Applied Surface Science 242 (2005) 177–184

www.elsevier.com/locate/apsusc

Research progress on laser surface modification of titanium alloys

Y.S. Tian, C.Z. Chen*, S.T. Li, Q.H. Huo
School of Materials Science and Engineering, Shandong University, Jinan Shandong 250061, PR China
Received in revised form 14 July 2004; accepted 10 August 2004
Available online 25 September 2004

Abstract

Recent developments on laser surface modification of titanium and its alloys are reviewed. Due to the intrinsic properties of
high coherence and directionality, laser beam can be focus onto metallic surface to perform a broad range of treatments such as
remelting, alloying and cladding, which are used to improve the wear and corrosion resistance of titanium alloys. In addition, the
fabrication of bioactive films on the surface of titanium alloys to improve their biocompatibility can be performed by the method
of laser ablation deposition. The effect of some laser processing parameters on the resulting surface properties of titanium alloys
is discussed. The problems to be solved and the prospects in the field of laser modification of titanium and its alloys are
elucidated.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Research progress; Laser surface modification; Titanium alloys

1. Introduction many years [1–4], they are bioinert materials and

Titanium and its alloys are extensively used in
aeronautical, marine and chemical industries owing to
their specific properties such as high strength,
excellent corrosion, oxidation and high-temperature
resistance. Nevertheless, the application of titanium
alloys under severe wear and friction conditions is
highly restricted due to their poor tribological
properties such as high friction coefficient and low
hardness. On the other hand, although titanium and its
alloys are commonly used as a medical implants for
* Corresponding author. Tel.: +86 531 8395991;
fax: +86 531 8392313.
E-mail address: felix@sdu.edu.cn (C.Z. Chen).
occasionally failure because of the corrosion-fatigue
which titanium implants suffered in body fluids [5]. In
addition, it is dangerous for Ti–6Al–4V to stay in the
human body for a long time, because the element
aluminum has strong neurotoxicity and vanadium is a
strong cytotoxin [6]. So, surface modification of
titanium and its alloys is a promising work in
enlarging their application scope.
Laser beams, owing to their high coherence and
directionality, are widely used in surface modification
of many kinds of metals. Thus, the disadvantages of
titanium alloys can be compensated for by laser
surface modification treatment on the workpieces
where they suffer in operation, or by laser cladding a
layer of bioceramic coatings on the surface of titanium

