Eur. Phys. J.

D 53, 69–73 (2009)

DOI: 10.1140/epjd/e2009-00030-0 THE EUROPEAN
PHYSICAL JOURNAL D
Regular Article

Stoichiometry analysis of titanium oxide coating by LIBS

H. Estupiñán1 , D.Y. Peña1 , Y.O. Garcı́a1, R. Cabanzo2 , and E. Mejı́a-Ospino2,a
1
Grupo de Investigaciones en Corrosión, Universidad Industrial de Santander, A.A. 678, Bucaramanga, Colombia
2
Laboratorio de Espectroscopia Atómica y Molecular, Universidad Industrial de Santander, A.A. 678, Bucaramanga, Colombia

Received 25 July 2008 / Received in final form 18 December 2008

Published online 13 February 2009 – c EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2009

Abstract. In this work, laser induced breakdown spectroscopy (LIBS) is used to determine the composition
of titanium oxide film produced by anodized of Ti6Al4V alloy. We have used Ti lines in the spectral
region between 470–520 nm to determine temperature of the plasma generated on anodized surface of
Ti6Al4V alloy for temperature determination by Boltzmann plot method. In order to measure the content
of oxygen and titanium ratio on the surface the alloy, we have used the oxygen lines 777.194, 777.417 and
777.539 nm, and titanium lines 780.597 and 782.491 nm observed in an ambient of argon. Finally, we report
the possibilities for the determination of the coating chemical composition using LIBS.
PACS. 79.20.Ds Laser-beam impact phenomena – 78.66.Bz Metals and metallic alloys – 52.25.Os Emis-
sion, absorption, and scattering of electromagnetic radiation – 52.38.Mf Laser ablation

1 Introduction analysis. In addition, LIBS also permit the possibility of

Titanium and Ti-alloys are the most used materials for
prosthesis in vivo applications, due to their good physi-
cal and mechanical properties such as low density, high
corrosion resistance and mechanical resistance. Since the
bioenvironmental in the human body is very complicated,
metallic implants could interact with surrounding tissues
and then cause corrosion [1–3]. Clinical experience has
shown that they are susceptible to localized corrosion in
human bodies causing the release of metal ions into the
tissues surrounding the implants. Biocompatible and cor-
rosion resistant layers are normally coated on alloys [2,3].
Many efforts have been made in recent years in the devel-
opment of processing methods for depositing coating on
implant alloy substrates such as Ti6Al4V in order to have
high strength, suitable specific density, good process abil-
ity, and excellent corrosion resistance in living bodies. One
way of generating a coating is by electrochemical anodized
to produce a layer of TiO2 . Different techniques, such as
X-ray fluorescence, Rutherford backscattering spectrome-
try, scanning electron microscopy or electron probe mi-
croanalysis, are used to determine the coating compo-
sition [4–8]. Laser induced plasma spectroscopy (LIPS
or LIBS) is an alternative elemental analysis technology
based on the optical emission spectra of the plasma pro-
duced by the interaction of high-power laser with gas, solid
or liquid [9–34]. The increasing popularity of this tech-
nique is due to the ease of the experimental set-up and
to the wide flexibility in the investigated material that
does not need any pre-treatment of the sample before the
a
e-mail: emejia@uis.edu.co
making in-situ and stand-off measurements (no contact
with the samples).
Here we have used LIBS to determine the stoichiom-
etry ratio of titanium to oxygen in a film produced by
anodized of Ti6Al4V alloy. In order to measure the ratio
Ti:O is necessary to know the temperature of the laser
induced plasma, we used Boltzmann plot method to de-
termine the plasma temperature.
2 Experimental
2.1 Electrolytic anodized
In this study we used different Ti6Al4V alloy plate elec-
trolytically anodized. The composition of the Ti6Al4V al-
loy plate conformed to the specification of ASTM standard
F-136. The Ti6Al4V alloy plate with a size of 12 mm of
diameter and 3 mm of width, was mechanically ground.
Finally, the Ti6Al4V plate was then washed thoroughly
by running distilled water before being ultrasonically de-
greased with ethanol and dried. Electrolyte was prepared
with 0.01 M and sulphuric acid and 0.01 M of monopota-
sium phosphate (KH2 PO4 ). Electrolytic anodized was
carried out placing Ti6Al4V plate as anode and the elec-
trochemical cell of steel as cathode. The anodized Ti6Al4V
samples were obtained using a potential maintained at
30 V by a potentiostat power supply (Thermo EC570-90)
for 15 min. The solution was stirred with a magnetic stir-
ring bar and the titanium oxide coating was deposited
on the Ti6Al4V plates. After coating, the plates were also
rinsed with distilled water and dried at room temperature.
70 The European Physical Journal D

Fig. 1. (Color online) Experimental setup.

