MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1

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Characterisation of titanium–titanium boride composites

processed by powder metallurgy techniques

M. Selva Kumara,⁎, P. Chandrasekarb , P. Chandramohanb , M. Mohanrajc

a
Department of Mechanical Engineering, Dr. Mahalingam College of Engineering and Technology, Pollachi-642003, India
b
School of Engineering, Professional Group of Institutions, Coimbatore-641662, India
c
Department of Mechanical Engineering, Info Institute of Engineering, Coimbatore-641107, India

AR TIC LE D ATA ABSTR ACT

Article history: In this work, a detailed characterisation of titanium–titanium boride composites processed
Received 8 November 2011 by three powder metallurgy techniques, namely, hot isostatic pressing, spark plasma
Received in revised form 5 July 2012 sintering and vacuum sintering, was conducted. Two composites with different volume
Accepted 20 July 2012 percents of titanium boride reinforcement were used for the investigation. One was
titanium with 20% titanium boride, and the other was titanium with 40% titanium boride
Keywords: (by volume). Characterisation was performed using X-ray diffraction, electron probe micro
Titanium–titanium analysis — energy dispersive spectroscopy and wavelength dispersive spectroscopy, image
boride composites analysis and scanning electron microscopy. The characterisation results confirm the
Hot isostatic pressing completion of the titanium boride reaction. The results reveal the presence of titanium
Spark plasma sintering boride reinforcement in different morphologies such as needle-shaped whiskers, short
Vacuum sintering agglomerated whiskers and fine plates. The paper also discusses how mechanical
properties such as microhardness, elastic modulus and Poisson's ratio are influenced
by the processing techniques as well as the volume fraction of the titanium boride
reinforcement.
© 2012 Elsevier Inc. All rights reserved.

1. Introduction [2,3]. Titanium-based composites possess several advantageous

Components used in many engineering applications, especially
in the aerospace and automobile industries and defence, are
required to meet certain property requirements, such as possess
a certain specific strength, elastic modulus, toughness, etc. [1].
Conventional metallic materials rarely meet such requirements.
However, recent advancements in the field of metal matrix
composites have overcome this difficulty, and many metal
matrix composites developed in recent years have the charac-
teristics to meet various combinations of property require-
ments. Titanium-based composites constitute an important
group of such metal matrix composites. Though titanium-based
composites are mostly used for aerospace applications, they are
finding increasing use in other applications such as in the
fabrication of automotive components and consumer utilities
properties such as high specific modulus, high specific strength,
good corrosion resistance and good wear resistance [4–7].
Various reinforcements are used in titanium-based composites.
The incorporation of reinforcements such as SiC, Al2O3 and B4C
leads to the formation of undesirable reaction products, which
act as major barriers to the development of viable titanium
composites. However, titanium boride (TiB) is well suited for use
as reinforcement due to the absence of any intermediate phase
between Ti and TiB [8–10]. Moreover, TiB reinforcement has
certain desirable characteristics such as high elastic modulus,
good thermal stability at high temperature and a density nearly
equal to that of titanium [11].
Many research studies on the processing of Ti–TiB compos-
ites using many techniques such as solidification, rapid solidi-
fication [12–14], combustion synthesis [15] and laser cladding [16]

⁎ Corresponding author. Tel.: +91 9865930803.

E-mail address: sel_mcet@yahoo.co.in (M. Selva Kumar).

