Journal of Nuclear and Related Technology Vol.

4, Special Edition 2007, 233-241

PRODUCTION OF TITANIUM CARBIDE BY THERMAL EXPLOSION

AND TIC/TI FUNCTIONALLY GRADED MATERIALS (FGMS)

R. Rahbari 1, R. Yahya2, M. Hamdi3, O. Farhudi 3 , M. Asmalina2, Z. Marzuki4

1
Department of Electrical Engineering, University of Malaya, 50603 Kuala Lumpur,
Malaysia.
2
Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia.
3
Department of Engineering Design and Manufacturing, University of Malaya, 50603
Kuala Lumpur, Malaysia.
4
Department of Physics, University of Malaya, 50603 Kuala Lumpur, Malaysia.

ABSTRACT
Self-propagating high-temperature synthesis (SHS) of powder compacts is a novel processing
technique being developed as a route for the production of engineering ceramics and other
advanced materials. The process, which is also referred to as combustion synthesis, provides
energy- and cost-saving advantages over the more conventional processing routes for these
materials. In the case of titanium or titanium alloy materials, prior researches employed powder
metallurgy technology for preparing metal matrix composites, MMCs and laminated structures
through the use of fine powders of an inert phase or phases (TiC, TiN, TiB and TiB2) dispersed in Ti
B

or Ti alloy powders. The present research relates to manufacture of titanium-ceramic composites

that are synthesized by combustion synthesis (SHS) and retains a multilayered composite
microstructure comprising one or more titanium-based layers and one ceramic titanium carbide
layers.

Keywords: Self-propagating high-temperature synthesis, metal matrix composites, powder

metallurgy

INTRODUCTION
Self-propagating high-temperature synthesis (SHS) of powder compacts is a novel processing
technique being developed as a route for the production of engineering ceramics and other advanced
materials. The process, which is also referred to as combustion synthesis, provides energy- and cost-
saving advantages over the more conventional processing routes for these materials. These kind of
high-temperature reactions can combine metals and non-metals to produce a wide variety of
advanced materials like ceramics, intermetallics, solid solutions and metal-matrix composites. In
many cases, these novel materials have very unique mechanical, physical, and chemical properties
(H. C. Yi and J. J. Moore, 1990).
In general, in the case of titanium or titanium alloy materials, prior researches employed powder
metallurgy technology for preparing metal matrix composites, MMCs and laminated structures
through the use of fine powders of an inert phase or phases (TiC, TiN, TiB and TiB2) dispersed in
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Ti or Ti alloy powders. These powders are thoroughly mixed and consolidated into a green body by
cold-compaction within a rigid die or by cold isostatic pressing within a flexible elastomer. The
green body is densified by sintering and canning followed by hot isostatic pressing. Densification of
the green body may also be accomplished by sintering to a state of non-connected porosity followed
by hot isostatic pressing (Abkowitz et al., 1988).
A limitation of the powder metallurgy art is the high pressures required for densification, and since
pressure tends to improve densification, the process often operates at the pressure limit of the
apparatus being used (Oden et al., 1993).
A further need exists in the art of preparing titanium composite materials whereby the provision of a
pressure-reaction synthesis (PRS) process will require short reaction times of about 5 to 30 minutes
in order to avoid excessive diffusional interaction (diffusional leveling) between components within
the MMC or PRS bonding layer (Oden et al., 1993).
A variety of refractory ceramic materials including nitrides, nitride-oxide and carbide-oxide
composites have been produced by combustion synthesis of powder compacts. The process uses
heat evolved during spontaneous chemical reactions between mixtures of solids, solids and liquids
or solids and gases. The heat produced as a combustion wave initiated by an ignition source rapidly
propagates through the compact. The key to self-propagating high temperature synthesis (SHS) is
that once initiated, highly exothermic reactions will become self-sustaining and will propagate
through the reactant mixture in the form of a combustion wave. As the combustion wave (front)
advances, the reactants are converted to products. A major advantage of SHS as a process for the
synthesis of materials is the energy savings associated with the use of self-sustaining reactions.
A combination of combustion synthesis and molten metal infiltration has been used to make
materials such as ceramic-metal composites (cermets). Solid-gas, solid-solid and solid-liquid
reactions of a powder compact produce a porous ceramic body which is infiltrated by molten metal
to produce a composite body of higher density (Holt et al., 1991).
The present research relates to manufacture of titanium-ceramic composites that are synthesized by
combustion synthesis (SHS) and retains a multilayered composite microstructure comprising one or
more titanium-based layers and one ceramic titanium carbide layers. This work is a continuation of
our previous work whereby SHS-pressing was also employed to produce Functionally Graded
Targets (FGTs) (E.A. Levashov et al., 2000).
The objectives of this research are to synthesize titanium carbide by combustion synthesis (SHS) in
thermal explosion mode (sample A- Table1) and to study the possibility of production of
functionally graded Ti/TiC material in this mode (Samples B and C - Table 1).