2.2 LIBS system

The second harmonic from a Q-switched Nd:YAG laser

(Spectra Physics, India), 532 nm, 10 ns (at 10 Hz) is fo-
cused through a quartz lens (f ∼ 100 mm) on the sam-
ple surface, inducing the formation of a transient plasma
plume in argon atmosphere. We have chosen to work in
an argon atmosphere instead of ambient air because we
do not want to measure the air oxygen and be able to
only measure the oxygen contained in the analyzed film).
The plasma emission is focused through a quartz lens
(f ∼ 50 mm) and collected with a quartz optical fiber,
and introduced into a 0.5 m spectrograph (Digikröm 740,
Spectral Products). A 1200 grooves/mm diffraction grat-
ing (spectral resolution 0.4 nm) is used to disperse the
emission spectrum, which is projected on the image plane
of the spectrograph and recorded on a charge coupled de-
vice (CCD) detector (128 H, Princeton Instruments).
Each spectrum is the result of the observation in total
lifetime of the plasma generated with a single pulse laser, Fig. 2. Typical LIBS spectra in the region between 380 and
because the CCD used here does not allow resolving tem- 410 nm.
porally the laser-induced plasma, however, it is possible
using delay-system to observe the plasma radiation. The
spectra of plasma were observed in the three regions; from
760 to 790 nm (to observe O lines and Ti lines), from 470 and two laser shots on the surface of anodized Ti6Al4V. In
to 520 nm (to measure the plasma temperature) and from the spectra (Fig. 2) are labeled some analytical line of the
380 to 410 nm (to verify the observation only the element elements of interest. The spectra of Figure 2 are observed
of film). The laser energy employed in the experiment was over a single position of the surface of the sample, the first
of 10 mJ/pulse (power densities ∼1.0 GW cm−2 ). The shot show no presence of aluminum. At energies per pulse
schematic diagram of our LIBS experimental setup is de- of 10 mJ, the anodized surface is removed completely and
picted in Figure 1. the laser-induced plasma is formed with the elements of
the coating.
For the compositional analysis of titanium oxide coat-
3 Results and discussion ing, we looked for a spectral region containing emission
lines of both Ti and O (Fig. 3a), the spectra obtained
To verify that single laser shot only vaporize anodized were measured by accumulating the plasma emission cor-
coating, we observed the spectral region between 380 and responding to a single shot laser. To resolve the oxy-
410 nm, in this region is possible to observe the 394.4 and gen atomic lines (777.192, 777.417 and 777.539 nm) was
396.2 nm aluminum lines, and 390.5 nm titanium line. necessary to do a de-convolution (Fig. 3b) of the lines
Figure 2 shows typical LIBS spectra obtained with one emitted by oxygen around 777.5 nm, supposing Gaussian
 H. Estupiñán et al.: Stoichiometry analysis of titanium oxide coating by LIBS 71

Table 1. Spectroscopic parameters of neutral Ti (I) transition

lines used to determine plasma temperature.
Iλ
Wavelength (nm) Ek (eV) Aki gk ln Aki gk
500.7 3.2936 49 200 000 7 –7.1222
474.3 4.8498 53 000 000 9 –9.3580
482.0 4.0738 14 900 000 7 –8.0942
484.1 3.4600 17 600 000 5 –7.0826
485.6 4.8081 52 000 000 15 –9.1730
517.4 2.3957 3 800 000 5 –5.5321
519.3 2.4080 3 490 000 7 –5.4206
521.0 2.4269 3 570 000 9 –5.6181