1044-5803/$ – see front matter © 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.matchar.2012.07.014
44 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1
have been reported. In all of these techniques, TiB reinforcement
is developed either by an in situ method or by the addition of
ceramic particles of TiB. Fibre-reinforced composites involve the
addition of costly fibres and intricate processing steps [9].
However, in situ composites are created using simpler fabrica-
tion steps and hence are more cost effective than fibre-
reinforced composites. Additionally, in situ titanium matrix
composites overcome the shortcomings associated with the
casting process, such as the pollution of reinforcements and the
wettability between ceramic particles and a matrix [17]. Consid-
erable research studies have also been carried out to understand
the mechanical properties of Ti–TiB composites [18–23]. With
respect to mechanical properties, hardness and the elastic
properties of Ti–TiB composites are of great interest due to the
higher modulus of TiB relative to that of Ti.
A review of the available literature reveals that no significant
work has been reported on Ti–TiB composites processed by
powder metallurgical techniques such as Hot Isostatic Pressing
(HIP), Spark Plasma Sintering (SPS) and vacuum sintering. Hence,
the main objective of this work was to process a high-density Ti–
TiB composites (aiming 20 and 40 volume percentage (vol.%) TiB)
using the above-mentioned powder metallurgical techniques.
The processed composites were characterised by X-ray diffrac-
tion (XRD), Electron Probe Micro Analysis (EPMA)-Energy Dispers-
ing Spectroscopy (EDS) and Wavelength Dispersing Spectroscopy
(WDS), optical microscopy (with an image analyser) and
scanning electron microscopy (SEM) techniques. In addi-
tion, the mechanical properties of the composites, including
microhardness, elastic moduli, shear moduli and Poisson's ratio
were measured.
2. Materials
The elemental powders used in this work were Ti (325 mesh,
99.5%) and TiB2 (325 mesh) and Ferro Molybdenum FeMo
(β stabilisers). The mixture was used to produce a composite
containing a 0.2 and 0.4 volume fraction of TiB according to the
following reaction:
Ti þ TiB2 →2TiB
Table 1 illustrates the target volume percentage and the
composition of the mixture in weight percentage. The first
step of the process consisted of the mechanical mixing of
elemental powders (Ti, TiB2 and FeMo). β-stabilising elements
(FeMo) were added to increase the fraction of the β phase in
the matrix, which is more ductile than the α phase. Powders
were prepared under vacuum to reduce the oxidation process.
Mechanical alloying was performed in a dry ball mill for
approximately 20 h. The weight ratio of stainless steel balls to
Table 1 – Compositions of Ti–TiB composites.
Target vol pct of TiB Composition of mixture
(wt. pct)
Ti TiB2 FeMo
20 78 6 16
40 70 15 15
powder was 10:1 during the mixing process. The as-milled
powder was preserved in the vacuum atmosphere for the
processing of the Ti–TiB composites.
3. Approach
The main drawback associated with the liquid route is the
high cost of material. This difficulty was overcome by
processing the composites through powder metallurgy tech-
niques (via in situ preparation). In earlier research studies,
rapid solidification and combustion synthesis were employed
to process Ti–TiB composites [9,23]. In this work, in situ Ti
composites (aiming 20 and 40 vol.% TiB) were processed by
HIP, SPS and vacuum sintering.
3.1. Material Processing Techniques
3.1.1. Hot Isostatic Pressing (HIP)
In the HIP process, a powder mixture is subjected to an
elevated temperature and pressure to eliminate internal
micro shrinkage. During the manufacturing process carried
out in this study, a powder mixture was placed in a container
(typically steel can) and maintained at a temperature of
1200 °C and at a pressure of 120 MPa under a high-vacuum
atmosphere (approximately 10− 6 m bar) for approximately 5 h
to remove air and moisture from the mixture. Then, the
container was sealed and pressed using HIP. The circulation of
inert gas at high pressure and temperature resulted in the
removal of internal voids and created a strong metallurgical
bond throughout the material. This produced a clean and
homogeneous material with nearly 100% density.
3.1.2. Spark Plasma Sintering (SPS)
Spark plasma sintering is a newly developed consolidation
technique that enables a composite powder to be fully
densified at a relatively low temperature and short time
(10–15 min) [24–27].
During the SPS process carried out in this study (at the
International Research Center for Advanced Newer Materials —
ð1Þ ARCI, Hyderabad, India), the as-milled powders were placed in a
graphite die and then pressed uniaxially at 20 MPa, and a direct
current pulse voltage was applied. The powders were heated by
spark discharge between the particles. The graphite die was
heated from both inside and outside. Hence, rapid heating
occurred and the sintering time was reduced. The sintering
temperature was maintained at approximately 1100 °C, with a
holding time of 5 min. Therefore, consolidation occurred rapidly
at a relatively low temperature, resulting in control over grain
structure and microstructure.
3.1.3. Vacuum Sintering
The milled composite powder was compacted in a Universal
Testing Machine (UTM-100 t) under a load of 350 kN. Then,
cylindrical green composite powder billets were consolidated by
sintering in a vacuum furnace (processed at Non-Ferrous
Technology Development Center — NFTDC, Hyderabad, India)
maintained at approximately 1200 °C for approximately 5 h. TiB2
reacted with the Ti powder and transformed into TiB during
sintering.
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1 45

