Materials Science and Engineering A 397 (2005) 92–97

Spark plasma sintering of functionally graded material

in the Ti–TiB2–B system
Haibo Feng ∗ , Qingchang Meng, Yu Zhou, Dechang Jia
School of Materials Science and Engineering, Harbin Institute of Technology, 92 West DaZhi Street, Harbin 150001,
PO Box 433, PR China

Received 1 October 2004; received in revised form 25 January 2005; accepted 3 February 2005

Abstract

A six-layer functionally gradient material (FGM) of Ti–TiB–TiB2 was rapidly fabricated by spark plasma sintering (SPS) in vacuum. Both
B and TiB2 were used and reacted with Ti to synthesize TiB. Adjusting the content ratio of B to TiB2 in individual layers could control the
amount of synthesized TiB by two steps during sintering. The composition and microstructure of the layers in FGM were investigated by
XRD, SEM and TEM. The synthesized TiB has needle-like, agglomerated and elongated morphologies. The content of agglomerated TiB
increased and that of needle shape TiB decreased with increasing the target TiB volume fraction ranging from 20 to 60%. The elongated TiB
was observed in the other two layers with higher target TiB volume fraction, which structure is similar to the agglomerated TiB. The FGM
with Ti on one side to Ti–TiB–TiB2 on the other were fabricated at relative low sintering temperature and short dwelling time by spark plasma
sintering.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Spark plasma sintering; Microstructure; TiB; Functionally gradient materials (FGMs)

1. Introduction known as spark plasma sintering (SPS) has been developed in

A functionally graded materials (FGMs) is a composite
material consisting of two or more phases in which the
volume fractions of the constituents change so that the
composition, microstructure and properties vary gradually
along one direction. Designing FGMs allows manipulation
of many material properties or new functions. Various
production methods are available for manufacturing graded
structures such as casting [1], deposition [2], laser cladding
[3], combustion synthesis [4] and powder metallurgy [5].
Among these, the powder metallurgy technique is applicable
to a wide range of material combinations with a close control
over the graded composition. There is also an increased inter-
est in devising new material systems and versatile methods of
fabrication. An innovative powder densification technology
∗ Corresponding author. Tel.: +86 0451 86418792;
fax: +86 0451 86413922.
E-mail addresses: fenghb@hit.edu.cn (H. Feng), mqch@hit.edu.cn
(Q. Meng), zhouyu@hit.edu.cn (Y. Zhou), dcjia@hit.edu.cn (D. Jia).
recent years. The SPS process is a synthesis and processing
technique which makes it possible to at low temperature and
in a short period by charging the intervals between powder
particles with electrical energy and effectively applying high
temperature spark plasma generated momentarily. The SPS
process is expected to find increasing usage in the fabrication
of FGMs, intermetallic compounds, fiber reinforced ce-
ramics, metal matrix composites, nanocrystalline materials,
which are difficult in sintering by common methods. The
basic configuration of a typical SPS system is shown in
Fig. 1. As a rapid consolidation technique, the SPS process
has many advantages on fabrication of advanced materials
and FGMs [6–8]. Since TiB exhibits extreme hardness, high
melting point, high electrical conductivity, good thermal
shock resistance and chemical inertness [9,10], a FGM with
composition changing from Ti alloy on one side to TiB on the
other side has many potential application fields specifically
in defense [5,11]. The interest in the Ti–TiB system is also
because of the ease of fabrication of the gradation scheme
due to the possibility of in situ processing and the fact that