0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.08.011
178 Y.S. Tian et al. / Applied Surface Science 242 (2005) 177–184
alloy substrates to meet the requirement for implanta-
tion in human body. In this paper, recent developments
on laser surface modification of titanium alloys are
reviewed and the problems to be solved in this field are
discussed.
2. Enhancing wear and corrosion resistance
Conventional chemical heat treatment such as
nitriding, carburizing and boriding has some dis-
advantages such as a long processing time and the
easy deformation of the workpiece being treated.
Thermal spray coatings also have some demerits such
as low coating density and limited bond strength
between the coating and the substrate. However, laser
treatment can be free from the above-mentioned
shortcomings. In addition, laser treatments have
several other advantages over commonly used heat
treatment and spraying methods including precise
control over the width and depth of processing,
ability to process complex parts, and to selectively
process specific areas of a component. The common
methods of enhancing wear and corrosion resistance
of titanium and its alloys by laser treatment are as
follows.
2.1. Laser surface remelting
Laser surface remelting of Ti and its alloys is using
a high power laser beam to melt the surface of
workpiece (or sample) to be treated. With the laser-
generated melt pool solidifying rapidly after laser
beam movement, a layer of fine martensite is thus
produced on the surface of the Ti alloy and a film of
TiO2 on the top surface, both of which have excellent
wear and corrosion resistance. Langlade et al. [7]
found in their work of laser remelting of pure Ti and
Ti–6Al–4V alloy that different titanium oxides such as
TiO, TiO2 and Ti2O3 were formed in the surface layers
of the samples by varying laser treatment parameters.
Pérez and Lavisse et al. [8,9] also obtained the similar
results as Langlade did. Ref. [10] showed that laser
surface remelting significantly improved the corrosion
resistance of the Ti–6Al–4V alloy. The pitting
potentials of the untreated and treated samples
measured were 3.51 and 5.56 V, respectively. In
addition, corrosion current could be reduced as much
Fig. 1. Polarization curves of base and laser surface remelted
sample.
as seven-fold after laser treatment. Fig. 1 [11] shows
the polarization curves of base and laser surface
remelted Ti sheets. The Epit is critical pitting potential,
which is used as a measure of resistance to pitting
corrosion. The Eprot is protection potential, below
which established pits presumably cannot continue to
grow. It means that the higher the value of Epit, the
better the pitting resistance. A sharp increase in the
current indicates the potential required for causing pit
initiation and appreciable pit propagation. In contrast,
the polarization curves for the remelted pure Ti display
a different behavior. The current is lower overall and a
pitting potential Epit was not observed within the
measured potential range. Both of them indicated that
the possibility of pitting initiation and propagation on
remelted pure Ti was very low and the corrosion
resistance improved considerably after it was laser
remelted. So laser surface remelting is a potential way
to improve corrosion resistance of titanium alloys and
thus extend their application range in harsh environ-
ments.
2.2. Laser surface alloying
During laser surface alloying, the pre-placed
powders or the powders/gases fed into the melt zone
with a feeder/nozzle dissolve into the laser-generated
melt pool and chemical reactions take place between
the additives and the melted substrate. With the laser-
generated melt pool solidifying, an alloyed layer of
0.5–1.0 mm thickness is thus produced on the surface
of the substrate.
 Y.S. Tian et al. / Applied Surface Science 242 (2005) 177–184
2.2.1. Laser gas surface alloying
Nitrogen gas is usually used in laser gas surface
alloying. Laser surface nitriding of pure titanium was
initiated by the work of Katayama et al. in 1980s and
since then there have been a number of other
investigations on laser surface nitriding of titanium
and its alloys. The results of laser gas nitriding of Ti–
6Al–4V showed that some 400–500 mm thickness of
TiN layer was formed on the substrate [12], which
increased the microhardness from 370HV0.5 to
750HV0.5 and enhanced erosion resistance significantly
compared with untreated Ti–6Al–4V. Refs. [13,14]
illustrated that the nitrided layer mainly consists of
tetragonal d0 -TiNx crystalline phase and which was
nothing to do with the concentration and pressure of
nitrogen gas. In the laser nitriding process, nitrogen
pressure intensity has an effect on the thickness of the
nitrided layers. In order to laser nitriding smoothly, the
nitrogen pressure intensity should higher than one
atmospheric pressure. But nitrided layer becomes
thinner with the higher nitrogen pressure intensity
because a large amount of heat is taken out with the
increasing nitrogen flow rate. When energy density and
nitrogen flow rate are invariableness, with laser
scanning velocity increasing, the microhardness of
the nitrided layer decreases [15]. When using con-
tinuous wave laser and processing parameters of energy
