Materials Sciences and Applications, 2011, 2, 1375-1382
doi:10.4236/msa.2011.210186 Published Online October 2011 (http://www.SciRP.org/journal/msa)
1375
Infrared Spectroscopy of Titania Sol-Gel
Coatings on 316L Stainless Steel
Daniela Cordeiro Leite Vasconcelos1, Vilma Conceição Costa1, Eduardo Henrique Martins Nunes1,
Antônio Claret Soares Sabioni2, Massimo Gasparon3, Wander Luiz Vasconcelos1*
1Department of Metallurgical and Materials Engineering, Federal University of Minas Gerais, Belo Horizonte, Brasil; 2Department of
Physics, Federal University of Ouro Preto, Ouro Preto, Brasil; 3School of Earth Sciences, The University of Queensland, St. Lucia,
Australia.
Received September 28th, 2010; revised December 10th, 2010; accepted March 20th, 2011.
ABSTRACT
Sol-gel titania films were deposited on 316L stainless steel using titanium isopropoxide as a chemical precursor. Dip-
coating was performed at withdrawal speeds of 6 mm/min, 30 mm/min, and 60 mm/min. Deposited gel films were heat
treated in air at 80˚C, 100˚C, 300˚C, and 400˚C. The structural evolution of the coatings was evaluated by infrared
reflection-absorption spectroscopy. The influence of the withdrawal speed and the heat treatment temperature on the
structure of the films was studied by varying the reflectance incidence angle during the infrared experiments and by
Glow Discharge Spectrometry. Free functional groups were detected. The results indicate the formation of bidendate
bridging coordination of carboxylic acid to titanium. Titanium atoms can also be pentacoordinated according to the
processing conditions of the films. We observed a tendency of increasing amounts of OH groups with decreasing re-
flectance incidence angle. The film hardness was measured via Knoop microindenation hardness test.
Keywords: Films, Sol-Gel, Infrared Spectroscopy, Glow Discharge Spectrometry, Knoop Hardness
1. Introduction
There are many different thin film processing techniques,
including physical and chemical techniques. Among these,
sol-gels offer potential advantages [1,2], including the
good homogeneity of the product, and the fine control
over composition. Another convenient feature of this
technology is the fact that sol-gel samples can be obtain-
ed as bulks, thin films, and powders [3,4].
Oxide coatings are the most investigated coating sys-
tems [5-8]. One advantage of the wet coating technique
is that molecular structures, developed by chemical syn-
thesis, can be used to develop new properties either to
preserve theses structures on the surface, or to develop
new desired molecular structures by heat-treatment and
subsequent chemical reaction on the surface. The appli-
cation potential results from the opportunity of synthe-
sizing unique material properties and combine it with
cost-effective coating techniques [9].
The coating of metallic surfaces by sol-gel films has
been proposed as a useful way to protect them from oxi-
dation and chemical attack [10-14]. Izumi et al. [15] re-
ported an increase in chemical resistance of aluminized
steel sheets coated with sol-gel silica and zirconia, in a
5% NaCl solution. Using tetraethylorthosilane as the start
material, Vasconcelos et al. [10] obtained sol-gel silica/
304 stainless steel composites with higher corrosion re-
sistance in a 1N H2SO4 and 3.5% NaCl medium. Based
on Rutherford Backscattering Spectroscopy data, the
authors concluded that the intermediate layer formed
between the silica film and the steel substrate is respon-
sible for the increase of the corrosion resistance of the
stainless steel. Atik et al. [16] studied the corrosion im-
provement of 316 steel using titania-silica and alu-
mina-silica sol-gel films. They observed that the coatings
allowed a remarkable increase of the stainless steel life-
time when placed in a 3% NaCl solution. Titania (TiO2)
films have attracted attention as photoelectrode, photo-
catalyst, gas sensor and biomaterial, when used for coat-
ing titanium alloys or 316L stainless steel.
In this work, we report the preparation of titania gel
coatings on 316L steel substrates from the hydrolysis and
polycondensation of titanium isopropoxide. We shall
investigate the effect of the withdrawal speed and heat
treatment temperature on the film structure by means of

