Scripta Materialia 48 (2003) 1337–1342

www.actamat-journals.com

Fabrication of functionally graded TiC/Ti composites

by Laser Engineered Net Shaping
Weiping Liu *, J.N. DuPont
Department of Materials Science and Engineering, Lehigh University, 5 E. Packer Avenue, Bethlehem, PA 18015, USA
Received 3 December 2002; received in revised form 7 January 2003; accepted 13 January 2003

Abstract
Crack-free functionally graded TiC/Ti composite materials were fabricated by laser engineered net shaping (LENS),
with compositions changing from pure Ti to approximately 95 vol% TiC. By delivering the constituent materials from
different powder feeders and through process control, the LENS process can be used for the fabrication of functionally
graded materials.
Ó 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Keywords: LENS processing; FGM; Composites; Microstructure; TiC carbide

1. Introduction structure in an intentional manner according to

the distribution of properties needed to achieve the
Functionally graded materials (FGMs) are a desired function [2]. Therefore, FGMs can be uti-
class of advanced materials of which the compo- lized for the realization of innovative properties
sition and microstructure change gradually from and functions to meet performance requirements
one side to the other, resulting in a corresponding that vary with location within a component.
variation in the properties. The concept of FGMs Among various FGMs, ceramic/metal FGMs are
was first proposed in 1987 to develop heat-resis- of great practical interest. These FGMs accom-
tant materials for the propulsion system and air- plish the integration of normally incompatible
frame of space planes [1]. Since then, much functions such as the refractoriness and wear re-
research has been done to develop FGMs for sistance of ceramics and the toughness of metals
various applications by using gradients in physical, for structural applications. The gradual composi-
chemical, biochemical, and mechanical properties tional variations from ceramics at one surface to
[2–4]. The main characteristic that distinguishes metals at the other lead to unique advantages of
FGMs from conventional composite materials is smooth transition in thermal stresses along the
the tailoring of graded composition and micro- thickness direction and minimized stress concen-
tration at the interface.
There are several methods such as CVD/PVD,
*
Corresponding author. Tel.: +1-6107584270; fax: +1-
plasma spraying, powder metallurgy and self-
6107586407. propagating high-temperature synthesis (SHS),
E-mail address: wel2@lehigh.edu (W. Liu). which are currently used for producing FGMs.

1359-6462/03/$ - see front matter Ó 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1359-6462(03)00020-4
1338 W. Liu, J.N. DuPont / Scripta Materialia 48 (2003) 1337–1342

CVD/PVD and plasma spraying are generally ap- is designed to automatically adjust the power of the
plied for fabrication of functionally graded coat- laser to maintain a constant surface area of the
ings [3], and the FGM coatings made by plasma molten pool, which is useful for deposition of
spraying are not dense. Although powder metal- variable materials (e.g. FGM deposits) and elimi-
lurgy and SHS processes can be utilized for pro- nating melt pool size variations that can occur due
ducing bulk FGMs, the shapes and sizes are to geometrical changes in the part. The powder
usually limited because of the use of dies for delivering nozzles in the LENS system are arranged
pressure-aided densification. Laser engineered net so that the powder streams converge at the focal
shaping (LENS) is a solid freeform fabrication point of the laser beam. Two powder feeders were
process, which involves laser processing fine pow- used to deliver Ti and TiC powders separately. The
ders into fully dense three-dimensional shapes di- powders were mixed in situ during feeding from the
rectly from a computer-aided design model. The powder feeders to the nozzles, and their feed rates
LENS process is able to fabricate complex proto- were controlled individually by regulating the ro-
types in near-net shape, leading to time and ma- tational speed of each powder feeder. For fabrica-
chining cost savings. A variety of metals and alloys tion of the FGM, the rotational speed for the
have been deposited by the LENS process, such as powder feeder of one material varied from zero to a
H13 steel, 316 stainless steel, nickel-base superal- maximum which was set according to the laser
loys and titanium alloys [5–8]. This process also power and traverse speed used. The rotational
exhibits potential for fabrication of FGMs and speed for the other powder feeder carrying the
structures [5]. In this work, a TiC/Ti ceramic/metal second material varied from a maximum to zero
FGM was fabricated by LENS processing. The stepwise as the number of layers increased. The
microstructure of the FGM was characterized and variation of rotational speed for the powder feed-
the hardness distribution was also evaluated. ing was program controlled, with a minimal step of
0.1 rotations per minute used in the experiment.
The FGM samples had a size of 12:7 mm 
2. Experimental procedures 12:7 mm  20 layers. For comparison, homoge-
neous TiC and TiC/Ti composite (with fixed TiC
The materials used in this work were TiC powder vol%) deposits were also produced. A 420 W laser
(99.9% purity) from Atlantic Equipment Engineers power and an 8.5 mm/s traverse speed were used in
and Ar gas-atomized CP Ti powder (>99.6% pu- this work. Successive layers were deposited with the
rity) obtained from PyroGenesis company. All the bead lines of two adjacent layers at an angle of 90°.
powders have a mesh size of
100/þ325 (particle The layer thickness, hatch spacing, and stand-off
sizes between 45 and 150 lm). A hot-rolled Ti–6Al– distance were set at 0.38, 0.38 and 152.4 mm re-
4V plate of 3.175 mm thickness was used as the spectively. The oxygen level in the glove box was
substrate material, which had a composition of 6.1 kept below 6 ppm during processing. Light optical
Al, 4.3 V (in wt.%). The substrate was ground with microscopy (LOM), scanning electron microscopy
320 grit SiC paper, and then degreased using ace- (SEM) coupled with X-ray energy dispersive spec-
tone and ethanol before deposition. trum (EDS) analysis, and X-ray diffraction (XRD)
An Optomec LENSe 750 system was used in were used for microstructure and phase analysis.
this study. The LENS system consists of a Nd:YAG Microhardness measurements were conducted us-
laser, a four-nozzle coaxial powder feed system, a ing a Vickers indenter under a 300 g load.
controlled environment glove box and a motion
control system. The Nd:YAG laser has a 0.5–1 mm-
diameter circular beam at the focal zone with the 3. Results and discussion
Gaussian intensity distribution and a maximum
output power of 750 W. The LENS system is Fig. 1 shows the results of XRD analyses con-
equipped with a melt pool sensor (MPS) subsystem ducted on the horizontal surfaces of the bottom
to provide closed-loop control. The MPS subsystem and top layers and on the vertical cross-section of
 W. Liu, J.N. DuPont / Scripta Materialia 48 (2003) 1337–1342 1339