density, beam diameter, scanning velocity and nitrogen
pressure are 5.0  104 W/cm2, 3 mm, 6 mm/s, and
0.4 MPa, respectively, fine TiN compounds are easily
formed in the alloying layers [16]. With Nd-YAG laser
and the optimum processing parameters of 500 W laser
power, 2 mm beam diameter, 5 mm/s scanning speed
and 60 L/min gas flow rate, the alloyed layers,
1000HV0.2–1500HV0.2 hardness, freeing from cracks
and pores, with a depth of about 0.5 mm can be ob-
tained. The cavitation erosion resistance (in 3.5% NaCl
solution) of the nitrided samples is much better than the
untreated [17]. Refs. [18–20] confirmed that TiN is of
excellent high-temperature and corrosion resistance,
and high degree of hardness. So, fine dendritic TiN
crystals are believed to contribute to the improved
erosion and wear resistance of Ti and its alloys.
2.2.2. Laser powder surface alloying
Many researchers have performed the work of laser
alloying of Ti and its alloys and different powders have
been used as alloying additives. The results of laser
179
alloying of Ti–6Al–4V with NiAl and ZrO2 mixed
powders indicated that the microstructure of the
alloyed layer was finer and its microhardness was
higher than that of the base material [21]. During laser
alloying processes, NiAl and ZrO2 powders were
dissociated and reacted with other elements in the
molten pool to form new compounds. The alloyed
layers consisting of TiAl3 + TiAl compounds were
obtained on the Ti–6Al–4V substrate by laser surface
alloying with Al + Nb [22]. Oxidation test results
carried out at 900 8C in air showed that a dense and
homogenous Al2O3 oxide film, which effectively
prevented the substrate from oxidation, was formed on
the surface of alloyed layers. Under the following
optimum conditions of 3–4.3 kW laser energy, 175–
450 mm/min scanning rate, 3.45 mm  2.4 mm beam
size, 16–20 mg/s powder feed ratio and 6 L/min Ar gas
flow, a uniform and defect-free alloyed layer was
obtained by laser surface alloying of pure Ti and Ti–
6Al–4V with Si/Al or both [23,24]. The test results of
cyclic oxidation between room temperature and
850 8C illustrated that laser surface alloying with Si
or Si + Al has a good effect on improving oxidation
resistance of pure Ti and its alloys. This enhanced
oxidation resistance is attributed to the presence of
uniformly distributed Ti5Si3 in the alloyed zone
underneath a SiO2/Al2O3 rich superficial oxide scale.
Refs. [25–27] reported that the alloyed layers
consisting of dendritic and thread-like TiC and Ti5Si3
compounds have high hardness and excellent wear
resistance under both abrasive and sliding wear
conditions. Dendritic crystals are formed easier in
the nitrogen environment than in the helium environ-
ment under the same processing parameters [28].
The alloyed layers containing TiB and TiN
compounds fabricated on the surface of Ti–6Al–4V
alloy by laser alloying with BN powder have a hardness
of about 1700HV and a good wear and corrosion
resistance [29]. Laser alloying of g-TiAl alloy with
carbon showed that platelet-like fine TiC reinforcing
phase had a gradient distribution in the alloyed layers
which exhibited high hardness and excellent high-
temperature sliding wear resistance [30]. The present
authors’ work [31] of laser alloying of pure titanium
with graphite powder illustrated that the microhardness
of the alloyed layer is up to 1200HV0.1 (Fig. 2), more
than four times that of substrates. Fig. 3 is the SEM
micrograph of alloyed layers.
180 Y.S. Tian et al. / Applied Surface Science 242 (2005) 177–184
Fig. 2. Microhardness profiles of laser alloyed layers.
2.3. Laser cladding
Laser cladding uses a defocused or a rastered laser
beam to melt powder or wire onto the surface of
titanium and its alloys. The laser energy melts the
cladding material forming a metallurgical bond with
the substrate. Some of the advantages that laser
cladding offers over commonly used cladding
methods include high deposition rates, low dilution
of the substrate, high cooling rates, and low distortion.
Lasers have the ability to clad both similar and
dissimilar materials, including materials impossible to
clad by conventional processes. As a surface coating
technique, laser cladding has being developed for
improving wear, corrosion and fatigue properties of
machine parts.
The commonly used materials for cladding of
titanium and its alloys are Ni-base alloy powders
because they have better high-temperature, wear and
corrosion resistance properties, and are easier to bond
Fig. 3. SEM micrograph of dendritic TiC.
to the substrate than that of any other alloy powders.
Compared with laser alloying, laser cladding should
ensure that the coating fuses to but is not diluted too
much by the substrate.
During laser treatment, the elements in the coatings
react with each other to form wear and corrosion
resistance compounds in situ. The coatings consisting
of TiB2, CrB, M23C6 and M23(CB)6 compounds were
obtained by Laser cladding NiCrBSiC and TiC mixed
powders on Ti–6Al–4Vsubstrates [32–35]. The aver-
age microhardness reaches 1000HV in the cladding
zone, 600HV in the dilution zone and 380HV in the
heat-affected zone. Compared with the untreated
titanium alloy, the coatings have a wear rate an order