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel
1376
reflectance-absorbance infrared spectrometry using vari-
able reflectance incidence angles (θ). Some important
information about bonding and coordination modes of
the films is provided by Fourier Transform Infrared
Spectroscopy (FTIR). The results of Knoop microinden-
tation tests are then compared with those obtained by
FTIR and Glow Discharge Spectrometry (GDS) analy-
ses.
2. Experimental Procedure
Titanium dioxide solutions were prepared by hydrolysis
and condensation of titanium isopropoxide, Ti(OC3H7)4,
(TIP). Ethanol (C2H5OH) was used as the solvent. The
molar ratio C2H5OH/TIP used was 16 or 64. Acetic acid
(HAc) and diethanolamine were added to the initial solu-
tion, using the molar ratio of TIP/HAc = 1.
The films were deposited by dip-coating from the pre-
pared batch solution on polished sheets of stainless steel
316L previously cleaned with water, detergent and ace-
tone. The film deposition was performed by dipping the
substrate in the sol and withdrawing it at speeds of 6
mm/min, 30 mm/min, and 60 mm/min. After deposition,
the films were heat treated in air for 30 minutes at 80˚C,
100˚C, 300˚C, and 400˚C.
The coating thicknesses were experimentally estimated
considering the withdrawal speeds and the heating tem-
perature. FTIR spectra of the sol-gel derived films were
recorded using a Perkin Elmer FTIR Paragon-1000. Re-
flection-absorption spectra at different angles of inci-
dence were measured using a variable angle specular
reflectance (VASR) accessory. This technique is most
useful in applications requiring specular reflectance spec-
tra on thin films and allows investigation of the sample in
depth layers by varying the incidence angle of the infra-
red beam. Spectra were collected with a 4 cm−1 resolu-
tion and 64 scans were accumulated for each spectrum.
In this arrangement the incidence angles are defined with
respect to the normal to the sample surface.
The chemical profile composition (varying from the
outermost surface towards the substrate) of the titania
composite was evaluated by GDS (depth resolved, radio
frequency glow discharge atomic emission spectrome-
try), using a Jobin-Yvon 5000RF. The elements ana-
lyzed in this work were Ti, O, Fe, Cr, Ni, Si and Mn.
The tested surface area of the samples was approxi-
mately 12.5 mm2. After each analysis the samples were
transferred to a diamond stylus profilometer (Tencor
P-10,) in order to determine the size of the crater formed.
For each sample, the time analysis was converted to
depth by multiplication of the size of the crater and the
average sputter rate.
The film hardness was obtained by performing a mi-
croindentation hardness test, using a Future Tech FM-1
Knoop indenter, and 10 g load with a dwell time of 15 s.
3. Results and Discussion
The determination of the structure of the deposited films
is discussed in terms of the withdrawal speed, the heating
temperature and the incidence angle (θ) used in the in-
frared spectroscopy.
In order to estimate the thickness of the TiO2 films, the
mass of the coatings and the area of the substrate were
measured and the density of an equivalent unsupported
film was determined by helium picnometry. The esti-
mated values for thickness range from 120 nm to 800 nm.
The influence of the withdrawal speed and temperature
of the thermal treatment on the TiO2 film thickness is
shown in Figure 1. The coating thickness increases with
the increase of the withdrawal speed, which is in agree-
ment with the Landau-Levich model [17]. The film thick-
ness is reduced for all withdrawal speeds when the heat-
ing temperature is increased. This is consistent with the
fact that in this temperature range water and organic
groups are removed from the titania films.
3.1. FTIR Spectroscopy: Withdrawal Speed
Figure 2 shows a typical infrared spectrum of all the
produced films, except for those prepared using 60 mm/
min and heated to 400˚C.
The broad absorption band centered at 3300 cm−1 is
attributed to stretching vibrations of molecular water and
OH groups [18]. Superimposed onto this band, two other
bands are clearly visible at 3365 cm−1 and 3257 cm−1.
These two bands have been ascribed, respectively, to the
asymmetric and symmetric stretching vibration of N-H
groups from diethanolamine. Additional peaks are noted
at 2930 cm−1 (CH2 asymmetric stretching mode) and at
2867 cm−1 (CH2 symmetric stretching mode) of the al-
0
100
200
300
400
500
600
700
800
900
0100200 300400 500
Temperature (
o
C)
Thickness (nm) .
60 mm/min
30 mm/min
6 mm/min
Figure 1. Thickness variation of the titania films deposited
with different withdrawal speeds as a function of the heat-
ing temperature.

