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Journal of

Materials
Processing
Technology
ELSEVIER Journalof Materials ProcessingTechnology 44 (1994) 54 60

Laser surface-treatment of titanium


H. Badekas*, C. P a n a g o p o u l o s a n d S. E c o n o m o u
Laboratory of Physical Metallurgy, National Technical University of Athens, Zografou Campus,
157 73 Athens, Greece

(ReceivedApril 2, 1993;accepted November 29, 1993)

Industrial Summary

The surface of laser-treated titanium specimens shows a succession of dark and white stripes.
The surface roughness of these specimens was observed to be a function of the power density of
the laser; the hardness of the top surface layers (35 lam) of the laser-treated titanium specimens
being greater than that of the deeper layers of the same specimens.

1. Introduction

A laser beam can be used in various ways in order to improve the surface properties
of different metallic and ceramic materials. Argon, ruby, C O / a n d N d : Y A G lasers are
today used in various areas of materials technology. With the aid of powerful lasers,
several metallurgical processes have been applied for the surface treatment of metallic
materials e.g. surface remelting, cladding and surface alloying, phase transformations,
laser-assisted physical and chemical vapour deposition, cutting and welding.
Recently, a new laser, the excimer laser, has been developed but it is not used widely
by the scientific and industrial communities. The most recent applications of the
excimer laser in the technological field of surface metallurgy are described briefly
below.
Ursu et al. [1] studied the change in the metallic surface micro-relief as a result of
multiple pulses from a powerful UV laser, showing that the metallic structure
produced depends on the laser power density, the number of laser pulses, the state of
the metallic surface and the nature of the ambient gas during the laser treatment.
Tosto [2] studied the effect of excimer laser irradiation on thin sheets of pure
copper, predicting by calculation and also observing the generation of shock waves in
the sheets of copper as a result of the irradiation.

*Corresponding author.

0924-0136/94/$07.00 1994ElsevierScienceB.V. All rights reserved.


SSDI 0924-0 1 3 6(93)E0 1 39-8
H. Badekas et al. / Journal of Materials Processing Technology 44 (1994) 54-60 55

Badekas et al. [3] examined the influence ofexcimer laser irradiation on the surface
properties of an aluminium alloy (A1-4 %Cu), observing that the laser surface
treatment changes the magnitude and the sign of the surface residual stress. They also
found that the laser treatment of the alloy increases its microhardness on the top
surface layers (30 ~m).
Jervis et al. [4] examined the influence of excimer laser treatment on the surface
chemistry and corrosion properties of AISI type 304 stainless steel. With the aid of
Auger spectroscopy, these investigators observed the enhancement of the chromium
concentration at the surface layers of the stainless steel. They also observed that the
laser treatment of the steel increases its resistance to pitting corrosion.
Panagopoulos and Michaelides [5] examined copper specimens irradiated with an
excimer laser, noting that the laser treatment of the copper changes the magnitude and
the sign of the surface residual stress from tensile to compressive. They also found that
the surface roughness of the laser-treated copper is a non-linear function of the power
density of the laser.
The present study deals with the excimer laser treatment of titanium, which has not
been reported previously.

2. Experimental method

Specimens with dimensions of 3 cml cm0.2 cm were cut from titanium foil of
99.85 % purity, the specimens being polished mechanically with SiC paper (800). The
titanium specimens were irradiated, in atmospheric air, with a Lambda Physik
high-power excimer laser using a KrF gas mixture with wavelength 2 = 248 nm and
a photon energy of 330 mj per pulse. The laser beam pulse had a Lorentzian shape.
Each titanium specimen was irradiated under different conditions, these conditions
being determined by changing the following lasing parameters: (1) the power density,
(2) the pulses per step, (3) the frequency of laser pulses. All the laser treatments of
titanium specimens were carried out with 70 % overlapping of two successive laser
steps.
The surface morphology of the laser-treated titanium specimens was studied with
a Zeiss optical microscope and a Philips scanning electron microscope, whilst the
surface structure of the specimens was examined with a Philips X-rays diffractometer
with Co ka radiation, 2 = 0.1791 nm, and an iron filter. The surface roughness of the
laser-treated titanium specimens were also studied with a Perthen profilometer. The
corrosion resistance of an as-received titanium specimen and some laser-treated
titanium specimens was studied also, in a 0.4 M NaC1 solution of pH = 5 and at
a temperature of 290 K.