0921-5093/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.02.003
 H. Feng et al. / Materials Science and Engineering A 397 (2005) 92–97
Fig. 1. The configuration of the SPS system.
TiB forms as whiskers and is very effective in stiffening and
strengthening Ti [12]. This kind of FGM has been fabricated
by hot pressing and combustion synthesis method, but the
earlier fabrication trials of FGMs based on Ti–TiB system
had cracking problems[4,12].
Combustion synthesis offers a fast and cheap method for
producing this FGM. The drawback of the process is in the
case of titanium diboride, it is extremely violent and energetic
leading to less than theoretical density in the product. In or-
der to control the exothermic reaction, diluents were added to
slow the reaction speed. The drawback of diluent addition is
that undesired phases may be present in the final composites.
As we know, both B and TiB2 can react with Ti and synthesize
TiB at different temperatures. In this study, the Ti–TiB2 –B
system was selected to reaction synthesize the FGM. The ad-
dition of TiB2 has two functions during the sintering process:
(1) as a diluent in the composite at low temperature; (2) reacts
with Ti to synthesize TiB at high temperature. No other unde-
sired phase can present in final production since TiB2 is stable
in the Ti–B binary system. Adjusting the content ratio of B
to TiB2 could control the amount of synthesized TiB by two
steps during sintering. And the composites can be densified
rapidly at relatively low temperature. So rapid fabrication of
reaction synthesized FGM in the Ti–TiB2 –B system by SPS
technique was explored and the microstructure of the final
product was investigated.
2. Materials and methods
2.1. Fabrication process
Elemental Ti (74 ␮m, purity >99%), Fe–65 wt.% Mo
(74 ␮m, purity: >99%), B (average size 2 ␮m, purity >95%)
powder and TiB2 (average size 5 ␮m, purity > 99%) pow-
der were used as raw materials. The Ti alloy matrix (Ti–4.0
Fe–7.3 Mo) was synthesized by blended elementals Ti and
FeMo powder. The TiB was synthesized by chemical reac-
tion of Ti with B and TiB2 during the SPSing. Powder mix-
tures with varying target volume fractions of 0, 20, 40, 60,
80 and 100% TiB were blended by planetary ball milling for
93
10 h. Then the FGM were stacked layer by layer in a cylinder
graphite die with an inner diameter of 35 mm. The SPS pro-
cessing was carried out in a vacuum by heating to 1000 ◦ C in
20 min, dwelling 5 min and cooling to the room temperature
in the furnace. The sintering pressure applied was 20 MPa.
The heating rate of sintering is about 50 ◦ C/min. The temper-
ature was measured by means of an optical pyrometer focused
on the graphic die surface. Heating and dwelling of the FGM
sintering was completed in 25 min.
2.2. Composition design of the FGM
In the Ti–TiB2 –B system, chemical reactions may take
place during the heating of the powder compact shown as
follows:
Ti + B = TiB (1)
Ti + TiB2 = 2TiB (2)
Ti + 2B = TiB2 (3)
The Gibbs free energy
G of reaction formation of reactions
Eqs. (1)–(3) have been calculated using the thermodynamic
data [13]. And the thermodynamic data curves for these re-
actions along with curves plotted elsewhere [14,15]. The
G
values of three reactions are all negative, which indicates that
all the above reactions can take place. Although the
G of
reaction (3) is the most negative, Ti and TiB2 can further re-
act to form TiB due to the small negativity of the free energy
of reaction (2). This means that the TiB2 will eventually be
converted to TiB as long as the average B concentration in the
reaction zone is less than 18–18.5 wt.% In theory, only TiB
can be synthesized when B concentration is less than 18 wt.%
in the composites.
Diffraction thermal analysis (DTA) results of Ti–B and
Ti–TiB2 milled mixture powders are shown in Fig. 2. The
both reactions are exothermic. It demonstrates that reaction
(1) occurs below 900 ◦ C, while reaction (2) does not occur
below 1000 ◦ C. The temperature difference between the two
chemical reactions makes it possible to synthesize in situ
TiB by a two-step sintering method. Because of its higher
thermodynamic stability, TiB2 phase is likely generated in the
layers with a high amount of boron. While in situ chemical
Fig. 2. DTA curves of reaction (1) and (2).
94 H. Feng et al. / Materials Science and Engineering A 397 (2005) 92–97
Table 1
Designed TiB volume fraction by different reaction in layers
Layer code Target volume Volume fraction of TiB (%)
fraction of TiB (%)
Synthesized Synthesized
by reaction (1) by reaction (2)
Layer 1 0 0 0
Layer 2 20 0 20
Layer 3 40 20 20