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel 1377
30060090012001500180021 0024002700300033003600
Wavenumber (cm
-1
)
Absorbance (a.u.) .

as
(OH), (NH), 
as
(NH
2
)

s
(NH
2
)

as
(CH
2
)

s
(CH
2
)

as
(CO O)

s
(CO O)
(C=O)
(CH
3
)
(Ti-O-C)
(Ti-O)
(Ti-O-Ti)
(Ti-O-Ti)
(Ti-O-T i
)
Figure 2. Infrared spectrum (  = 80˚) of sol-gel titania film
deposited at 30 mm/min and heated to 400˚C. νas = asym-
metric stretching mode; νs = symmetric stretching mode; δ
= angular deformation mode.
coxide [19,20].
Even in films heated up to 100˚C the band around
1750 - 1735 cm−1, characteristic of the stretch vibration
of the C=O bonds of free carboxylic acids, is absent. This
excludes the presence of an ester from the reaction of
titanium isopropoxide with acetic acid in the sol-gel coat-
ing [20].
According to Urlaub et al. [20] and Venz et al. [21],
three coordination modes of carboxylic acids to a metal
atom are possible, namely monodentate via one oxygen
atom, bidendate chelating via both oxygen atoms, and
bidendate bridging between two metal atoms (see Figure
3).
The absorption bands at 1638 cm−1 and 1445 cm–1 are
assigned respectively to the asymmetric 
as(COO) and
symmetric 
s(COO) stretching vibrations. The presence
of these two bands suggests a bidentate bridging coordi-
nation for the acid group [22]. The separation of 193
cm−1 observed for the 
as(COO) and

s(COO) peak posi-
tions is typical for bidentate bridged carboxylic acid tita-
nium complexes [22].
The band at 1080 cm–1 is assigned to the  (Ti-O-C)
bridging vibrations of isopropoxy groups [20,23]. On
adding nucleophilic ligands like acetic acid to titanium
isopropoxide, the coordination number of the central
atom increases from 4 to 6 and oligomeric species
[(Ti(OPri)3(OAc)]n (n = 2 or 3) are formed [16]. In bi-
dentate bridging coordinations, the isopropoxy groups
are present between two titanium atoms. Our results
suggest the formation of a dimeric complex, with the
acetic acid acting as a carboxylate ligand, (CH3COO−).
The structure complex suggested (see Figure 4) is in
agreement with the literature [19,24,25].
Unlike the other samples, the films deposited at 60
mm/min and heated to 400˚C do not exhibit the charac-
teristic peaks of the isopropoxy bridging group. In this
case, the complex should have the structure proposed in
Figure 5, where the titanium atoms are pentacoordinated.
Urlaub et al. [20] suggested the same type of structure in
complexes formed by titanium isopropoxide and trans-
propene-1,2,3-tricarboxilic acid, and also mention the
existence of another complex of titanium pentacoordi-
nated titanium.
The bands related to the

as(COO) and

s(COO) vibra-
tions, which indicate the coordination mode of the ace-
tate group in the titanium alcoxide and thus the structure
of the molecule formed, are relatively large and may
represent the convolutions of two or more signals. This
feature is an indication that other different binding modes
of acetate group are present.
Additional bands were observed at 1560 cm–1, 1380
cm–1, and 1263 cm–1. The bands at 1560 cm–1 and 1263
cm–1 are due to the respective
 (C=O) and δ(CO) modes
[20]. The band at 1380 cm–1 is caused by the symmetric
deformation band of a CH3 group from the isopropoxide
structure [19,26].
MOR
O
M
O
R
O MO
MO
R
mo no dentat
e
b
idendate chelating
b
iden
d
ate bridging

as(COO) = 1720 cm-1
s(COO) = 1295 cm-1
(as-
s
) = 425 cm-1

as(COO) = 1550 cm
-
1
s(COO) = 1470 cm-1
(a
s
-
s
) = 80 cm-1
as(COO) = 1590 cm
-
1
s(COO) = 1430 cm-1
(a
s
-
s
) = 160 cm-1
Figure 3. Possible coordination modes in metal carboxilates.
O
CH3
Ti
O
CH3
OO
OROR OR
OR OR
Ti
OR
Figure 4. Proposed structure for the complex of titanium
isopropoxide and acetic acid.
OO
CH3
Ti Ti
OO
CH3
OR
OR
OR
OR
OR
OR
Figure 5. Proposed structure of the complex titanium iso-
propoxide-acetic acid for the sol-gel films deposited at 60
mm/min and heated to 400˚C.

