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(Ti,Al)/(Ti,Al)N coatings produced by laser

surface alloying

Article in Materials Letters · March 2002

DOI: 10.1016/S0167-577X(01)00451-7

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 March 2002

Materials Letters 53 Ž2002. 44–51

www.elsevier.comrlocatermatlet

žTi,Al/ r žTi,Al/ N coatings produced by laser surface alloying

´ ) , J. de la Fuente, J.J. de Damborenea
I. Garcıa
Department of Corrosion and Protection, National Center for Metallurgical Research (CENIMr CSIC), AÕenida Gregorio del Amo,
8, E-28040 Madrid, Spain
Received 22 June 2000; received in revised form 25 May 2001; accepted 1 June 2001

Abstract

Ti–Al intermetallic coatings on titanium have been produced by laser surface alloying. A 5-kW CO 2 laser was employed
to melt the surface of the titanium specimens and to alloy it with aluminium powder in a nitrogen atmosphere. The
combination of titanium, aluminium and nitrogen and the specific characteristics of the high-power laser allow a new coating
structure of titanium aluminides and nitrides to be produced. These coatings present a surface Al–TiAl 3 composition that
gradually evolves to Ti 3 Al close to the titanium base. A dendrite structure of titanium nitrides ŽTiN and Ti 2 N. and titanium
aluminium nitrides ŽTi 2 AlN. is formed throughout the laser track. The different structures obtained are described as a
function of laser energy input during the process. q 2002 Elsevier Science B.V. All rights reserved.

Keywords: Laser; Surface alloying; Titanium aluminides; Titanium nitrides; Intermetallics

1. Introduction made of the aluminization of titanium and titanium

Titanium intermetallics are a successful substitute
for titanium and titanium alloys wherever an im-
provement in wear or oxidation properties is needed.
Among those intermetallics, titanium aluminides such
as TiAl have received considerable attention because
of their low density, good high-temperature strength,
and good resistance to creep, fatigue, oxidation and
corrosion w1x. However, TiAl alloys present limited
oxidation resistance at high temperatures due to their
relatively low Al content. A more Al-rich intermetal-
lic such as TiAl 3 could improve oxidation resistance
by self-developing a thicker and denser Al 2 O 3 scale
at high temperatures. To this end, a study has been
)
Corresponding author. Tel.: q34-1-553-8900; fax: q34-1-
534-7425.
´ ..
E-mail address: igarcia@cenim.csic.es ŽI. Garcıa
alloys to obtain a TiAl 3 surface layer. However, the
Al 2 O 3 scale grown on TiAl 3 at high temperature
presents serious problems of brittleness due to severe
crack formation w2x, and some chemical or mechani-
cal anchorage of the Al 2 O 3 scale is thus necessary.
This can be achieved by incorporating high-tempera-
ture reinforcing phases w3,4x such as Cr-stabilized
cubic Al 3Ti w5x. This new trialuminide alloy
ŽAl,Cr. 3Ti provides excellent oxidation protection at
high temperatures and similar mechanical properties
to g-TiAl. Another approach is to microalloy with
substitutional or interstitial elements ŽCr, Nb, Mo, B,
C or N.. In this respect, it has been reported that
carbon and nitrogen as interstitial elements increase
the yield and fracture stresses of TiAl alloys w6x.
Traditional process methods such as ingot-mak-
ing, casting, forging and extrusion present a series of
complications for the production of Ti–Al and Ti–Al
bulk composites. In contrast, laser surface alloying