3.2. Characterisation
4. Results and Discussion
Small cylindrical samples were cut from the sintered Ti–TiB
composites by electrical discharge machining. The densities of The microstructural characterisation and the mechanical prop-
the Ti–TiB composites were measured by the Archimedes erties of the Ti–TiB composites (processed by HIP, SPS and
method (water immersion method). These densities were vacuum sintering) are discussed in this section.
compared to the theoretical density values calculated using
the volumetric rule of mixtures (shown in Table 2). The samples 4.1. Estimation of TiB Volume Fraction Through Image
were etched with Kroll's reagent. The microstructures of the Analyser Technique
composites were observed using an optical microscope with an
image analyser (Envision 3.0 software) attachment and a The volume fraction of TiB phases measured by an image
Scanning Electron Microscope (HITACHI S-3000 H). The identi- analyser with acceptable accuracy [12] is shown in Table 3.
fication of Ti and TiB phases present in the composites after Through this method, the TiB phases were identified and their
sintering were confirmed by XRD (Rigaku Ultima, model-IIIX- volume percentages were estimated using an image analyser
Ray Diffractometer, CuKα radiation, λ = 1.540598 A°) and EPMA attached to an optical microscope. All dark boride phases in
(EDS and WDS) techniques (JOEL JXA-8530F Electron Probe Micro the matrix were identified, and their volumes in all of the
Analyzer). Moreover, the Vickers hardness of the specimen was composites were estimated after a few iterations. TiB was
measured using a Mitutoya microhardness tester at a load of determined to be the predominant boride phase. The average
300 g for a dwell time of 15 s. The Young's modulus, shear value of the resulting volume fraction of TiB is presented in
modulus and Poisson's ratio were determined from the Table 3.
longitudinal and transverse velocity of ultrasonic waves As shown in Table 3, the estimated TiB volume percentages of
propagating through the material. all of the composites processed using the three techniques (HIP,
SPS and vacuum sintering) agreed reasonably well with another,
3.3. Estimation of Elastic Properties Through Ultrasonic revealing the target volume percentage with acceptable de-
Technique viations. The HIP and SPS processes yielded highly dense sintered
composites whose densities are closer to the theoretical densities
The velocity of ultrasonic waves in a solid medium is directly and also closer to the target volume percentage of TiB (as shown
related to the elastic properties and density of the material. in Table 2). However, the composites fabricated by vacuum
The velocity of ultrasonic waves in materials is generally sintering show some marginal differences in density and TiB
obtained from the time of flight of ultrasonic waves through a volume fraction from the theoretical values as shown in Table 2.
known thickness of the sample. Hence, the elastic modulus of
a material measured by the ultrasonic technique is a good 4.2. Microstructure
representative bulk material property [28,29]. The relation-
ships between ultrasonic velocity and the elastic properties of The composites were investigated by X-ray diffractometry,
materials are presented below: SEM (SEI mode) and EPMA to reveal the morphology of the TiB
fabricated in situ in a Ti matrix.
3V2L −4V2T
E ¼ ρV2L ð2Þ
V2L −V2T 4.2.1. X-ray Diffraction Technique
XRD analysis was carried out on metallographically polished
G ¼ ρV2T ð3Þ composite specimens. The XRD patterns of the composites
processed using the three different powder metallurgical


