Journal of Renewable Energies xx (20xx) xx – xx; DOI: ……………..

Journal of Renewable Energies

Revue des Energies Renouvelables

journal home page: https://revue.cder.dz/index.php/rer

Researchpaper

Physico-chemical characterization of Al2O3/Ti6A4V type thermal

barrier systems

Djamel Amaria, Khaoula Rahmounib, Nadia Saoulac Youcef Khelfaouid

a
Laboratoire de génie de l’environnement (LGE), Université de Bejaia, route de Targa Ouzamour, Bejaia,
Algérie
b
laboratoire des matériaux et composantes actives (LMCA), Institut des sciences et technologies appliquées
(ISTA), Université de Oum El Bouaghi, 04000, Algérie.
c
Centre de Développement des Technologies Avancées (CDTA), Cité, 20 Août 1956, Baba Hassen, Alger,
Algérie
d
Laboratoire de mécanique, matériaux et énergétique (L2ME), Université de Bejaia, route de Targa Ouzamour,
Bejaia, Algérie

ARTICLEINFO ABSTRACT

Articlehistory: Al2O3 alumina deposits were deposited on Ti6A4V titanium alloy substrates
Received by rf-PVD at different substrate polarizations 0V, -50V, -100V and without
Accepted polarization (wp). SEM images, at the surface of the deposits, showed a very
good substrate coverage with a dense morphology. Quantitative EDS analysis
Keywords: of these deposits revealed the presence of the elements Al and O in these
Al2O3 deposits. The mass percentage of these elements, at different polarizations of
Ti6A4V the substrate, varies between 51.72% and 56.19% for Al and between
deposits 43.80% and 48.27% for O. The images, revealed by AFM, showed well-
Rugosité spread deposits on the surface of the substrates with relatively uniform
Cristallisation grooves. The values of the arithmetic roughness Ra, ranging from 3.45 to
Polarisation 4.75 nm, testify to the low crystallinity of these deposits and an appreciable
density. The DRX of these deposits in 2θ mode showed a weak
crystallization of the Al2O3 phase and characteristic peaks of the partially
crystallized phases Al0.3Ti1.7, and Ti0.7V0.3, resulting from the interaction of the
elements of the Ti6A4V substrate and those of the Al2O3 deposit.
 1. INTRODUCTION

Understanding and predicting the behavior of matter are sources of progress and technological
innovation. Today, materials, and in particular oxides, occupy a prominent place in many
industrial sectors. Among these, aluminum oxide Al2O3, known as alumina, is a material with
strong application potential due to its mechanical and electronic properties 1-3. Aluminum
oxide, in its amorphous state, is a good thermal and electrical insulator 4. The
microelectronics industry is interested in this material to develop new high-purity dielectrics
at submicrometer scales [4, 5]. It is thus seeking to precisely determine its thermal properties
over a wide temperature range

Titanium alloys Ti6A4V are commonly used in extreme temperature and environmental
conditions. Ti6A4V is the most commonly used of all dual-phase titanium alloys, originally
developed for the aerospace market and widely used in aerospace structural members [6].
More recently, it has been used extensively in the oil and gas industry where a combination of
high strength, high corrosion resistance and low weight is essential [6]. The exceptionally
high hardness-ductility ratio with good fatigue resistance makes these alloys good candidates
for the space industry [7, 8].

Their mechanical properties, their resistance to creep at high temperatures, and their lightness
make these alloys attractive materials for the aeronautics, space and biomedical industries.
Their use is already widespread in this sector, and many alloys have been developed to meet
specific needs of the aeronautics and space industries. In particular, turbine engine
manufacturers, whose requirements for improving the efficiency and reducing the fuel
consumption of their turbo machines mainly involve making engines lighter and increasing
operating temperatures [9]. The density of the Ti6A4V alloy is half that of nickel alloys and
stainless steels. They have a high strength-to-weight ratio [3]. However, extending these
alloys to higher engine temperature zones or increasing the operating temperature of the
engines poses the problem of oxidation [7]. While their oxidation kinetics remain acceptable
up to temperatures of around 400°C, beyond 500°C [7], oxidation phenomena and their
corollaries (scaling, embrittlement, etc.) can no longer be neglected [7-10]. The oxidation
phenomenon is manifested by the rapid appearance of a TiO 2 type oxide layer followed by a
significant loss of mass [9].

This drawback, which has so far limited the use of these titanium alloys, is therefore
becoming increasingly restrictive. The creation of alloys resistant to oxidation while retaining
their mechanical properties does not seem likely to occur in the short term [10]. This is why
the solution of protective coatings is emerging as one of the simplest and most effective
solutions [11-13].