00167-577Xr02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X Ž 0 1 . 0 0 4 5 1 - 7
 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa
offers good prospects for the production of both
Ti–Al intermetallic coatings and Ti–Al matrix inter-
metallic composites. Regarding Ti–Al compounds,
Abboud and West w7–9x have shown the ability of
lasers to synthesize all the phases of the Ti–Al
system by surface alloying of Al with titanium sub-
strates. More recently, Nirdhu et al. w10,11x have
produced titanium and titanium–aluminium nitrides
by laser nitriding of near g-TiAl alloy. Ti–Al inter-
metallic coatings have demonstrated good resistance
to high-temperature oxidation w12–15x and good wear
resistance w12x. SiC-reinforced Ti–Al composites
have also been produced by laser melting of pre-
synthesized Ti–Al pellets mixed with SiC powders
w16x.
The aim of this work is to produce titanium
aluminides reinforced with hard titanium nitrides by
means of the laser surface alloying method. Both
aluminium and nitrogen are simultaneously fed over
a titanium substrate. The process parameters and the
ŽTi,Al.rŽTi,Al.N structures obtained will serve as
the starting point for future studies of oxidation and
wear.
2. Experimental
Surface laser alloying was carried out using a
Spectra-Physics transverse flow CO 2 laser with a
10.6-mm wavelength, operating in TEM 20 form,
with an output power of 5 kW. The output beam
diameter supplies a spot area of approximately 40
mm2 over the base material. The beam sweep over
the surface was monitored using a computer-con-
trolled two-axis table. Laser movement speeds of
300, 800 and 1100 mmrmin over the samples were
selected. The base material utilized was chemically
pure Ti ŽASME SB348 GR2; C, 0.007%; N, 0.008%;
H, 0.0048%; Fe, 0.14%; O 2 , 0.12%; and balanced
Ti. with a thickness of 10 mm. Aluminium powder
Ž99.9% purity. was fed into the melt zone of the
beam at a rate of 3 grmin using a jet of nitrogen gas
Žflow of 50 lrmin..
After laser treatment, the specimens were cut
lengthways and prepared for metallographic observa-
tion by optical and scanning electron microscopy
ŽSEM.. The energy dispersive spectroscopy tech-
45
nique ŽEDS. was used for quantitative analysis. Tita-
nium phases were also identified by X-ray diffrac-
tion ŽXRD. using a SIEMENS D5000. Vickers mi-
crohardness measurements were performed on
cross-sections of the laser track using a 500-g load.
3. Results and discussion
Titanium specimens alloyed at different laser
speeds presented different microstructures, composi-
tions and distribution zones across the laser track.
These microstructures are described below as a func-
tion of laser speed and distance from the surface
using metallographic, EDS and XRD techniques.
Fig. 1 shows a macrograph of the cross-section of a
laser track processed at a laser speed of 1100
mmrmin. Zones with different microstructures are
identified in Fig. 1 to illustrate the description of the
laser track microstructure. At the laser speeds used in
this work, no cracking was appreciated in the laser
tracks.
XRD spectra were measured from the surface,
and thus, show only the most superficial phases due
to the limited penetration of X-rays in this material.
Fig. 2 shows XRD spectra for samples processed at
three different laser speeds. The presence of Al and
TiAl 3 can be observed in all the samples, as well as
Ti 5 Al 11 and nitrides like TiN, Ti 2 N and Ti 2 AlN in
the coatings processed at the higher laser speeds. On
the other hand, EDS measurements were recorded by
spotting the different phases throughout the cross-
section of the laser track and have permitted the
correlation of XRD-identified phases with SEM ob-
servations.
Fig. 3a shows the outermost part Žzone I. of the
cross-section of a laser track produced at the lowest
laser speed Ž300 mmrmin.. This zone of the track
consists mostly of a solid solution of aluminium
Ž99.6%., containing less than 0.6% of titanium ac-
cording to EDS. The minor phase, lighter in the
SEM image, was identified as TiAl 3 by a combina-
tion of EDS Ž75% Al. and XRD. In the bottom zone
of the image in Fig. 3a, a fine dendrite structure
appears over the Al–TiAl 3 structure. These dendrites
can be identified as a titanium nitride with an alu-
minium content of less than 0.2% according to EDS.
46 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa
Fig. 1. Macrograph of the cross-section of a titanium sample alloyed with aluminium by laser surface alloying at a speed of 1100 mmrmin.
Labels I to V indicate different microstructures as a function of distance from the surface.
As the distance from the surface increases, Fig. 3b
Žzones III–V., the Al solid solution disappears, and
the amount of TiAl 3 increases until it occupies the
whole volume. At the same time, the composition of
the matrix phase gradually changes, with an increase
in the proportion of titanium. According to EDS, in
the zone nearest to the substrate, the amount of
titanium reaches to 75%, suggesting the transforma-
tion of the matrix phase to Ti 3 Al. As can be seen in
Fig. 3b, TiN dendrites are present also in the inner
zones of the track. Finally, the interface with the
titanium substrate shows a certain dilution Žabout
8%. of aluminium in the base material.
Fig. 4 displays the SEM image Žzone I. of a
sample alloyed at the intermediate laser speed Ž800
mmrmin.. Fig. 4 reveals the presence of two phases.
The first is an aluminium solid solution containing
up to 15% titanium according to EDS near the
surface. The extent of this Al solid solution is smaller
than that in the sample produced at the lowest laser
speed, Fig. 3a. The second phase observed near the
surface is TiAl 3 . On the other hand, the titanium
nitride dendrites containing up to 9% aluminium
according to EDS appear closer to the surface in the
specimens treated at this laser speed. XRD of this
sample shows the presence of TiN, Ti 2 N and
Ti 2 AlN, suggesting that the dendrites are composed
of this mixture of nitrides. XRD also shows the
presence of Ti 5 Al 11. This phase is equivalent to
Ti 2 Al 5 , and its formation can be attributed to the
reaction L q Ti 2 Al 5 s TiAl 3 , for a liquid composi-
tion of about 60% aluminium, since the high cooling
rate in laser alloying promotes a shift towards the
right of this equation w17x. As in the sample treated at
the lowest laser speed, the proportion of titanium
measured by EDS increases with the distance from
the surface, from 25% near the surface to 75% near
the base material. This increment in the proportion of
titanium in the laser track suggests a change of the
phase composition from TiAl 3 to Ti 3 Al.
The appearance Žzone I. of the surface alloyed at
the highest laser speed Ž1100 mmrmin. is shown in
Fig. 5. In this case, the outermost zone presents less
aluminium solid solution, as is corroborated by the
smaller aluminium peak in the XRD spectrum. On
the other hand, the major outer phase is again identi-
fied as TiAl 3 by XRD. However, in this sample,
EDS shows a maximum aluminium content of about
70%. As with the samples processed at the other
laser speeds, the amount of aluminium decreases to
25% in the zone closest to the base material. A
higher aluminium content up to 12% is detected by
EDS in the nitride dendrites. This fact, supported by
the XRD spectrum, indicates that the dendrite com-
position presents a higher proportion of Ti 2 AlN. It
can be also seen in Fig. 5 that the number of nitride
 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa 47