VL 2 techniques (HIP, SPS and vacuum sintering) are shown in
−2
V Fig. 1a and b. The diffractogram confirms the completion of
ν ¼ "
T 2 #
VL the chemical reaction. The patterns of all of the composites
2 −1
VT ð4Þ show the presence of β Ti and α Ti peaks, suggesting that the
matrix contains both β and α phases. It is ascertained that the
V L −longitudinal velocity; V T −transverse velocity;
addition of β-stabilising agents (FeMo) resulted in a β Ti
ρ−density of the samples; ν−Poisson0 s ratio; G−shear modulus;
matrix. The patterns also reveal that there is no existence of
E−Young0 s modulus:
Ti3B4, which is a possible intermediate phase in the matrix
[9,27]. The observation also confirms the transformation of
Table 2 – Density of Ti–TiB composites. TiB2 particles into TiB in the resultant matrix.
Technique Composite Theoretical Measured Density
density density %
g/cm3 g/cm3 Table 3 – Actual Vol pct of TiB.
Target vol Composition of Estimated vol pct of TiB
SPS Ti-24% TiB 4.963 4.90 98.73
pct of TiB mixture (wt. pct)
Ti-38.5% TiB 4.933 4.75 96.29
HIP Ti-20.6% TiB 4.963 4.92 99.12 Ti TiB2 FeMo SPS HIP Vacuum sintering
Ti-38.3% TiB 4.933 4.9 99.33
Vacuum Ti-17.6% TiB 4.963 4.2 84.62 20 78 6 16 24 20.6 17.6
Sintering Ti-37.9% TiB 4.933 4.685 94.97 40 70 15 15 38.5 38.3 37.9
46 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1
Fig. 1 – XRD Pattern of Ti–TiB composite. (a) Vacuum
sintering — Ti-17.6 vol.% TiB, HIP — Ti-20.6 vol.% TiB,
SPS — Ti-24 vol.% TiB. (b) Vacuum sintering — Ti-37.9 vol.%
TiB, HIP — Ti-38.3 vol.% TiB, SPS — Ti-38.5 vol.% TiB.
The XRD pattern of the composites processed through
vacuum sintering (Fig. 1a) shows a few TiB2 peaks. The presence
of TiB2 (001) and (002) peaks at 2θ =27.64° and 57.36°, respectively,
in the composites (17.6 and 37.9 vol.% TiB) are observed. This
indicates the slow diffusion of boron atoms in TiB, which is
similar to the result reported in an earlier reported study [12]. In
the composites (both 17.6 and 37.9 vol.% TiB), the dominant
TiB (112), (111) and (201) peaks at 2θ = 52.44°, 37.62° and 34.7°,
respectively, are observed. It is evident from the pattern
(shown in Fig. 1a and b) that the peak corresponding to TiB
increases with the volume fraction of TiB. Additionally, the
intensity of the TiB peaks in the 37.9 vol.% TiB composite is
quite higher than that of the peaks in the composite containing
17.6 vol.% TiB. The pattern also reveals the presence of Ti (101)
and β Ti (211) at 2θ = 39.74° and 70.16°, respectively, in the
composites containing 17.6 and 37.9 vol.% TiB. Moreover, there
is evidence of FeMo, with a small (310) peak at 2θ = 35.94°, in the
composite containing 17.6 vol.% TiB.
Fig. 1b shows the XRD pattern of the composite (38.3 vol.%
TiB) processed through HIP. The existence of β Ti and α Ti is
evidenced from the peaks. However, the composite with
20.6 vol.% TiB contains few TiB2 peaks, indicating a minimal
probability of an incomplete reaction. The overlapping of α Ti
(101) and β Ti (110) peaks at 2θ = 39° to 40° is observed in Fig. 1.
Accordingly, more TiB (101), (201), (112), and (210) peaks exist
between 2θ = 35° and 50° in the 38.3 vol.% TiB composite. The
intensities of the Ti and TiB peaks in both composites are
considerably lower than those of the composites processed
through vacuum sintering, as depicted in the diffractogram
(Fig. 1).
The spectra of the composites sintered through SPS are
shown in Fig. 1a and b. The sintered composite matrix mainly
consists of β Ti and few α Ti phases. Unlike the composites
prepared through vacuum sintering and hot isostatic press-
ing, it is reasonable to conclude that the full transformation of
TiB2 into TiB has occurred. The spectra of the composites
reveal the existence of dominant TiB (101), (112) and (201)
peaks at 2θ values of 24.3°, 52.3° and 35.3°, respectively, with
high intensity. The intensity of the TiB (101) peak is found to
be marginally higher in the composite with 38.5 vol.% TiB
than in that with 24 vol.% TiB.
Moreover, the spectra clearly indicate that the composites
sintered through the SPS process feature more dominant TiB
and Ti phases than the composites processed through the
other two techniques (HIP and vacuum sintering). It is noted
that the β Ti (112) peaks are common to the spectra of all of
the composites, regardless of the processing route. It is known
that the β phase is relatively more ductile than the α phase in
Ti alloys [23,27].
4.2.2. Electron Probe Micro Analysis (EPMA)
The EPMA (EDS) results obtain in normal mode are depicted in
Fig. 2a and b for the composites processed through SPS and
vacuum sintering. The results (as shown in Table 4 and 5)
confirm the distribution of Ti and boride phases in the
composites, which have not been reported in earlier studies
[17]. Fig. 3a and b (observed using WDS) show three distinct
regions: one is a very dark boride-rich region, which is
predominantly composed of TiB, and the other regions are
lighter and grey, which confirm the presence of titanium.
However, the presence of a few TiB whiskers in the titanium
outer matrix may be due to the diffusion of boron atoms to the
Ti-rich regions during sintering.
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1 47