where λ0 is the central wavelength (in m) of the emission

Fig. 3. (Color online) (a) LIBS spectrum in the spectral region
between 760 to 790 nm. (b) De-convolution of the spectral lines
of oxygen emitted at 777.194, 777.417 and 777.539 nm.
distribution of the line intensities. Assuming local ther-
modynamic equilibrium (LTE) and optically thin con-
ditions, the measurements of intensity of emission lines
coming from the laser-induced plasma can be used to
check the composition (Eq. (1)) and the ratios of atomic
concentrations among the plasma species (Eq. (2)). At
power density higher than 0.3 GW cm−2 (of a nanosec-
ond laser pulse), the process involved are predominantly
non-thermal (vaporization is not affected by the thermal
properties of the target), therefore, we can consider that in
our conditions, the plasma elemental composition reflects
the target composition [35]
e2 λ20 gi e−Ei /kT  −(Ek −Ei )/KT
 where Aki is the transition probability, gk is the statistical
kt = f ik 1 − e (1)
4ε0 mc2 Z(T )
ITi kt, Ti NTi
= (2)
IO kt, O NO
line, fik the transition oscillator strength (dimensionless),
gi the degeneracy (dimensionless) of the lower energy level,
Ei and Ek the energies (in J) of the lower and upper en-
ergies levels, respectively, k the Boltzmann’s constant (in
J K−1 ), T the absolute temperature (K), Z(T ) the par-
tition function (dimensionless), e the elementary charge
(in C), ε0 the permittivity of free space (in F m−1 ), m the
electron mass (in kg) and c is the speed of light in vacuum
(in m s−1 ). ITi and IO are the integrated intensity of the
spectral line emitted by Ti and O species, respectively,
in optically thin conditions; NTi and NO are the number
density of the emitting species.
In order to calculate kt,Ti and kt,O coefficients is neces-
sary to know the plasma temperature. In order to measure
the laser-induced plasma temperature at the wavelength
and energy per pulse laser used here, we have assumed lo-
cal thermodynamic equilibrium (LTE) condition [36–39].
Temperature measurements were carried out on the an-
odized Ti6Al4V samples, using Ti lines in the spectral re-
gion between 470–520 nm. The spectroscopic parameters
of the Ti emission lines studied in this work are collected in
Table 1. The values of the oscillator strengths, all of them
having a 10% uncertainty, were taken from [40]. Although
LIPs do not have a homogeneous temperature, the spa-
tial variation in temperature is small in the region where
most of the line emission takes place. Therefore, the use of
a spatially integrated value of temperature to evaluate the
optical depth seems to be reasonable. In this condition the
electrons dominate the reaction rate, so the measured in-
tensity Iλ of the emission line of a single species is derived
from the Boltzmann equation as:
Aki gk − KT
Ek
Iλ = F Cs e (3)
Zs (T )
and
Iλ 1 Cs F
ln =− Ek + ln (4)
Aki gk kT Zs (T )
weight for the upper level, Ek is the excited level energy, T
is the temperature, k is the Boltzmann constant, Zs (T ) is
the partition function of the species, F is an experimental
factor and Cs is the species concentration. Plotting the
72 The European Physical Journal D

Table 2. Spectroscopic parameters of neutral O (I) and Ti (I) nm (TiI). Line 777.539 was not used due is not possi-
transition lines used to determine kt coefficients. ble reach a good resolution. According to reference [41]
the titanium oxide can be present as a sub-oxide series,
Wavelength Ei (eV) Ek (eV) Aki gi gk kt (10−34 m3 )
Tin O2n−1 , with 9  n  4. However, our results show a
(nm) stoichiometry ratio close to Tin O2n .
777.194 (OI) 9.1461 10.7409 49 200 000 5 7 9.4231
777.417 (OI) 9.1461 10.7405 53 000 000 5 9 6.7486
777.539 (OI) 9.1461 10.7402 14 900 000 5 7 4.0503 4 Conclusions
780.597 (TiI) 8.8607 10.4487 17 600 000 – 5 1.1047
782.491 (TiI) 8.9208 10.5049 52 000 000 – 15 7.2592 This work shows that the LIBS technique can be used to
determine the composition of thin film obtained by elec-
trolytic anodized. The possibility to obtain the composi-
tional ratio without using standard samples made LIBS
technique very appropriate to surface analysis. In addi-
tion, with our system is possible to monitor all surfaces
and to determine the uniformity of the coating.

This work was performed with financial support form

COLCIENCIAS and VIE-UIS. The authors thank Henry
Sanchez for technical support.

Fig. 4. (Color online) Boltzmann plot for several atomic lines
emitted by titanium.
left hand side of equation (4) versus the excited level en-
ergy Ek , the plasma temperature can be obtained from
the slope of obtained straight line (Fig. 4). The results
obtained were the same for five anodized Ti6Al4V sam-
ples, within experimental error, so the mean temperature
value of 7526 ± 200 K was used in the calculation of the
kt coefficients.
If the kt,Ti and kt,O coefficients are calculated, ratio
atomic densities may be deduced from the intensity ratios
measured of the plasma emission. With this procedure we
can check the stoichiometry of the film composition. In
this work we have calculated the kt coefficients for the
emission the lines of O (777.194, 777.417 and 777.539 nm)
and Ti (780.597 and 782.491 nm) using spectral data pro-
vided by HARVARD databases [40]. The spectroscopic pa-
rameters of the oxygen and titanium emission lines stud-
ied in this work are collected in Table 2. The values of
the oscillator strengths, all of them have a 10% uncer-
tainty, according reference [40]. The results obtained using
equation (1) show an intensity ratio Ti/O of 0.55 ± 0.03
using the lines 777.194 (OI) and 780.597 (TiI), 0.53 ± 0.04
when is used the lines 777.194 (OI) and 782.491 nm,
0.56 ± 0.03 for the lines 777.417 (OI) and 780.597 (TiI),
and 0.57 ± 0.05 with the lines 777.417 (OI) and 782.491
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