3. Results and discussion

Figure 1 shows the surface morphology of a laser treated titanium specimen, from
which can be noted a pattern of successive dark and light stripes on the surface of the
56 H. Badekas et al. / Journal ~f Materials Processing Technology 44 (1994) 5 4 60

Fig. I. Plan view of a laser-treated titanium specimen. Lasing conditions: 1 - 150 MW/cmZ; 50 pulses per
step; f = 20 Hz; and 70% overlapping.

specimen, the dark stripes corresponding to the maximum value of the incident laser
power and the light stripes corresponding to the overlapping area of two successive
laser steps. The dark stripes can be attributed to the thicker titanium oxides formed
during the laser irradiation. Patterns with successive dark and light stripes on the
surface of laser-treated titanium were mainly observed when the overlapping of two
successive laser steps was less than 70-75 %.
Figure 2 shows the surface morphology, at higher magnification than in the
previous figure, of a laser-treated titanium specimen, from which can be observed the
formation of surface cracks on the specimen. In addition, it can be seen that intensive
oxidation of titanium has occurred across these cracks.
Figure 3 shows the transverse section of a laser-treated titanium specimen. In this
figure the laser-affected zone, with an average width of 20-25 ~tm, can be seen and for
depths greater than 25 ~m the heat-affected zone can be seen also. As observed, the
depth of the laser-affected zone is not uniform, which might be due to the non-uniform
heat transfer from the top to the deeper layers of the titanium during its laser
irradiation as a result of different defects existing in the surface layers.
Figure 4 shows the surface roughness of laser-treated titanium as a function of the
power density of the laser. For laser power densities of less than 130 M W / c m 2, the
surface roughness of the laser-treated titanium is seen to be independent of the power
density. In the laser power-density range 130 240 M W / c m z, an abrupt increase of the
surface roughness can be observed. For laser power-densities of greater than
240 M W / c m 2, a decrease of the surface roughness is observed, which might be
H. Badekas et al. / Journal of Materials Processing Technology 44 (1994) 54-60 57

Fig. 2. Plan view of a laser-treated titanium specimen. Lasing conditions: I = 200 MW/cm2; 30 pulses per
step; f = 20 Hz; and 70% overlapping.

Fig. 3. Transverse view of a laser-treated titanium specimen. Lasing conditions: 1 = 100 M W / c m 2 ;


30 pulses per step; f = 50 Hz; and 70% overlapping.
58 H. Badekas et al. /Journal of Materials Processino Technology 44 (1994) 54 60

~2
t
+
._.=
.<
el;

'i ++
o I I
+
1,o lt,0 240 340
P (HW/cm 2 )

Fig. 4. Surface roughness of laser-treated titanium as a function of the incident power density. Lasing
conditions: 30 pulses per step; f = 30 Hz; and 70% overlapping.

E 140
{

=o 130 +
I:i

E
120

110 I
20 40
I
60
I

depth (I.cmI

Fig. 5. Microhardness of a laser-treated titanium specimen as a function of depth. Lasing conditions:


I = 150 MW/cm2; 50 pulses per step; f = 20 Hz; and 70% overlapping.

a t t r i b u t e d to the existing plasma being detached from the t i t a n i u m surface due to the
high density of the laser irradiation; a first result of this p h e n o m e n o n m u s t be the
decrease of laser energy a b s o r p t i o n by the t i t a n i u m surface a n d a second indirect
result the decrease of the surface roughness of the titanium.
Figure 5 shows the m i c r o h a r d n e s s of a laser-treated t i t a n i u m specimen as a function
of the depth from the surface of the specimen d o w n to 40 ~tm, the microhardness being
H. Badekas et al. / Journal of Materials Processing Technology 44 (1994) 54-60 59