MATERIALS AND EXPERIMENTAL METHOD

Preparation of metal/ceramic particular articles of titanium/titanium carbide (Ti/TiC)

High purity powders of Ti ( 150 m) and graphite (50 m) were mixed in ball mill for 6 hours
with the ratio of masses Mpowders : Mballs of 1:5. The mono- and multi-layered briquettes based on Ti
and Ti + C mixture have been prepared to form the porous mixture compact. The diameter of all the
samples was about 20 mm.

Table 1 below shows the three samples characteristics and the goal of their investigations.

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Table 1 - Sample A, B, and C specifications and the goal of their investigations

SAMPLE DESCRIPTION
A Mono-layered briquette of (Ti + C) mixture;
Goal: production of titanium carbide by combustion synthesis(SHS)

B Two layer briquette comprising rich metallic (Ti) and rich carbide particulate
(Ti + C) mixture layers;
Goal: studying the infiltration of molten Ti from the metallic zone to the carbide zone;

C Three layer briquette comprising carbide particulate mixture between two Ti metallic
layers;
Goal: studying the possible differences of unfiltered Ti from both sides

Characterization of metal/ceramic articles of titanium/titanium carbide (Ti/TiC)

Powdered samples synthesized were characterized by X-ray diffraction (XRD) for compositional
and phase analyses and scanning electron microscopy (SEM) for microstructure and morphological
information.

RESULTS AND DISCUSSION

The major disadvantage of combustion synthesis is that the product formed is a very porous (about
50% dense) and tightly bonded solid, or a powder. The porous solid may be useful as formed, or can
be easily attrited into a powder. It is generally difficult to form a fully dense product by combustion
synthesis. Typically the combustion process is carried out with the simultaneous application of high
external mechanical pressure. Pressure techniques include uniaxial rams, explosive compaction,
isostatic pressing, and application of shock waves generated by gas guns. However, in this
experiment no external pressure after the synthesis was employed.
In the first step, mono-layer carbide mixture (sample A) has been synthesized in air up to 1050C
(C.R. Bowen, B. Derby, 1997). Although, compositional analysis detects only the phase of titanium
oxide (Rutile) on the surface, XRD results show another two phases under the oxide layer. Free
graphite and titanium carbide along with the oxide phase in the composition have been detected
(Table 2). This shows oxidation of titanium has occurred in the whole body of the sample, and most
predominately on the surface.
The results of compositional analysis (XRD) of the products which were synthesized under inert gas
(Ar) show effective prevention of oxidation. Thus, titanium carbide has been formed successfully
by thermal explosion of elements (titanium and graphite). In the metallic rich layer of samples B
and C, the oxide phase has not been detected, although the carbide phase existed.
The formation of the oxide phase in a small amount in the carbide sub-layer is due to the trapped air
in the pores. This indicates that at high temperature, the trapped air must have reacted with titanium
before formation of carbide phase.
The results of XRD show the ratio of C/Ti in the carbide phase is not the same in different zones
and samples (Fig. 7 and 8). The carbide phases Ti 5.73 C 3.72 and Ti8C5 have been detected in samples
B and C, respectively. The parameter in TiC is = 0.6-0.7 in all the cases. It means
concentration of titanium in the reaction with graphite is different. It possibly confirms the
penetration of titanium from the metallic rich zone to the carbide zone.

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Table 2- The phases detected by XRD in different zones of the samples A, B, and C
Sample zone Ti Graphite Titanium Titanium oxide
(C) carbide
Sample A ( on the surface) - - - +
Sample A ( under the surface) - + + +
Sample B (metallic zone + - + -
layer) (At the (At the center)
edge)
Sample B (Carbide zone - - + +
layer) (very less than
A)
C (metallic zone layer) + - + -
(At the (At the center)
edge)
C (carbide zone layer) + - + +
(very less than
A)

The second step of investigation is to study the possibility of production of the metallic/ceramic
functionally graded materials (FGMs) based on Ti/TiC. It includes reasons why we took certain
measurements to reduce the temperature gradient. Therefore, the microstructures of different zones
and layers of the samples have been studied by SEM. Increasing the holding time at high
temperature throughout the sample helps to complete the progress of reaction and infiltration.
The formation of pores around the body of the cylindrical sample prevents the edge zone to reach to
the highest temperature. Due to high cooling rate at the edges, titanium has not infiltrated into the
sub-layer carbide zone.
Visually, a ring of 1 mm width can be seen at the edge of the surfaces of the both rich metallic sides
(Fig. 1 and 2). Inside the ring the carbide phase has been detected while only titanium phase was
presented at the ring area of the rich metallic zones (Table 2). The depth of the surface increases
toward the center from the edge. The depth difference between outer line of the ring and the center
of the sample (C) at the upper and bottom sides are 1.65 mm and 1.38 mm, respectively. This fact
confirms that titanium infiltrated into the carbide mixture zone in the process from both sides.
Although there no external pressures have been exerted during the process, molten titanium rose up
and penetrated to the upper carbide zone against gravity.
The melting point of Ti is 1941 K and the processing temperature was 1323 K. The adiabatic
temperature of SHS process for the reaction (Ti + C TiC) is 3210 K (E.A. Levashov et al., 1999).
Obviously, the furnace temperature is not enough to melt titanium powders. The heat for melting
the titanium powders has been provided by the exothermic chemical reaction between titanium and
carbon. The final shapes and different depths at the edge and center confirm this fact. On the other
hand, the highest temperature (Tad. = 3210 K) has been achieved in the middle of the carbide
mixture zone. The temperature of the surface of the cylindrical samples is the same as the furnace
temperature (T=1323 30 K). Therefore, a temperature gradient of T= 1887 K existed between
the middle and the surface body of the samples. The heat release of the reaction has heated up the
central part more than the edges. So, the cooling rate on the ring area is much higher than inside it
(central part). Due this fact, different microstructures just beside each other on the surface have
been observed (Fig. 3). The molten titanium powders in the central part had enough time and empty
spaces to penetrate into the carbide zone, but at the edges it has not happened. It is probably due to
the high cooling rate at the edges. The XRD and microstructures results confirm the melting and
infiltration of titanium into the carbide zone too (Table 2 and Fig. 3-5).