The major worry of manufacturers is how to improve the resistance to surface oxidation of
these alloys by reducing the diffusion of oxygen and nitrogen, and consequently, reduce their
mass loss for operating temperatures above 600°C [13-16]. The chemical and thermal stability
of these alloys at high temperatures also constitutes a major challenge that seems far from
being resolved [14, 16].

Direct deposition of an oxide layer resistant to oxygen and nitrogen diffusion is therefore the
targeted strategy. Various materials have been applied, such as Si3N4, silica, or enamel layers
[13, 15, 16] deposited by PVD or plasma spraying. Nitride-based ceramic multilayers have
also been tested. Two types of structures have been tested, CrN/NbN and TiAlCrYN or
TiAlYN/CrN. Applied to an α-TiAl titanium alloy, the TiAlCrYN/CrN system shows good
resistance to isothermal oxidation between 750 and 1000°C by developing a surface oxide
layer, which can even exceed the performance of the α-TiAl alloys tested in parallel under the
same conditions [17-18]. However, prolonged oxidation periods induce the formation of
defects in the nitrides that lead to oxidation of the substrate [18]. However, the mechanical
cohesion of the system also remains to be demonstrated.

Ion implantation has been performed, particularly on TiAl alloys. Silicon implantation does
not improve resistance to cyclic oxidation. However, after annealing at 830°C for 10 h, the
development of a mixed SiO2-Al2O3 layer creates an effective oxide barrier [19]. The
implantation conditions have little influence on the performance of these systems.

The application of metallic coatings that develop a protective oxide layer has also been tested.
Coatings combining aluminum and transition metals (Al, Cr), (Al, Ti), or (Al, Ni) deposited
by PVD are widely used. They are developed at low temperature T˂ 200 °C and low pressure
P = 0.5 Pa [20, 23]. The incorporation of transition metals makes it possible to increase the
hardness of the aluminum layers and to modify the corrosion resistance properties.
In this work, we proposed to carry out deposits of Al 2O3 type oxides (alumina) on a titanium
alloy of the Ti6A4V type at different polarizations of the latter. The applied substrate
polarizations are 0V, -50V and -100V and without polarization (wp). The deposits carried out
were carried out by PVD.

2. EXPERIMENTAL PROCEDURE
2.1 Deposition technique
The deposition of Al2O3 films on the Ti6A4V alloy is carried out by PVD-radio frequency (rf)
at the Center for the Development of Advanced Techniques (CDTA) in Algiers. This device is
designed and produced by the plasma and application team of the center. The deposition
parameters used are illustrated in Table 1.

Table 1. Paramètres de dépôt de films Al2O3 sur le substrat Ti6A4V.

Generator Target Distance Power Time Substrate Gaz flow Substrate

(cm) (W) (min) (sccm) polarization
(V)
 Radio Al2O3 3 300 60 Ti6A4V Ar 8 wp, 0V, -
frequency 50, -100
(rf)
Before making these deposits on the Ti6A4V substrate, the latter was cut into (1×1) cm 2
surface samples. To ensure a good surface condition of the substrate, polishing with SiC type
abrasive papers, and with decreasing grain size, was carried out until its mirror state. The
work [24] gives us more details on the operating conditions of PVD-rf deposits.

2.2 Microscopy SEM-EDS and AFM characterization

Microstructures of deposits were observed on its surface using scanning electronic
microscope (SEM) from JEOL-DAC in high vacuum. Chemical composition was analyzed
using an energy dispersive spectroscopy (EDS). The surface condition of the Al 2O3 deposits
and the roughness profile were carried out by AFM.
2.3 X-ray diffraction characterization
X-ray diffraction in 2 Mode was performed on Al 2O3/Ti6Al4V deposits by a Bruker AXS
D8 Advance diffractometer of Al2O3/Ti6Al4V deposits at different substrate polarizations.
The radiation wave used is of the monochromatic Cu Kα type with wavelength λ(CuKα) = 1.54
Å for 2θ scan ranging from 20° to 120°.
2.4 AFM characterization
Surface images (1×1) µm2 were obtained for Al2O3 deposits in contact mode, using an AFM,
Asylum Research an Oxford Instruments Company MFP 3D, under ambient laboratory
conditions. The pyramid tip radius used is 50 nm. A constant force of 0.032 N was applied.