6
i...-

6
6 o
Z
i:

1 80
I I
70
I
60 50
I ii
2@()
40

Fig. 6. X-rays diffraction spectrum of a laser-treated titanium specimen. Lasing conditions: I = 150 M W /
cm2; 50 pulses per step; f = 20 Hz; and 70% overlapping.

w
u -0.2

0 0 0 0 0 0
0
0
0
0 0
-0.6
I I I
10 100 loo0
time(rain)

Fig. 7. Corrosion potential of an as-received (O) and a laser-treated (O) titanium specimen as a function of
the corrosion time in a NaCI solution.

seen to decrease until a depth of 30 ~tm,after which it is approximately constant. From


these observations it might be said that the surface layers of the titanium specimen
(0-30 lam) have become less defective and undergone hardening due to the laser-
treatment procedure.
Figure 6 shows the X-rays diffraction spectrum of a laser-treated titanium speci-
men. Apart from the titanium diffraction planes, it can be seen that diffraction planes
from titanium nitride compound have been detected also, the formation of this
compound having occurred during the laser treatment of the titanium. If, during
the laser irradiation, the surface temperature is kept lower than the boiling point of
the titanium, 3550 K, then the surface product of titanium i.e. titanium nitride, is
supposed to be formed by a liquid titanium-ambient gas reaction I-6].
Figure 7 shows the corrosion potential of an as-received titanium specimen and
a laser-treated titanium specimen, as a function of time of immersion in NaC1 solution.
60 H. Badekas et al. / Journal of Materials Processin9 Technology 44 (1994) 54 60

For the laser-treated titanium specimen, it can be noted that its corrosion potential is
approximately constant with increasing time, which means that the corrosion rate of
these specimen is also approximately constant. In the case of the as-received titanium
specimen, its corrosion potential increases gradually up to 200 min and then becomes
constant up to 2000 min. This change in the corrosion potential with time indicates
that during the first period of time a passivating film is formed continuously on the
surface of the specimen, whereas during the second period of time the corrosion rate of
the specimen is constant.
Comparing the corrosion potential of the two specimens, it can be seen that the
corrosion potential of the laser-treated specimen is more noble than that of the
as-received titanium specimen, which indicates that the first specimen is more anti-
corrosive than the second specimen.

4. Conclusions

In this study, specimens of pure titanium were surface treated with a high-power
excimer laser, the main conclusions of the study being given below.
(i) The surface of laser-treated titanium shows a succession of dark and white stripes.
(ii) The laser-affected zone of the titanium was found to be about 30-35~tm.
(iii) The surface roughness of the titanium was noted to depend on the power density
of the laser.
(iv) The surface layers were found to be harder than the deeper layers of the
laser-treated titanium.
(v) The laser-treated titanium was observed to be more anti-corrosive than the
as-received titanium.

5. Acknowledgements

The authors wish to thank Dr. E. Hontzopoulos, FO.R.T.H. (Crete) for provision of
the laser facilities. They also thank Dr. A. Koutsomichalis for his valuable experi-
mental assistance.

References
[1] 1. Ursu, I. Mihailescu, A. Popa, M. Prokhorov and V. Konov, J. Appl. Phys., 58 (1985) p. 3909.
[2] S. Tosto, Gr-I International conference "New Laser Technologies", Olympia, Greece, 1988, p. 153.
[-3] H. Badekas, A. Koutsomichalis and C. Panagopoulos, Surf. Coat. Techn., 34 (1988) 365.
[-4] T.R. Jervis, D.J. Frydrych and D.B. Bear, Matter. Lett., 6 (1988) 225.
[-5] C. Panagopoulos and A. Michaelides, J. Mater. Sci., 27 (1992) 1280.
[-6] S. Nishitani, H. Yamaoka and M. Yamaguchi, Jap. J. Appl. Phys., 29 (1990) 2477.

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