Fig. 2. X-ray diffraction obtained for titanium surfaces alloyed with aluminium in a nitrogen atmosphere by means of a laser moving at
different speeds over the surface.

dendrites in the whole laser track has increased in
this sample compared with the coatings produced at
lower laser speeds.
Table 1 summarizes the different phases present
in the laser tracks as a function of laser speed and
distance from the surface. The most outstanding
feature of these results is the progressive aluminium
enrichment of the Ti–Al phases as the distance from
the surface becomes shorter and as the laser speed
becomes lower. However, it is important to bear in
mind that a lower laser speed implies a higher dose
of aluminium powder since the aluminium feed was
kept at a constant rate of 3 grmin. Therefore, the
lower the specimen’s travelling speed, the higher the
amount of aluminium per volume unit of the track.
The microhardness measured for all the speci-
mens indicates typical values of 600–700 H V for
the TiAl 3 phase and 1000 H V for ŽTi,Al.N.
The results involving only Ti–Al compounds cor-
roborate other studies of Ti–Al synthesis without the
presence of nitrogen. High-resolution transmission
electron microscopy of Ti–Al produced by rapid
solidification melt spinning identified the formation
of TiAl 3 and a large number of long-period super-
structures such as Ti 5 Al 11 for the Al-rich side of the
phase diagram w18,19x. The evolution of TiAl 3 to
48 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa

Fig. 3. SEM micrographs showing the microstructure of a titanium sample alloyed with aluminium by means of laser surface alloying at a
speed of 300 mmrmin. Ža. Surface zone showing a two-phase structure ŽAl and TiAl 3 . over a microstructure of TiAl 3 with banded nitride
dendrites Žzone I., and Žb. interface with the heat-affected Ti substrate showing banded nitride dendrites over Ti 3 Al Žzones III–V..