Fig. 2 – EPMA (EDS) of Ti–TiB composites processed through SPS and vacuum sintering. (a) EPMA (EDS) of Ti‐38.5 vol.% TiB
composites processed through SPS. (b) EPMA (EDS) of Ti‐37.9 vol.% TiB composites processed through vacuum sintering.

4.2.3. Scanning Electron Microscopy (SEM)
High-magnification micrographs were taken in SEI mode
using SEM after deep etching the samples to reveal the
distribution of TiB whiskers. The morphologies of the TiB
whiskers formed in the composites (38.3 and 20.6 vol.% TiB)
processed by HIP are considerably different from those in the
composites synthesised using the other techniques (SPS and
vacuum sintering) and hot pressing [12]. The composite with
38.3 vol.% TiB (Fig. 4a) shows fine irregular reinforcement,
with a diameter of approximately 1 μm and an aspect ratio
close to unity. Additionally, hard spherical TiB particles are
embedded in the matrix. Fig. 4b illustrates the microstructure
of the composite with 20.6 vol.% TiB. The image shows that α
platelets nucleated within the β matrix. Few TiB whiskers are
also observed in the composite. FeMo particles were not
detected in the composites, which confirm the notion that all
of the Fe and Mo dissolved in the Ti matrix, a result similar to
that reported in a previous work by Feng et al. [24].
The microstructure of the Ti–TiB composites (with 38.5 and
24 vol.% TiB) consolidated using SPS is shown in Fig. 5a and b.
The figures show both β Ti and α phases, which are consistent
with the XRD results. It is ascertained that the addition of a
β-stabilising agent (FeMo) results in a β Ti matrix. The different
types of TiB whisker morphologies observed are as follows. (i) A
small amount of fine TiB needles on the order of 1 μm in length
and 0.6 μm in width is present along the β Ti grain boundaries
in the composites with 38.5 vol.% TiB; (ii) some TiB whiskers are
grouped into colonies of monolithic form, which is not so in the
case of the 24 vol.% TiB composite; (iii) spherical TiB particles
nucleated in the α and β Ti regions in the composite with

Table 4 – EDS analysis of Ti‐38.5 vol.% TiB composites Table 5 – EDS analysis of Ti‐37.9 vol.% TiB composites
processed through SPS. processed through vacuum sintering.
Composition of element (pct) Composition of element (pct)