the FGM deposit, respectively. The results indicate The laser absorption coefficient (a) of a material
that the LENS FGM deposit contains a-Ti (hcp) is a function of temperature, its electrical resistivity
and TiC (B1 NaCl type). The bottom layer con- and the laserÕs wavelength [9]. The larger the
sists essentially of a-Ti with a very small amount of electrical resistivity of a material, the higher its
TiC while the top layer is mostly TiC with a small laser absorption coefficient. The values of electrical
amount of a-Ti. Fig. 2(a) shows a cross-sectional resistivity for TiC and Ti at room temperature are
LOM photomicrograph of the FGM deposit. A 138–188 lX cm [10] and 42–55 lX cm [11], re-
crack-free and dense TiC/Ti functionally graded spectively. Therefore, the TiC powder particles
composite was fabricated. Fig. 2(b)–(g) show SEM have a higher laser absorption coefficient. In ad-
photomicrographs of the microstructures with in- dition, the heat conductivity of TiC is lower. As a
creasing TiC contents in different locations of the result, partial melting of the TiC powder, in spite
FGM deposit. EDS analysis of the unmelted TiC of its high melting point, would occur at the pe-
particles, the matrix and dendritic phases indicated riphery of the particles. Moreover, dissolution of
that carbon peaks appear in the unmelted TiC and TiC particles into the molten Ti is also expected
the dendritic phase. These results confirm that the during LENS processing. Consequently, the mel-
dendritic phase is resolidified primary TiC. In ad- ted/dissolved TiC would resolidify during the
dition to the dendritic shape, a small amount of cooling process. The different morphologies of the
much finer equiaxed TiC particles can also be ob- resolidified TiC phase can be interpreted according
served in the microstructure (Fig. 2(b)). The un- to the solidification process. At lower TiC contents
melted TiC particles are in a large blocky shape in the FGM deposit, very few large, blocky un-
(Fig. 2(e)). It can be seen from Fig. 2 that the melted TiC particles were observed. This indicates
microstructure of the LENS FGM gradually that most of the injected TiC particles were melted/
changes from pure Ti to approximately 95 vol% dissolved (Fig. 2(b)–(d)). According to the binary
TiC with the variation in composition. Ti–C phase diagram [12], C concentrations from
approximately 0.5 to 16 wt.% C will form primary
TiC during solidification. When the temperature
decreased to the eutectic temperature (1648 °C),
TiC formed in equiaxed shape in the eutectic
(consisting of TiC and b-Ti). As the content of TiC
in the injected powder mixture increased, the
amount of unmelted/undissolved TiC increased in
the melted pool. The resultant microstructure
consists of resolidified TiC/Ti distributed in the
network of unmelted TiC (Fig. 2(e) and (f)). Fi-
nally, when the content of Ti in the injected pow-
der mixture decreased to a minimum (5 vol%),
the unmelted TiC particles appear to be bonded to
each other by the resolidified TiC particles, with
the minimum Ti phase distributed in the inter-
particle boundaries (Fig. 2(g)).
It is known that TiC has an fcc lattice structure
in which the C atoms reside inside the octahedral
interstices. According to the Ti–C phase diagram
[12], TiC has an extraordinarily wide range of
composition (from approximately 32 to 49 at.% C)
Fig. 1. XRD patterns obtained from the different locations in
depending on the degree of carbon vacancies.
the FGM deposit: (a) first layer; (b) cross-section; and (c) last From the XRD data of a Ti–10vol%TiC com-
layer. posite deposit free of unmelted TiC particles, the
1340 W. Liu, J.N. DuPont / Scripta Materialia 48 (2003) 1337–1342