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel
1378
It was observed that the bands at 1000 cm–1 and 850
cm–1 are not present in the infrared spectra of the coat-
ings produced. The band at 1000 cm–1 is related to transi-
tion metal isopropoxides (  (CO) mode) and to the iso-
propoxide group (C-C skeleton vibration). The peak at
850 cm–1 is also related to the isopropoxide group. The
absence of these two bands in the infrared spectra of the
coatings produced strongly suggests that the titanium
isopropoxide has been consumed during the sol prepara-
tion [19].
The only two products of the hydrolysis reaction are
the titanium hydroxide and the isopropanol. No band can
be clearly associated to the Ti-OH group, suggesting that
the condensation occurred immediately after the hy-
drolysis of the titanium alcoxide. The bands for Ti-O and
Ti-O-Ti bonds are present in the 800 - 400 cm–1 region,
the former being observed in a higher wavenumber than
the latter [19, 23]. The titania sol-gel films produced in
this work show an infrared band around 805 cm–1 related
to the
 (Ti-O) mode. The bands at 760 cm–1, 680 cm–1,
560 cm–1, 500 cm–1, 468 cm–1, 410 cm–1, 385 cm–1 and
350 cm–1 are associated to
 (Ti-O-Ti) vibrations [27-32].
The peak around 800 cm–1 is assigned to a ν(Ti-O) vi-
bration, where the oxygen atom is in the non-binding
condition. The peaks at 760 cm–1, 680 cm–1, 600 cm–1,
560 cm–1, 500 cm–1, 468 cm–1, 410 cm–1, 385 cm–1 and
350 cm–1 are assigned to the
 (Ti-O-Ti) stretching vibra-
tion [27-31].
3.2. FTIR Spectroscopy: Effects of Incidence
Angle (θ) and Heat Treatment Temperature
The variation of the incidence angle in the infrared re-
flection-absorption spectroscopy allows the analysis of
the film’s surface and depth profile. Thus, for
 = 20˚
and 45˚ the inner layers of the film are considered, and
for
 = 80˚ the surface of the film is accessed.
Figure 6 shows typical infrared spectra of titania films
obtained with
 = 80˚, 45˚, and 20˚ (films prepared using
6 mm/min and heated to 400˚C).
The relative amount of OH, CH2, and CH3 groups in-
creases from the surface to the inner layers of the film.
Besides from being sub-products of the condensation
reaction, water and alcohol are also used as reagents in
the film synthesis procedure. The spectra suggest that the
film is more condensed near the substrate surface. If this
is true, it should be expected that Ti-O-Ti bonds are gen-
erated during the condensation process and contribute to
the formation of the TiO2 lattice [19,32].
Figure 7 shows the intensity ratio between the hy-
droxyl band and the Ti-O– band (800 cm–1) as a function
of the incidence angle and of the heat-treatment tem-
perature of the film.
The amount of OH groups increases as the incidence
300600900120015001800210024002700300033003600
Wavenumber (c
m
-1
)
Absorbance (a.u.) .
80
o
45
o
20
o
Figure 6. Infrared spectra (  = 80˚, 45˚, and 20˚) of sol-gel
titania film deposited at 6 mm/min and heated to 400˚C.
0
1
2
3
4
5
6
7
8
9
0100200 300400 500
Temperature (oC)
Ratio (OH/Ti-O) .
80o
45o
20o
20°
45°
80°
Figure 7. Evolution of the absorbance intensity ratio of OH/
Ti-O peaks with θand temperature.
angle (θ) is reduced. Also, the content of OH groups de-
creases for increasing heating temperatures.
The intensity ratio between the Ti-O-Ti band (680 cm–1)
and the Ti-O band (800 cm–1) as function of the inci-
dence angle and of the heating temperature of the films is
shown in Figure 8. This intensity ratio increases when
the incidence angle changes from 80˚ to 45˚, indicating
that Ti-O-Ti bonds are formed at the expense of Ti-O
bonds. This result suggests a more condensed structure in
the inner part of the sample.
Table 1 gives the corresponding wavenumbers of Ti-O
and Ti-O-Ti vibrational modes as function of the inci-
dence angle and of the heating temperature. The separa-
tion (Δ(Ti-O)-(Ti-O-Ti)) between the Ti-O and Ti-O-Ti bands
increases when the heating temperature is increased.