3. RESULTS AND DISCUSSION

3.1 MEB-EDS microscopy

SEM images Figure 1, were obtained to identify the morphology of the Al 2O3 deposits at
different polarizations of the Ti6A4V substrate (wp, 0V, -50V and -100V). The micrographs
show an identical morphology of the Al 2O3 deposits for different polarizations of the Ti6A4V
substrate. The polarization of the substrate does not seem to have a significant influence on
the morphology of the Al2O3 deposits [25]. It should be noted, however, that the Ti6A4V
substrate has an acceptable coverage of the Al 2O3 deposit, and this, for the different
polarizations of the substrate. The micrographs also show a relatively acceptable density of
the Al2O3 deposit with porosities characteristic of PVD deposits [26]. The furrows observed
on the micrographs are probably due to polishing.

Quantitative EDS analysis Figure 2, performed on the Ti6A4V substrate without deposition,
indicates a mass percentage (wt)% of the elements Ti, Al and V of 85.14 (wt)%, 8.74 (wt)%
and 6.11 (wt)%, respectively. On the other hand, the corresponding atomic percentage (at)%
of these elements Ti, Al and V are 80.02 (at)%, 14.57 (at)% and 5.40 (at)%, respectively.
wp

Furrows

0V

Porosity
 -50V

-100V

Furrows

Porosity

Fig 1. SEM micrography of Al2O3 deposits at different polarizations on Ti6A4V substrate.

 Substrat Ti6A4V

Fig 2. Quantitative EDS analysis of Ti6A4V substrate without deposition.

Regarding the quantitative analysis of Al 2O3 deposits at different substrate polarizations figure
3, these were deposited on glass slides because the substrate also contains aluminum. The
results of the analysis are shown in Table 2 below.

Table 2. Quantitative EDS analysis of Al2O3 deposits at different polarizations of Ti6A4V substrate.

Polarisation 0V -50V -100V

Elements present in the Al O Al O Al O
Al2O3 deposit (wt %) 55.89 44.10 51.72 48.27 56.19 43.80

The results in Table 2, indicate the presence of Al and O elements in the Al 2O3 deposits, and
this at different polarizations of the Ti6A4V substrate. For the 0V polarization of the
substrate, the presence of Al in the deposit is 55.89 (wt)% and 44.10 (wt)% of O. On the other
hand, for the -50V polarization of the substrate, the aluminum present in the Al 2O3 deposit is
51.72 (wt)% for 48.27 (wt)% of O. Finally, for the -100V polarization, the presence of both
Al and O elements in the Al2O3 deposit is 56.19 (wt)% and 43.80 (wt)%, respectively.
 wp

0V

-50V

Fig 3. Quantitative EDS analysis of Al2O3 deposits at different substrate polarizations.

 3.2 X-ray diffraction

X-ray diffraction in 2θ mode of Al2O3/Ti6Al4V deposits at different substrate polarizations

reveals identical spectra. The identification of the phases formed in the Al 2O3 deposit and at
different substrate polarizations Ti6A4V shows the formation of the phases Al 0.3Ti1.7 (ICDD:
01-077-6855), Ti0.7V0.3 (ICDD: 01-081-9817) and Al2O3 (ICDD: 01-074-7230) [27]. The
elements Ti and V come from the substrate. We note that the spectrum of samples polarized at
-100V, presents a peak with relatively lower intensity than those of samples polarized at -
50V, 0V and wp. This phenomenon can be attributed to the partial crystallization of the
phases [27]. 120°, we also note the presence of two phases Al 0.3Ti1.7 and Al2O3 but at low
intensity which indicates the partial crystallization of the latter. For the diffraction peaks at
80°   2 120° where we record the majority presence of the Al 0.3Ti1.7 phases. Likewise for
the diffraction peaks between 50°  2 80°, the Al2O3 phase is present at low intensity for a
diffraction angle 2θ ~ 57° and 75°.
The appearance of the low intensity diffraction peaks, representing the Al 2O3 phase are less
sharp compared to the peaks of the crystallized phases. This lets us say that the Al2O3 deposits
made on the Ti6A4V substrate are of amorphous structures [27].

▪ Al0.3Ti1.7 (01-077-6855)
▪ *Al2O3 (01-074-7230)
× Ti0.7V0.3 (01-081-9817)
▪▪ ▪ ×* ▪ ▪*▪ -100 V

-50 V

0V

wp

Fig 3. X-ray diffraction of Al2O3/Ti6A4V deposits at different substrate polarizations.

3.3 The crystallites size of phases

Calculation of the mean crystallite size (MCS) of the phases as a function of substrate
polarization was determined by the following formula [28].

K.
MCS  (1)
FWHM .cos

Where, K is a constant (k = 0.9),  is the wavelength used ( = 0.054 nm), FWHM is the
width at half-height of the most intense peak in the spectrum of each deposit and  is the
diffraction angle of the most intense peak. Table 3, below summarizes these calculations.

