and titanium oxide films covered by nanoscale evaporated Au
layers. Fresenius Journal of Analytical Chemistry 1999;365:231.
[14] Paulin I, Mandrino D, Donik C, Jenko M. AES and XPS characterization of
titanium hydride powder. Materiali in Tehnologije 2010;44:73.
[15] Davis GD, Natan M, Anderson KA. Study of titanium-oxides using auger line-
shapes. Applied Surface Science 1983;15:321.
[16] Kennedy AR. The effect of TiH2 heat treatment on gas release and foaming in
AleTiH2 preforms. Scripta Materialia 2002;47:763.
[17] Bhosle V, Baburaj EG, Miranova M, Salama K. Dehydrogenation of TiH2.
Materials Science and Engineering A-Structural Materials Properties Micro-
structure and Processing 2003;356:190.
[18] Asavavisithchai S, Lopez VH, Kennedy AR. Non-isothermal decomposition of
as-received and oxidised TiH2 powders, vol. 48. Japan Inst Metals; 2007. 2712.
[19] Matijasevic-Lux B, Banhart J, Fiechter S, Gorke O, Wanderka N. Modification of
titanium hydride for improved aluminium foam manufacture. Acta Materialia
2006;54:1887.
[20] von Zeppelin F, Haluska M, Hirscher M. Thermal desorption spectroscopy as
a quantitative tool to determine the hydrogen content in solids. Thermochi-
mica Acta 2003;404:251.
[21] von Zeppelin F, Hirscher M, Stanzick H, Banhart J. Desorption of hydrogen
from blowing agents used for foaming metals. Composites Science and
Technology 2003;63:2293.
[22] Fairley N. CasaXPS VAMAS Processing Software. http://www.casaxps.com/.
[23] Paulin I, Donik C, Jenko M. Mechanisms of HF bonding in dry scrubber in
aluminium electrolysis. Materiali in Tehnologije 2009;43:189.
[24] Chopovskaya EV, Nosenko VY, Pivovarov AL. X-ray photoelectron studies of
TiCo surface treated in RF-plasma in H2 atmosphere. Journal of Electron
Spectroscopy and Related Phenomena 1994;68:699.
[25] Liu GW, Li W, Qiao GJ, Wang HJ, Yang JF, Lu TJ. Microstructures and interfacial
behavior of zirconia/stainless steel joint prepared by pressureless active
brazing. Journal of Alloys and Compounds 2009;470:163.
[26] Lisowski W, AHJvd Berg, Leonard D, Mathieu HJ. Characterization of titanium
hydride films covered by nanoscale evaporated Au layers: ToF-SIMS, XPS and
AES depth profile analysis. Surface and Interface Analysis 2000;29:292.
[27] Chastain J, King RCJ, editors. Handbook of X-ray photoelectron spectroscopy.
Minnesota, USA: Physical Electronics, Inc.
[28] Donik C, Kocijan A, Mandrino D, Paulin I, Jenko M, Pihlar B. Initial oxidation of
duplex stainless steel. Applied Surface Science 2009;255:7056.
[29] Donik C, Kocijan A, Paulin I, Jenko M. The oxidation of duplex stainless steel at
moderately elevated temperatures. Materiali in Tehnologije 2009;43:137.
[30] Donik C, Kocijan A, Grant JT, Jenko M, Drenik A, Pihlar B. XPS study of duplex
stainless steel oxidized by oxygen atoms. Corrosion Science 2009;51:827.
[31] Davis LE. Handbook of Auger electron spectroscopy: a reference book of
standard data for identification and interpretation of Auger electron spec-
troscopy data. Eden Prairie, Minnesota: Physical Electronics Industries; 1976.