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel 1379
Table 1. IR absorption wavenumbers (cm−1) of the Ti-O e Ti-O-Ti vibrational modes for different temperatures and IR
incidence angles (θ).
Wavenumber (cm−1)
80˚ 45˚
Temperature
Ti-O Ti-O-Ti Δ(Ti-O)-(Ti-O-Ti) Ti-O Ti-O-Ti Δ(Ti-O)-(Ti-O-Ti)
100˚C 795  2 687  5 109
300˚C 815  10 680  1 135 796  3 673  1 122
400˚C 824  10 684  4 140 816  10 675  2 141
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
0100200300 400 500
Tem
p
erature
(
o
C
)
Ratio (Ti-O-Ti/Ti-O) .
80
o
45
o
45°
80°
4005006007008009001000
Wavenumber (cm
-1
)
Absorbance (a.u.) .
(Ti-O)
(Ti-O-Ti)
100
o
C
300
o
C
400
o
C
v(Ti-O)
v(Ti-O-Ti)
Figure 8. Evolution of the absorbance intensity ratio of
Ti-O-Ti/Ti-O peaks with θ and temperature. Figure 9. Infrared spectra (
 = 80˚) of sol-gel titania film
deposited at 30 mm/min and heated to 100˚C, 300˚C and
400˚C.
From Figure 9 it can be seen that the Ti-O band is more
affected by heating than the Ti-O-Ti band. The shifting
of the Ti-O band to higher wavenumbers is related with
the formation of stronger bonds and with the generation
of a more resistant film.
4005006007008009001000
(Ti-O
)

(
Ti-O-Ti
)
80o
45o
20o
Wavenumber (cm
-1
)
Absorbance (a.u.)
For the same final temperature of heating, the separa-
tion between the peaks tends to decrease from the surface
towards the interior of the film mainly due to the reduce-
tion in the intensity of the Ti-O band. This band is absent
for θ = 45˚ in films dried to 100˚C, and in all films for θ
= 20˚. Again, the hypothesis that the interior of the film
has a more developed titanium oxide network is sup-
ported by our experimental results. As shown in Figure
10, only the films deposited at 60 mm/min and heated to
400˚C have a well-defined Ti-O band for
 = 20˚.
Figure 10. Shift of the bands attributed to Ti-O and Ti-O-Ti
vibrations in relation to θ.
3.3. Glow Discharge Spectrometry―GDS
The composition depth profile of the sol-gel titania films,
prepared with ethanol/TIP = 16, were evaluated by GDS.
The intensity of the detected signal is proportional to the
amount of the element present in the plasma, which is
controlled by the concentration in the samples and by the
sputter rate. The intensities of O, Mn and Si have been
normalized for each sample by multiplying the signal by
10, 5 and 2, respectively, so that all the element profiles
could be presented in the same figures.
Figures 11 to 14 show the chemical depth profile of
the composites obtained from films deposited at with-
draw speeds of 6 mm/min, 30 mm/min and 60 mm/min
and heat treated at 300˚C and 400˚C. Since the depths on
the graphs are obtained by multiplying the time data by
the average sputter rate, their values are approximate.