Ti B Fe Mo Ti B Fe Mo

67.67 17.22 6.18 8.93 72.17 14.95 4.21 8.66

48 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1
Fig. 3 – EPMA (WDS) of Ti–TiB composites processed through
SPS and vacuum sintering. (a) SEM-WDS picture of Ti-37.9
vol.% TiB composite processed by vacuum sintering.
(b) SEM-WDS picture of Ti-38.5 vol.% TiB composite
processed by SPS.
24 vol.% TiB; (iv) it is interesting to note that the TiB
whiskers(1.4 μm in length and 0.7 μm in width, with an aspect
ratio of 2) are short and agglomerated and appear to be inter-
connected and randomly oriented in the composite.
The distribution of TiB whiskers throughout the compos-
ites with 37.9 and 17.6 vol.% TiB and processed using vacuum
sintering are illustrated in Fig. 6. Three types of whiskers are
observed: (i) short agglomerates or clusters of short whiskers,
(ii) coarse needle-shaped whiskers and (iii) fine plates of TiB.
The short agglomerated TiB whisker clusters appear to be
interconnected and uniformly distributed in the composite
with 37.9 vol.% TiB, as shown in Fig. 6a. The short whiskers
are approximately 1.5 μm long and 0.6 μm wide, with an aspect
ratio of 2. Such clusters of short TiB whiskers have been
reported in previous studies [9]. A few coarse, elongated TiB
whiskers growing from the homogeneous layer into the β
matrix of the composite with 17.6 vol.% TiB are shown in Fig. 6b.
The long needle-shaped structures measure approximately
Fig. 4 – SEM images of Ti–TiB composites processed through
HIP. (a) SEM pictures of Ti–TiB composites processed through
HIP (Ti-38.3 vol.% TiB). (b) SEM pictures of Ti–TiB composites
processed through HIP (Ti-20.6 vol.% TiB).
30 μm in length and 4.5 μm in width, with an aspect ratio of 7.
Additionally, fine plates of TiB on the order of 20 μm in length,
5 μm in width and 1 μm in thickness are shown in Fig. 6b. Fine
plates are not observed in the composite processed through
hot pressing, as reported by Sahay et al. [9] and Panda and
Ravichandran [30].
4.3. Comparison of Processing Techniques
The materials characterisation confirms that the composites
processed through HIP and SPS yield highly dense sintered
composites, as their densities and volume percentages are closer
to the theoretical values. Concerning the microstructure, the hot
isostatic pressed composites possess very hard TiB particles with
embedded α platelets, which are not observed in the composites
processed by SPS and vacuum sintering. These α platelets
contribute to the high elastic modulus of the composite [28].
Short agglomerated TiB whiskers are detected in both the SPS
and vacuum sintered composites, though with densely packed
short fibres in the latter. Very fine TiB needles with an aspect
ratio of 2 are distributed in the matrix of the SPS-processed
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1 49

Fig. 5 – SEM images of Ti–TiB composites processed by SPS. Fig. 6 – SEM images of vacuum-sintered Ti–TiB composites.
(a) SEM pictures of Ti–TiB composites processed by SPS (a) SEM pictures of vacuum sintered Ti–TiB composites
(Ti-38.5 vol.% TiB). (b) SEM pictures of Ti–TiB composites (Ti-37.9 vol.% TiB). (b) SEM pictures of vacuum sintered
processed by SPS (Ti-24 vol.% TiB). Ti–TiB composites (Ti-17.6 vol.% TiB).