Layer 4 60 30 30
Layer 5 80 40 40
Layer 6 100 50 50
reactions (1) and (2) are expected in the layers with a low
amount of boron. In this research, both B and TiB2 were
used and reacted with Ti to synthesized TiB. And the volume
fraction of synthesized TiB in the composites below 900 ◦ C
during the sintering process can be controlled by adjusting
the content ratio of B to TiB2 . At a higher temperature, the
in situ TiB be synthesized between Ti and TiB2 by reaction
(2). So, the TiB2 is diluent at low temperature and reactant at
high temperature during the sintering.
Moreover, the densification process of composites will be
more difficult with the increasing of TiB volume fraction.
So the densification process of each layer must be consid-
ered. Similar densification properties of different layers are
favorable factor of the FGM fabrication. Target TiB volume
fraction by different reaction is shown in Table 1 and the
layer codes are used in the following discussion. Taken into
account the different reaction temperature of the two reac-
tions, both B and TiB2 were used in layers of 40, 60, 80 and
100% TiB volume fraction. In these layers, the synthesis of
TiB has two steps during the sintering: reaction (1) occurs
when the sintering temperature is low; reaction (2) occurs at
high temperature. In the layers of 20 vol.% TiB, only reac-
tion (2) is expected to occur at high sintering temperature.
Although the holding time at high temperature is only a few
minutes, mass TiB is synthesized. So the growth process of
TiB is restrained at low temperature which will do bene-
fit to densification process. The reaction heating of the first
step is advantageous to induce the second and to sinter the
composites at relatively low temperature. As a contrast, the
FGM of these corresponding layers only containing B powder
was sintered. The target 100 vol.% TiB layer is porous and a
crack passed though several layers which confirmed that the
two-step reaction synthesis of TiB is advantageous for the
consolidation process of the Ti–TiB–TiB2 system FGM.
3. Results and discussion
The phase constitution was analyzed by XRD with Cu K␣
radiation. The interfaces and surfaces of the functionally
graded composite sample were examined using SEM. The
compositionally graded layers of the FGM resulted in a well-
bonded composite structure. No significant shape change or
cracks were detected in the cross section of the FGM, which
Fig. 3. XRD spectra of different layers in the SPSed.
confirms that the design of the two-step sintering method is
feasible.
3.1. X-ray diffraction analysis
The sample was cross-sectioned and graded layers were
cut through the interface boundaries. For phase identification,
XRD was utilized on each layer. XRD spectra from individual
layers of the FGM after being SPSed are shown in Fig. 3. The
Ti matrix consists of mass ␤-Ti phase and small amount of
residual ␣-Ti phase in these layers. Fe and Mo elements are ␤-
Ti stabilizing elements, which diffused into titanium and re-
sulted in ␤ phase’s forming during the sintering process. The
sintering process was short (less than 25 min) and the solution
of Fe and Mo was heterogeneous, which lead to the ␣-Ti phase
being remained when cooled to room temperature. The peaks
of TiB presented in the spectrum of layer 2, and the intensities
of TiB peaks increased from layers 2–6. This indicates that the
volume fraction of TiB is increasing. No peaks of TiB2 pre-
sented in the spectra of layers 2–4, indicating that in these lay-
ers chemical reaction (1) and (2) were completed during the
sintering process and only TiB was synthesized as expected.
While, the peaks of TiB2 present in spectra of layer 5 and
layer 6, which indicates that the two layers consisted of syn-
thesized TiB, and TiB2 and small amount of titanium. TiB2
phase is more stable than TiB phase when excess boron exists
(weight percent >32%) in the titanium matrix. So TiB2 phase
was maintained in the composite of layer 5 and layer 6. But
it is unclear that these TiB2 is residuum of original additions
or is reaction synthesized during the sintering process. Thus,
the FGM consists of three kinds of ordinal layers: Ti (layer
1), Ti + TiB (layers 2–4) and Ti + TiB + TiB2 (layers 5 and 6).
3.2. Microstructure
The photograph of the cross section of the sintered FGM is
shown in Fig. 4. It can be seen that uniform layered structure
without porosity and crack has formed in the FGM. No inter-
layer cracks were detected in the cross section of the FGM,
which indicates that a well-bonded composites structure can
 H. Feng et al. / Materials Science and Engineering A 397 (2005) 92–97 95