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel
1380
0,0
0,5
1,0
1,5
2,0
0200 400 600 800100
0
Fe
N
i
Mn
Ti
O
Si
Cr
Depth (nm)
Intensity (V)
0.0
0.5
1.0
1.5
2.0
Figure 11. GDS of a titania sol-gel film deposited at 30 mm/
min and heated at 300˚C.
0,0
0,5
1,0
1,5
2,0
0200 400600 800100
0
Fe
Ni
Mn
Ti
O
Si
Cr
Depth (nm)
Intensity (V)
0.0
0.5
1.0
1.5
2.0
Figure 12. GDS of a titania sol-gel film deposited at 6 mm/
min and heated at 400˚C.
0,0
0,5
1,0
1,5
2,0
0200 400600 800100
0
Fe
N
i
Mn
Ti
O
Si
Cr
Depth (nm)
Intensity (V)
0.0
0.5
1.0
1.5
2.0
Figure 13. GDS of a titania sol-gel film deposited at 30 mm/
min and heated at 400˚C.
The thicknesses of the sol-gel films were estimated
from the depth profile of Ti, considering the interval
where the intensity of Ti begins to decline, and the inten-
sity of Cr (first detected element of the substrate) be-
comes significant. The approximate thicknesses of the
titania sol-gel films were 420 nm for the composite ob-
0,0
0,5
1,0
1,5
2,0
0200400 600 8001000
Fe
N
i
Mn
Ti
O
Si
Cr
Depth (nm)
Intensity (V)
0.0
0.5
1.0
1.5
2.0
Figure 14. GDS of a titania sol-gel film deposited at 60 mm/
min and heated at 400˚C.
tained at 30 mm/min and 300˚C (Figure 11), and 260 nm
(6 mm/min, Figure 12), 320 nm (30 mm/min, Figure 13)
and 360 nm (60 mm/min, Figure 14) for the composites
heated to 400˚C. These results are in agreement with
those from the literature showing that the increase of the
withdraw speed led to the formation of thicker films
while an increase in the drying temperature reduces the
film’s thickness.
The intensity of the observed emissions is a combina-
tion of the concentration of the analyzed elements and of
the rate of sputtering/excitation in the plasma. Thus, in a
given sample the intensity of Fe, which is the most
abundant element in stainless steel, is lower than the in-
tensity of the other elements that make up the alloy, such
as Cr. The explanation for this apparent paradox is that
Cr has a higher sensitivity to the used wavelength than
Fe. Also, the response difference among the sensors used
in this technique for the different elements must also be
considered. Thus, a rigorous quantitative analysis re-
quires the use of reference standards. Considering, how-
ever, that all the samples have nominally the same com-
position and that the conditions of discharge are the same
for each profile, the intensity detected should be repre-
sentative of actual concentrations, making it possible to
compare different samples.
In all analyzed samples the increase of the Ti signal is
gradual. This result confirms a lower Ti concentration in
the film surface. The increase in Ti content corresponds
to a decrease in the oxygen profile.
The composite obtained from the withdraw speed of
60 mm/min and heated to 400˚C (Figure 14) shows the
highest Ti intensity. In all other composites, the intensity
of Ti is similar of that observed for the Ni from the sub-
strate. This is an important indication that in the compos-
ite shown in Figure 14, either the Ti content in the sol-
gel film is quite high, or this film has a much higher den-
sity than the others. Indeed, as discussed before with the

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel 1381
results obtained by FTIR, the sol-gel film of this com-
posite has a different structure when compared to the
others.
By using the Knoop microindentation hardness tests,
we observed that the titania film heat treated to 400˚C
shows a higher hardness value (410 GPa) than steel (330
GPa). This is consistent with the interpretation of the
GDS results, indicating that this film in particular shows
the highest Ti concentration in the outermost surface.
4. Conclusions
Thin films of titania deposited on 316L stainless steel
have been prepared using the sol-gel method. The infra-
red reflectance-absorbance spectra indicated the forma-
tion of a dimeric complex in a bidantate bridging coor-
dination between the titanium isopropoxide and the ace-
tic acid. According to the processing conditions of the
film, the titanium atoms can also be present as pentaco-
ordinated. We have established a qualitative procedure
for the investigation of the film structure by changing the
beam incidence angle in the infrared experiments. We
observed that the relative amounts of OH, CH2, and CH3
groups increase from the surface to the inner layers of the
film, indicating that the films are more condensed near
the substrate surface. The composite prepared with with-
draw speed of 60 mm/min and heated to 400˚C has the
highest Ti content. By using the Knoop microindentation
hardness test, we observed that this titania film, when
heat treated, tended to be harder than the steel substrate.
5. Acknowledgements
The authors acknowledge financial support from the Mi-
nas Gerais Research Agency (Fapemig), Brazilian Re-
search Agency (CNPq), Brazilian Graduate Agency
(CAPES), Minerals and Metallurgy Pole of Excellence of
The Minas Gerais State, and The National Institute of
Science and Technology on Mineral Resources, Water,
and Biodiversity (Acqua).
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