of magnitude less. The results of laser cladding of pure
titanium with NiTiSi mixed powders demonstrated
that Ti5Si3, NiTi2, NiTi and Ti2Ni3Si compounds were
formed in the coatings [36,37], which have excellent
wear resistance and very low load sensitivity under dry
sliding wear test conditions.
Researchers have performed laser cladding of
titanium and its alloys with other materials. Laser
cladding of Ti alloy with ZrO2 powder showed that a
ZrO2/Ti gradient layer was fabricated on the substrate
[38,39]. Under the unlubricated sliding wear test
condition, the cladding layers containing TiN dentrites
of different size and unmelted TiN particles exhibiting
an excellent wear resistance compared with that of the
substrate [40]. Refs. [41,42] reported that with a
proper power density and ratio of Ti to Cr3C2
additives, the laser cladding coatings consisting of
TiC particles dispersed in a-Ti matrix can greatly
enhance the surface hardness and wear resistance of
the substrate. Our present investigation [43] of laser
cladding of Ti–6Al–4V with graphite and silicon
mixed powders also showed that a significant amount
of SiC, TiC and Ti5Si3 compounds were formed in situ
in the coatings (Fig. 4) which have a high
microhardness value of about 2000HV0.1 and lower
wear coefficient (about 0.30) than that of the substrate
(about 0.55).
3. Improving biocompatibility
Although titanium and its alloys have been
extensively used as implanting materials in different
medical applications for many years due to their
 Y.S. Tian et al. / Applied Surface Science 242 (2005) 177–184
Fig. 4. The constituent of the coatings: (a) X-ray diffraction spec-
trum; (b) EPMA secondary electronic image.
excellent mechanical properties and high corrosion
resistance, they are bioinert materials and have poor
biocompatibility with human tissue. On the other
hand, hydroxyapatite (HA) is increasingly used as an
implant material for medical applications owing to its
very good biocompatibility. But its poor mechanical
properties are not favorable for bone-repair purposes.
The combination of the good biocompatibility of HA
and the excellent mechanical properties of titanium
alloy is a potential way to expand their biomedical
applications. The common way of fabricating coatings
on Ti substrate is plasma spraying. However, the long-
term stability of the plasma spray coated HA is a
problem because of occasional failure at the interface
between coatings and substrate. In addition, the
formation of amorphous calcium phosphate phase
reduces the crystallinity and changes the chemical
constituent in the coatings. So, the experiment of laser
remelting after plasma spraying for improving the
crystallinity and bonding strength between the coat-
ings and the substrate have been performed by Khor et
al. [44]. XRD results for laser treated coatings showed
increased crystallinity of HA the phase and the
favorable amount of crystalline HA was found when
4.5 J laser pulse energy, 400 mm/min scanning speed
and 3 mm laser spot size was employed.
181
Recent years, researchers have made use of
deposition techniques for fabrication of ceramic film.
Among them pulsed laser deposition (PLD) is a
potential method for fabricating bioactive film on to a
Ti alloy substrate. Nelea et al.’ work [45] of PLD
fabricating HA coatings on Ti–5Al–2.5Fe alloy
showed that the PLD film mostly containing HA
phase exhibits good mechanical characteristics. Ref.
[46] showed that PLD produced HA coatings exhibits
much higher adhesive strength with substrates than
that of conventional plasma-sprayed coatings. In
addition, PLD coatings are more ductile than titanium
substrates and are not delaminated from the substrates
by scratch. Also, the results showed that the crystalline
HA coatings are superior in internal cohesion to the
amorphous one. Ref. [47] illustrated that the thickness
of deposition layers has an effect on the morphology
and the adhesion strength of the coatings. The coatings
start to grow as amorphous calcium phosphate.
However, hydroxyapatite is synthesized in the film
350 nm thick, whereas thicker coatings present some
alpha tricalcium phosphate in addition to hydroxya-
patite. The resulting coating to substrate adhesion was
evaluated through the scratch test technique and found
that adhesive strength decreases as thickness
increases.
4. The main problems
4.1. Problems in enhancing wear and corrosion
resistance
At present, the main problems in laser cladding and
alloying are still the cracks, which result from the very
high cooling rate of the melted pool after laser beam
movement, and the poor result reproducibility.
Unfortunately, the reports of controlling cracks
formed in the surface layers of laser-treated Ti and
its alloys are rarely reported. Robinson et al. [48]
measured the residual stress in the remelted layers of
Ti–6Al–4V caused by laser irradiation by using X-ray
diffraction. The results showed that the residual stress
value induced by multiple overlap tracks is much
higher than that of single track. This is why cracks
may occur in multi-track samples, even no cracks
detected in single-track samples produced under
identical conditions. Mridha et al. [49] investigated
182 Y.S. Tian et al. / Applied Surface Science 242 (2005) 177–184