composite (38.5 vol.% TiB). The same is observed in the vacuum- values. Details regarding these properties are presented in this
sintered composites, which show long needle-shaped structures subsection.
with an aspect ratio of 7. It is noted that the SPS-sintered
composite is significantly different from the composites fabri- 4.4.1. Microhardness
cated using the other processing techniques with respect to their The microhardness of the composites processed through spark
monolithic TiB whiskers (with an aspect ratio of 10), which are plasma sintering, hot isostatic pressing and vacuum sintering
randomly distributed in the composites with 38.5 vol.% TiB. techniques is illustrated in Table 6. The average microhardness
These colonies of fibres do not exist in the HIP- or vacuum- values of the spark-plasma-sintered Ti–TiB composite with
sintered composites. However, fine plates of TiB whiskers are 24% TiB and 38.5% TiB (by volume) are 710 HV and 890 HV,
found in the vacuum-sintered composite. These are not evident respectively.
in the composites synthesised through SPS or vacuum sintering.
Though SPS, HIP and vacuum sintering yield highly dense
composites, as shown in Table 2, there is a considerable dif- Table 6 – Vickers hardness of Ti–TiB composite.
ference in the density (84.6 g/cm3) of the vacuum-sintered
Technique Composite Hardness (HV)
composite (17.6 vol.% TiB) compared to the composites processed
using HIP and SPS. SPS Ti-24% TiB 710
Ti-38.5% TiB 890
HIP Ti-20.6% TiB 658
4.4. Mechanical Properties
Ti-38.3% TiB 823
Vacuum Sintering Ti-17.6% TiB 424
The Ti–TiB composites exhibit good mechanical properties such Ti-37.9% TiB 618
as high hardness and high Young's modulus and shear modulus
50 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1

The microhardness values of the composites (Ti-20.6 vol.%
TiB and 38.3 vol.% TiB) processed by hot isostatic pressing, are
658 HV and 823 HV, respectively. The microhardness of the
composites (Ti-17.6 vol.% TiB and 37.9 vol.% TiB) processed
through vacuum sintering was found to be 424 HV and 618 HV,
respectively.
It is interesting to note that the maximum hardness value
(890 HV) was observed for an SPS-processed composite, in
which the microstructure was controlled. This may be attribut-
ed to the short time required for consolidation at a high heating
rate, which leads to the formation of fine TiB needles and short
agglomerated interconnected fibres in the matrix. This resulted
in the high hardness of the composites. Similarly, for the
composites processed through HIP, hard TiB particles embed-
ded in the matrix and the fine irregular TiB whiskers in the
composites led to an increase in hardness, though to marginally
lower value than that obtained by SPS processing. However, the
results indicate that the vacuum-sintered composites contain
coarse interconnected and long needle-shaped whiskers in the
matrix, which contributed to lower hardness values than those
of the composites fabricated using the other two processing
techniques.
The results confirm that the microhardness increases with
the volume fraction of TiB. The effect of TiB on the Ti matrix
results in high composite hardness [13,23].
and HIP. It is also ascertained that the Young's moduli of the Ti–
TiB composites are higher than the Young's modulus of the Ti
matrix (110 GPa).
The synthesis of TiB reinforcement leads to an increase in
shear modulus with an increase in the TiB volume fraction, as
shown in Table 7. The shear modulus values range between
48.80 GPa and 72.54 GPa in the composites processed through
vacuum sintering and SPS, respectively. It is evident that
there is a marginal difference in the shear modulus values of
the composites processed by HIP. This may be due to the
existence of α platelets, which exhibit higher elastic modulus
values. The average shear modulus values of the composites
(Ti-20.6 vol.% TiB and 38.3 vol.% TiB) processed by this tech-
nique are 61.90 GPa and 67.88 GPa, respectively. The results
show that the presence of the TiB phase in the form of whiskers
in all of the composites may contribute to the increase in the
modulus of TiB, aside from the increase in volume fraction [18].
As expected, the Poisson's ratio was reduced to a value lying
between 0.27 and 0.31 with an increase in the amount of TiB
[18]. The composites with both volume fractions processed
through SPS and vacuum sintering exhibited the same range of
Poisson's ratio (0.31–0.27), with an average deviation of 0.3.
However, the Poisson's ratio of the composites (Ti-17.6 vol.%
TiB and 37.9 vol.% TiB) processed by HIP are almost identical
(0.29), as shown in Table 7.