Ti 3 Al, as the distance from the surface increases, has nium with the distance from the surface presents two
also been reported in similar laser alloying processes advantages. On the one hand, the high amount of
w9x. The progressive increase in the amount of tita- aluminium on the surface leads to the expectation of
 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa 49

Fig. 4. SEM micrograph of the microstructures close to the surface of a Ti sample alloyed with Al using a laser speed of 800 mmrmin
Žzone I.. The superficial Al phase is reduced in comparison with Fig. 2, with TiAl 3 being the major phase. The nitride dendrites are also
closer to the surface.

good Al 2 O 3 scale formation at high temperature. On An innovating feature of this work has been the
the other hand, the progressive rise in the proportion successful incorporation of nitrogen throughout the
of titanium from 25% to 75% leads to the expecta- melting zone and its reaction with the titanium and
tion of a good bond with the titanium base material. aluminium. Specifically, nitrogen becomes part of

Fig. 5. SEM micrograph of the microstructures close to the surface in a Ti specimen processed at a laser speed of 1100 mmrmin Žzone I..
The superficial Al phase disappears and the microstructure is comprised of TiAl 3 plus nitride dendrites even at the surface.
50 ´ et al.r Materials Letters 53 (2002) 44–51
I. Garcıa

Table 1 titanium aluminium nitrides has been produced by

Phases present in the laser-alloyed coatings along a cross-section surface laser alloying. Some unique characteristics of
Laser speed Žmmrmin. laser alloying in nitrogen atmospheres, such as its
300 800 1100 extremely fast cooling rate, have permitted the ob-
Surface I Al, TiAl 3 Al, TiAl 3 TiAl, TiAl 3 , tainment of composites with intermetallic phases.
ŽTi,Al.N The TiAl 3 q Ti 2 AlN q TiN coating obtained in this
II TiAl, TiAl 3 , TiAl, TiAl, work by means of laser surface alloying needs to be
ŽTi,Al.N ŽTi,Al.N ŽTi,Al.N
further characterized, though previous studies on
III Ti 3 Al, Ti 3 Al, Ti 3 Al,
ŽTi,Al.N ŽTi,Al.N ŽTi,Al.N similar materials allow good results to be expected.
IV TiŽAl. TiŽAl. TiŽAl.
Substrate V Ti Ti Ti

Zones I–V are indicated in Fig. 1. ŽTi,Al.N represents the pres- Acknowledgements
ence of Ti 2 N, TiN and Ti 2 AlN.

Part of this work has been supported by project

three compounds, namely two titanium nitrides ŽTiN
and Ti 2 N. and one titanium aluminide nitride
ŽTi 2 AlN., as identified by XRD in Fig. 1. According
to the ternary diagram Ti–Al–N, the solubility limit
of N at 1000 8C is around 0.3% atm, and therefore,
the TiN phase can only exist at the highest tempera-
tures w20,21x. Thus, TiN has been formed at the start
of solidification and transformed to the low tempera-
ture stable compound Ti 2 AlN during cooling w20x.
The high solidification speed of laser melting pre-
vents the evolution of TiN to Ti 2 AlN, causing this
important retention of titanium nitrides.
Some properties of the nitrides obtained in this
work have already been reported elsewhere, allowing
an estimation of the laser-processed composite coat-
ing properties produced in this work. In this way, it
is known that the precipitation of Ti 2 AlN causes a
decrease in grain size and an increase in tensile
elongation and creep resistance in the intermetallic
TiAl w20x. On the other hand, recent work on HIP
nitriding of TiAl alloys w22x shows an improvement
in the wear resistance by the formation of a surface
TiN layer. However, the TiN layer shows slightly
worse high-temperature oxidation behaviour. Never-
theless, other studies have reported better high-tem-
perature oxidation resistance by mixed nitrides
ŽTi,Al.N than by TiN w23x.
4. Conclusions
An intermetallic titanium aluminium coating rein-
forced by a fine dendritic structure of titanium and
MAT93-0630-002-01 of the Spanish Ministry of Ed-
ucation.
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