the cracks formed on the surface of nitrided pure

titanium and found that with the laser scanning speed
increasing and the nitrogen gas flow rate decreasing
the number of cracks decreased. On the other hand,
they also found nitriding in a dilute environment
(nitrogen–helium and nitrogen–argon mixed gases)
can free from cracks totally. The formation of less
dendritic TiN in mentioned condition is the reason for
lower cracks occurred in the nitrided layers. In the
experiment of laser cladding of Ti–6Al–4V with SiCp
[28], they also found that dendritic TiC is a main cause Fig. 5. Sketch of laser-assist laser ablation deposition.
to the cracks. Hu et al.’s work [50] illustrated that
preheating by laser glazing under argon prior to density of the HA film are improved [53,54]. High
nitriding, not only was the tendency to cracking energy N+ ion beam implantation treatment of pulsed
reduced, but also a more uniform depth of the nitrided laser-deposited HA thin film on a Ti alloy substrate
layer was produced. also demonstrated that the dynamic mechanical
The poor result reproducibility, especially in laser properties in the implanted zones are enhanced [55].
alloying/cladding with ceramic powder, is another
major issue of laser processing. From our present
investigations [31,43] we notice that the laser 5. Concluding remarks
alloying/cladding with metal and ceramic mixed
powders has a better processability and reproducibility Despite the demerits such as cracks, pores and over
than that of with only ceramic powder under the dilution of the composition etc occurred occasionally
identical processing environment. The reason of poor in the laser-modified layers, laser treatment is still a
results reproducibility is that ceramic powder, which potential way for improving the surface properties of
has a poorer affinity to metallic substrate than that of titanium and its alloys. On the other hand, laser
metal and ceramic mixed powders, is not easy to ablation deposition HA film has been proved to be
dissolve uniformly in the melted pool. preferable for osteoblasts cultured [56]. So, laser
treatment will find increasing uses in the surface
4.2. Problems in enhancing biocompatibility modification of Ti alloys in the coming years.

The major problems in the HA thin films

fabrication process are the changes in constituents,
the lack in density and the poor bonding strength
between the films and the substrates. In order to solve
these problems, Katto et al. [51] fabricated HA film on
the surface of Ti–6Al–4V by using laser-assisted laser
ablation deposition method (Fig. 5). The test results
proved that the adhesion to the substrate and the
crastallinity of HA coatings is improved. Ref. [52]
showed that a buffer interlayer can significantly
improve the crystalline structure and mechanical
characteristics of HA film because the buffer layers
prevent Ti diffusion into the HA film during the
thermal treatment. The results of using high energy
Ar+ ion beam implantation treatment of pulsed laser-
deposited HA thin films on Ti–5Al–2.5 Fe alloy
substrates showed that both the bonding strength and
Acknowledgements
This work is financial supported by Department of
Science and Technology of Shandong province, PR
China (Grant No. 032090107).
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