4.4.2. Elastic Properties

The elastic modulus and Poisson's ratio values of the compos-
ites determined through ultrasonic wave propagation [22] are
presented in Table 7. The Young's modulus and shear modulus
values increase remarkably, while the Poisson's ratio decreases
with an increase in the volume fraction of TiB [20].
The maximum Young's modulus was 185 GPa, observed in
the composite (with 38.5 vol.% TiB) processed by SPS, which is
marginally higher than the Young's modulus of the composites
processed through HIP and vacuum sintering. This resulted
from randomly oriented interconnected TiB whiskers and fine
TiB needles in the composites. It is interesting to note that the
Young's modulus of the composite (with 37.9 vol.% TiB) pro-
cessed by vacuum sintering is comparable with that of the
composite processed by HIP. This may be due to the lower
amount of TiB2 in the processed composite, as evidenced by the
XRD studies and SEM micrographs. This TiB2 content can
substantially increase the modulus beyond that of the Ti–
TiB composites due to the high elastic modulus (540 GPa) of
TiB2 [18]. However, for the composite (with 17.6 vol.% TiB)
processed by vacuum sintering, the elastic modulus (127.86 GPa)
is relatively lower than that of the composites processed by SPS
5. Conclusion
Ti–TiB composites with two different volume fractions (aiming
20 and 40 vol.% TiB) were processed through HIP, SPS and
vacuum sintering. The following conclusions can be drawn:
• The EPMA results reveal the distribution of Ti and boride
phases in the composites. TiB is identified as the predom-
inant boride phase in the Ti matrix. The same is confirmed
by the XRD results (Fig. 2a and b).
• The processed composites also reveal the presence of an
unreacted TiB2 phase.
• There is no evidence of a Ti3B4 phase in any of the
composites.
• The volume fractions of the TiB phase in the composites
were determined through image analysis, which confirms a
reasonable agreement with the target volume percentages
of 20 and 40 of TiB as reinforcement.
• The microstructure of TiB reinforcement reveals three
morphologies, namely needle-shaped whiskers, short ag-
glomerates or clusters of whiskers and very fine plates.

Table 7 – Experimental values of Young's modulus, shear modulus and Poisson's ratio.
Technique Composite Measured Longitudinal Transverse Young's Shear Poisson's
density (g/cm3) velocity (m/s) velocity (m/s) modulus (GPa) modulus (GPa) ratio

SPS Ti-24% TiB 4.90 6484 3429 150.94 57.61 0.31

Ti-38.5% TiB 4.75 7016 3908 185.00 72.54 0.28
HIP Ti-20.6% TiB 4.92 6418 3547 159.70 61.90 0.29
Ti-38.3% TiB 4.90 6788 3700 172.88 67.88 0.28
Vacuum sintering Ti-17.6% TiB 4.20 6488 3409 127.86 48.80 0.31
Ti-37.9% TiB 4.685 6572 3661 160.12 62.77 0.27
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 3 (2 0 1 2) 4 3–5 1
• The HIP and SPS processes yield highly dense sintered
composites.
• The elastic modulus was measured by the ultrasonic method.
The elastic modulus, shear modulus and microhardness were
found to increase with the increasing volume fraction of TiB.
• The composites processed using SPS and HIP exhibit better
elastic properties and higher hardness compared to the
composites processed by vacuum sintering.
• The Poisson's ratio of the composites is reduced with an
increase in the volume fraction of TiB.
Acknowledgements
The authors acknowledge the All India Council for Technical
Education (AICTE), New Delhi for providing a grant to carry
out this work at the Dr. Mahalingam College of Engineering
and Technology, Pollachi, India. The authors also acknowl-
edge Dr. G. Apparao, DMRL, Hyderabad, Dr. Anish Kumar,
IGCAR, Kalpakkam, Mr. Govindaraj, NFTDC, Hyderabad and
Dibyendu Chackravarthy, ARCI, Hyderabad for their support
in processing the composites. The guidance received from
Dr. B. Ravisankar, NIT-Trichy, Ms. Kalavathy, IGCAR-Kalpakkam,
Dr. V. Balusamy, and Dr. R. Subramanian, PSG Tech, Coimbatore
is also gratefully acknowledged.
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