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Generally, the microstructures of carbide zone products in all the samples are similar (Fig. 6). The
carbide product features a porous solid that can be attrited easily into a powder, while the rich
metallic layer after processing presents a very condensed and hard material.

Depth
difference

Fig. 1. The photograph of upper metallic layer of sample C after synthesis

Depth
difference

Fig. 2.- The photograph of the bottom metallic layer of sample C after synthesis

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Fig. 3. Effect of temperature gradient on the microstructures of center and edge of metallic layer
after synthesis in sample C

Fig. 4. Microstructure of the edge of the metallic layer after synthesis in sample C

Several researchers have produced substantial improvements in SHS product material densities by
endeavoring to balance the intrinsic and extrinsic causes of porosity by incorporating diluents into a
reaction system that results in a zero or minimum volume change and conducting the reaction in
vacuum (H. P. Li, S. B. Bahaduri and J. A. Sekahar, 1992). However, fully dense materials have not
been obtained using this approach. Materials synthesized by SHS processing may also be densified
with the aid of heat obtained from the SHS reaction coupled with a liquid phase developed during
the reaction and used in a similar way to that of liquid phase sintering of dense sintered products.
During the combustion synthesis of intermetallic compounds, the combustion temperature can
exceed the low melting point of the intermetallic compound product. If the amount of the liquid
phase generated can be controlled using SHS parameters, e.g. diluents, heating rate, green density
etc., it should be possible to apply liquid phase sintering in the combustion synthesis of dense

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Generally, the microstructures of carbide zone products in all the samples are similar (Fig. 6). The
carbide product features a porous solid that can be attrited easily into a powder, while the rich
metallic layer after processing presents a very condensed and hard material.

Depth
difference

Fig. 1. The photograph of upper metallic layer of sample C after synthesis

Depth
difference

Fig. 2.- The photograph of the bottom metallic layer of sample C after synthesis

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Titanium Carbide
60

50
Oxide
40
peaks
Lin (Cps)

30

20

10

5 10 20 30 40 50 60 70 80

2-Theta - Scale
File: JK-Rosiyah-A-TiC.raw - Type: 2Th/Th locked - Start: 5.000 - End: 80.000 - Step: 0.030 - Step time: 2. s - Temp.: 25 C (Room) - Time Started: 5 s - 2-Theta: 5.000 - Theta: 2.500 - Chi: 0.00
Operations: Import
01-077-1089 (C) - Titanium Carbide - Ti5.73C3.72 - Y: 89.29 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 3.06000 - b 3.06000 - c 14.91000 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P31

Fig. 7. XRD of carbide mixture zone after synthesis in sample B

Titanium Carbide
70

60

50
Oxide
peaks
Lin (Cps)

40

30

20

10

5 10 20 30 40 50 60 70 80

2-Theta - Scale
File: JK-Rosiyah-B-TiC.raw - Type: 2Th/Th locked - Start: 5.000 - End: 80.000 - Step: 0.030 - Step time: 2. s - Temp.: 25 C (Room) - Time Started: 13 s - 2-Theta: 5.000 - Theta: 2.500 - Chi: 0.00
Operations: Import
01-072-2496 (C) - Titanium Carbide - Ti8C5 - Y: 95.50 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 6.11500 - b 6.11500 - c 14.90000 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3m

Fig. 8.- XRD of carbide zone after synthesis in sample C

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CONCLUSION
The compositional (XRD) and microstructure (SEM) results of the thermal explosion in Ti-C
system has shown the possibility of the production of FGM materials. Under appropriate
measurements in the process the product of the synthesis can be optimized to produce Ti/TiC FGM.

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Materials, British Ceramic Transactions, v. 96, No. 1.
E.A. Levashov, A.S. Rogachev, V.I. Yukhvid, and I.P. Borovinskaya, (1999), Physico-chemical
and technological Foundations of self-propagating High Temperature synthesis, Binom, Moscow.
E.A. Levashov, R.G. Rahbari, I.V. Shtanskaya, and A.N. Pityulin, Tsevetnye Metally, (2000),
Development of new functional gradient targets based on non-stoichiometric titanium carbide,
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