be achieved by spark plasma sintering in the Ti–TiB2 –B sys-

Fig. 4. Photograph of the cross section of the sintered FGM.
tem FGM. It was reported that the absence of cracking is
possibly due to the addition of ␤ stabilizing elements to the
Ti matrix in these layers [16].
The microstructure of the individual layers were observed
using SEM, as shown in Fig. 5. These figures illustrate
the varied morphologies of individual layers observed in
the FGM. Fig. 5(a) shows the morphology of the layer 1
near the boundary of layer 2. The Ti alloy matrix consisted
of equiaxed ␤-Ti grains. Solution of Fe and Mo elements
into the titanium matrix led to the formation of ␤-Ti phase
during the sintering process. And a small amount of needle
shape TiB whiskers were present along the grain boundaries.
It is because of the diffusion of B element that led to the
degradation of layered structure during the SPS process.
Fig. 5(b) reveals the presence of needle shape TiB whiskers

Fig. 5. Morphologies of individual layer: (a–f) are morphologies of layers from layers 1–6, respectively.
96 H. Feng et al. / Materials Science and Engineering A 397 (2005) 92–97
Fig. 6. SEM image of the agglomerated TiB.
distributed randomly in the titanium matrix. Microstructures
of layers 2–4 are shown in Fig. 5(b)–(d), which show that
two different types of TiB morphologies are observed in
these three layers. One is the randomly distributed needle
shape whisker and the other is a short agglomerated whisker.
In these three layers, the volume proportion of agglomerated
TiB whiskers increased and the size of needle shape TiB
decreased with the increasing of target TiB volume fraction.
In high resolution, these agglomerated TiB were the rod-like
whiskers that appeared to be interconnected, as shown in
Fig. 6, and mass needle shape TiB were observed around
them. Microstructure of layer 5 and layer 6 are shown in
Fig. 5(e) and (f). These two layers consisted of coarse and
elongated TiB particles. And between these elongated TiB
particles, fine and randomly distributed needle shape TiB
were observed as shown in Fig. 7. And the titanium between
the TiB particles was etched. While the microstructure of
the TiB2 phase could not be evaluated using SEM.
As TiB has a B27 structure [17], characterized by zigzag
chains of boron atoms parallel to the b-direction, with each
B atom lying at the center of a trigonal prism of six Ti atoms,
TiB should exhibit much faster growth along b-direction than
a or c direction, which results in the formation of TiB with
needle shape or rod-like morphology. The distribution of B
and TiB2 in the milled particles was heterogeneous and the
Fig. 7. SEM image of needle shape TiB between elongated TiB particles.
Fig. 8. TEM image of elongated TiB in layer 6.
growth of mass agglomerated TiB consumed the titanium ma-
trix, which led to the needle shape TiB became smaller with
the volume increasing of agglomerated TiB. Moreover, the
volume proportion of agglomerated TiB whiskers increased
with the increasing of TiB volume content in the first four
layers, which can be explained as follows: with increasing
content of B and TiB2 particles, the mass of TiB nucleat-
ing and growing simultaneously and the growing up of TiB
were restricted which promoted the formation of agglomer-
ated TiB. The SEM image of the agglomerated TiB at high
magnification is shown in Fig. 6, which identified the agglom-
erated TiB, was composed of much small rod-like TiB. This
is the reason why the content of agglomerated TiB increased
with the increasing of target TiB volume fraction from layers
2–4. The elongated TiB particles of layer 5 and layer 6 were
observed by TEM. The typical morphology of elongated TiB
is shown in Fig. 8. These particles consisted of small rod-like
TiB similar to the structure of agglomerated TiB, but their
size was much smaller than that of agglomerated ones. So
the growth mechanism of agglomerated and elongated TiB is
the same as needle shape TiB. The composition of the com-
posite determines the final product and the morphologies of
synthesized TiB. Similar composition was obtained by self-
propagating high temperature combustion synthesis method
[18,19]. Since the heating and dwelling time was only about
25 min and the sintering temperature was only 1000 ◦ C, the
diffusion rate of B into TiB is very small, many small B-
rich areas were formed during the sintering process which
led to the residual of TiB2 in the matrix. Although there was
residual TiB2 in TiB-rich layers, the spark plasma sintering
is an effective method to fabricate the FGMs in Ti–TiB2 –B
system at relatively low sintering temperature within a short
dwelling time.
 H. Feng et al. / Materials Science and Engineering A 397 (2005) 92–97
4. Conclusions
The Ti–TiB–TiB2 FGM composite has been synthesized
by spark plasma sintering (SPS). The FGM consisted of three
kinds of ordinal layers: Ti, Ti + TiB and Ti + TiB + TiB2 . The
chemical reaction between B, TiB2 and Ti was completed
when the target volume fraction of TiB was less than 60%.
In these layers, the synthesized TiB were needle shape and
short agglomerated whiskers, and the volume proportion of
agglomerated TiB whiskers increased and the size of the nee-
dle shape TiB decreased with the increasing of target TiB vol-
ume fraction. In the last two TiB-rich layers, the elongated
TiB was observed with a structure which is similar to that
of agglomerated TiB. The growth mechanism of agglomer-
ated and elongated TiB is the same as the needle shape TiB.
The FGM in Ti–TiB2 –B system can be fabricated at rela-
tively low sintering temperature and in short dwelling time
by spark plasma sintering. Ball milling accompanied with
spark plasma sintering can provide a powerful and rapid fab-
rication method for the FGMs with high performance.
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