Fig. 2. Microstructures of the FGM deposit: (a) LOM photomicrograph of the deposit; (b)–(g) SEM photomicrographs with increasing
TiC contents in different locations (UMC and RSC denote unmelted and resolidified TiC carbide respectively).

lattice parameter of the resolidified TiC is mea- fabricated by the LENS process. By comparison,
sured to be 4.2975 A  from the TiC (3 1 1) diffrac- an attempt to directly deposit eight layers of 100%
tive peak. The stoichiometric TiC has a lattice TiC onto the Ti–6Al–4V substrate resulted in large
parameter of 4.3278 A  [13]. The lattice parameters vertical cracks throughout the deposit and small
for TiC0:75 and TiC0:55 have been determined to be transverse cracks near the substrate (Fig. 3(a)). In
4.3122 and 4.2832 A  respectively [14]. Therefore, another homogeneous Ti–80vol%TiC composite
the resolidified TiC in the LENS deposit is non- deposit, a long transverse crack was observed near
stoichiometric, with its composition estimated to the deposit/substrate interface (Fig. 3(b)). The
be TiC0:65 through interpolation by assuming a crack was found to originate near the interface as
linear relationship in the composition range be- shown schematically in Fig. 3(c). It is believed that
tween TiC0:75 and TiC0:55 . these cracks resulted from a high level of combined
It is interesting to note that crack-free FGM processing-generated thermal stresses and interfa-
deposits with TiC contents up to 95 vol% were cial mismatch stresses. In brittle materials, relief of
 W. Liu, J.N. DuPont / Scripta Materialia 48 (2003) 1337–1342 1341

Fig. 3. Cracks observed in the homogeneous deposits: (a) full TiC deposit; (b) Ti–80vol%TiC composite deposit; (c) a schematic
showing the originating position of the crack in the composite deposit.

thermal stresses can generally only occur in the properties can also be tailored by the design of
form of cracking, whereas in ductile materials the compositional profiles via controlling the feed
stress relief can be accomplished by plastic defor- rates of the constituent materials and dilutions
mation. In the FGM deposit, both kinds of stres- between the layers. Future study in these aspects is
ses can be significantly reduced and the ductility needed.
can be improved by the gradual compositional
variations, and cracking can therefore be avoided.
Fig. 4 shows the Vickers microhardness distri- 4. Conclusions
bution of the FGM deposit along the thickness
direction. The hardness in the deposit increases A functionally graded TiC/Ti composite mate-
from about 200 Vickers hardness number (VHN) rial was successfully fabricated by LENS process-
at the Ti side to approximately 2300 VHN at the ing, with the composition changing from pure Ti
top layer as the TiC content increases. The non- to approximately 95 vol% TiC. In comparison to
linear variation of hardness might be due to the homogeneous composite deposits of high TiC
fact that the resolidified non-stoichiometric TiCx contents, the FGM fabrication effectively prevents
has a lower hardness value than the unmelted TiC. the formation of cracks. With the ease of deliver-
In spite of the non-linear distribution, the hardness ing the constituent materials and available process
exhibits a gradual and continuous variation in the control, the LENS process can be used for the
FGM. The distribution of hardness and other fabrication of FGMs.

Acknowledgements

The authors gratefully acknowledge support of

this work by the National Science Foundation
through a PECASE Award, grant no. DMI
9983968, made through the Division of Manufac-
turing and Industrial Innovation of NSF.

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