Table 3. Calculation of the average size of MCS crystallites.

Phases Position (2°) of FWHM (2°) MCS (nm)

the most intense
peak
Al2O3 40.46 0.2424 0.263
Al0.3Ti1.7 40.46 0.2423 0.263
Ti0.7V0.3 39.96 0.9001 0.070

Based on calculations of the mean crystallite size of the phases at the most intense peak, we
note that the mean crystallite size in the majority Al 2O3 and Al0.3Ti1.7 phases is the same, equal
to 0.263 nm. In contrast, the Ti0.7V0.3 minority phase shows a very small crystallite size of
0.070 nm.
From this observation, we can deduce that the microstructure of the deposits is composed of
very fine dense grains.

3.3 AFM microscopy

Figure 4, represents the 3D topography and roughness profile for each Al 2O3 deposit as a
function of the polarization of the Ti6A4V substrate. These micrographs are determined by
the contact mode and for a scanned surface of (1 x 1) µm 2. The results of the arithmetic
roughness Ra of these deposits give values between 3.45 and 4.75 nm. We note that the Al 2O3
deposits have a relatively uniform surface state, with regular geometry and with small grains.
The low roughness observed for these deposits lets us say that they are dense and have a low
stress concentration. This low surface stress concentration plays a key role in determining the
corrosion resistance of these deposits.

We note, however, that the arithmetic roughness R a of the Al2O3 deposits increases as a
function of the negative polarization of the Ti6A4V substrate. The favorable role of negative
substrate bias on the texture of Al2O3 deposits is explained by the increase in kinetic energy
and positive ion flux in the plasma with the negative bias voltage [29, 30]. The energy
provided by these ions increases the mobility of species on the surface of the film and
promotes the rearrangement of adatoms according to the densest planes of the Al 2O3 structure
[31]. A moderate increase in substrate bias improves the texture of the deposits [31]. For a
larger negative bias, the crystallographic orientation of the deposit layers deteriorates [32].
These results are in agreement with the study conducted by Lee and Lee [32] concerning the
influence of substrate bias on the preferential orientation of AlN layers developed by rf-
magnetron sputtering on silicon substrates. These studies suggest that the significant increase
in negative substrate bias also increases the roughness of Al2O3 deposits.

wp Ra = 3.45 nm

0V Ra = 3.82 nm
 -50V Ra = 4.32 nm

-100V Ra = 4.75 nm
CONCLUSION

This work of physicochemical characterization of Al2O3/Ti6A4V films, deposited by PVD-rf

at different polarizations of the substrate, allowed us to conclude the following bridges:

 The morphology at the SEM of the Al 2O3 deposits is identical, fine, dense and well
spread on the Ti6A4V substrate, and this for the different polarizations. The porosities
observed on the deposits are typical of PVD deposits;
 The polarization of the Ti6A4V substrate seems not to have any influence on the
morphology of the deposits;
 The DRX indicates the presence of the crystallized phases Al 0.3Ti1.7 and Ti0.7V0.3 of the
substrate. On the other hand, the Al2O3 phase, at low intensity, is amorphous;
 The crystallites of the deposits are fine with a dimension of 0.26 nm, testifying to the
density of these deposits;
 AFM indicates a uniform and regular morphology of the Al 2O3 deposits, well spread
on the Ti6A4V substrate. A relatively uniform roughness profile indicates a roughness
Ra varying between 3.45 and 4.75 nm. This roughness increases as a function of
increasing the negative polarization of the Ti6A4V substrate.

ACKNOWLEDGEMENTS

The authors would like to thank the Advanced Technology Development Center (CDTA) in Algiers,
in particular Prof. N Saoula, research director at the center, for the realization of the Al 2O3/Ti6A4V
deposits by PVD-rf. We would also like to thank Dr. Rahmouni from the Institute of Applied Sciences
and Technology (ISTA) in Oum el Baouaghi for his contribution to the realization of the SEM
micrographs.
NOMENCLATURE

Al2O3 alumina
Ti6A4V Titanium alloys
PVD-rf physical vapor deposition radio
frequency
SEM scanning electron microscopy
EDS energy dispersive spectroscopy
AFM atomic force microscopy
DRX X-ray diffraction
P Pression [Pa]
wp Withou polarization
T Temperature [°C]
CDTA Centre de développement des
technologies avancées
Sccm standard cubic centimeters per minute
λ wavelenth [Å]
Cu-Kα type of cathode used
θ diffraction angle [°]
(wt) masse percentage
(wa) atomic percentage
ICDD international center for diffraction data
base
MCS mean crystallites size
FWHM with at half height of the most intense
peak [rad]
Ra arithmetic roughness [nm]

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