Trans Indian Inst Met (2017) 70(3):709–719
DOI 10.1007/s12666-017-1076-z
TECHNICAL PAPER
Microstructural Characterization and Mechanical Properties
of Diffusion Bonded Ti–Ni In Situ Metal Intermetallic Laminates
N. Thiyaneshwaran1 • M. Ashfaq2 • R. Sidharth1 • G. Saikiran1 • K. Sivaprasad1
B. Ravisankar1
Received: 7 January 2017 / Accepted: 6 February 2017 / Published online: 21 February 2017
Ó The Indian Institute of Metals - IIM 2017
Abstract In this work, Ti–Ni based in situ metal inter-
metallic laminates (MILs) were prepared and the various
intermetallic phases formed were analyzed. Solid state
diffusion bonding technique was adopted to produce tran-
sition joints between commercially pure Ti and Ni sheets of
thickness 0.5 and 0.2 mm respectively at three different
temperatures such as 770, 800 and 850 °C for various
bonding duration. Microstructural characterization and
phase analysis along the cross section of the bonded sam-
ples revealed the presence of three different intermetallic
phases namely Ti2Ni, TiNi and TiNi3. Quasi static com-
pression tests carried out on the MILs along the parallel
and perpendicular direction revealed that the strength of the
MILs increased with increase in total intermetallic layer
thickness. The fractographs taken on fracture surface
revealed that the failure of the MILs was mainly due to the
formation of brittle cracks and de-bonding in the inter-
metallic layers. However, the metallic layers added
strength to the MILs.
Keywords Metal intermetallic laminates 
Diffusion bonding  Compression strength 
X-ray diffraction
& N. Thiyaneshwaran
thiyaneshdinesh@gmail.com
1 diffusion couple are available, studies emphasizing the
Advanced Materials Processing Laboratory, Department of
Metallurgical and Materials Engineering, National Institute
of Technology, Tiruchirappalli, Tamil Nadu 620015, India
2
FARCAMT Professor, Advanced Manufacturing Institute,
King Saudi University, Riyadh, Saudi Arabia
•
1 Introduction
Intermetallic compounds are well known for its high tem-
perature strength, lower density, relatively good oxidation
and corrosion resistance. Even though these compounds
have interesting physical and mechanical properties, they
found less application in structural, turbine and aerospace
industries as most of the intermetallic compounds are
brittle in nature at room temperature [1–3]. A number of
techniques have been proposed for the past few decades to
improve the room temperature ductility and toughness of
the intermetallic compounds. One of the most efficient
method is to reinforce ductile phase in the form of lami-
nates with the brittle intermetallic phase. It is reported that
the laminated metallic phase with the intermetallic com-
pounds had improved the ductility by arresting the cracks
from propagating near the interface [4, 5]. Such laminates
are termed metal intermetallic laminates (MILs) and are
made in situ from the parent metallic phases capable of
forming intermetallic compounds [6]. Various processing
methods have been adopted for the preparation of these
MILs among which solid state diffusion bonding has been
proven to be the most economical and efficient technique.
The strength of these bonded laminates depend on the
property and thickness of the metallic phase and can be
varied according to the application. A number of studies on
different MIL systems such as Ti–Al, Ni–Al, Ti–Cu etc.
has been reported in the recent past emphasizing good
room temperature mechanical properties [7–13]. Though
numerous studies on phase formation analysis on Ti–Ni
mechanical aspects of Ti–Ni MILs are very less. The
intermetallic phase formation analysis by Bastin et al. [14]
in various Ti–Ni based diffusion couples revealed the
formation of three different intermetallic (IM) phases such
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as Ti2Ni, TiNi and TiNi3. He reported that only the growth
of b-Ti(Ni), Ti2Ni and TiNi phases obeyed the parabolic
law. Similar kind of IM phase formation was reported by
Kundu and Chatterjee [15] and Kundu et al. [16] while
bonding Titanium to stainless steel using Ni interlayer.
Garay et al. [17] reported that the growth rate and growth
rate constants of the intermetallic phases in the Ti–Ni
system increased with the application of direct current. The
results also showed significant decrease in the activation
energy for the IM phase formation with the increase in
current density. These studies are mainly focused on the IM
phase growth behavior in the Ti–Ni and more of the
mechanical aspects of the Ti–Ni MILs are needed to be
addressed. To fill the gap, the present investigation mainly
focuses on evaluating the mechanical properties of the Ti–
Ni MILs with varying intermetallic layer thickness pre-
pared through solid state diffusion bonding. The mechan-
ical property of the MILs have been examined by quasi
static compression tests carried out in room temperature.
The growth behavior and activation energies of the various
IM phases formed have been discussed to a particular
extent and the failure analysis of the compression tested
samples has been done to understand the failure phe-
nomenon in the MILs.
2 Experimental Procedure
The Ti–Ni MILs of thickness 6 mm were prepared through
solid state diffusion bonding technique using commercially
available Titanium and Nickel sheets of 0.5 and 0.2 mm
thickness respectively. For the preparation of lightweight
and high strength MILs, the Ni sheet thickness was chosen
lesser than Ti sheets which reduced the total volume
fraction of Ni present in the MILs, as the density of Ni was
relatively higher. The as received sheets were further cut to
square shape of dimension 25 9 25 mm for bonding.
These cut Ti and Ni sheets were then cleaned with 10% HF
and 40% HNO3 ? 40% H2SO4 ? 20% H2O solutions
respectively to remove the surface impurities and oxide
layers. The cleaned sheets were ultra-sonicated in distilled
water for 10 min and dried thoroughly. The surface cleaned
Ti and Ni sheets (9 and 8 Nos respectively) were then
stacked alternatively in the die setup with Ti at both the
ends for MIL preparation. Solid state bonding was
accomplished by keeping the diffusion couple for a certain
period of time at an elevated temperature usually 50–70%
of the lowest melting temperature (Tm) of the diffusion
couple. In this case, as Ni have the lowest melting tem-
perature of 1455 °C (Tm), the diffusion temperatures were
selected between 0.5 and 0.7 Tm. The bonding between the
sheets was carried out in a diffusion bonding setup at three
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Trans Indian Inst Met (2017) 70(3):709–719
different temperatures such as 770, 800 and 850 °C with
bonding time varying from 0.5- to 6 h. An uniaxial pres-
sure of 8 MPa was applied to the sheets to ensure good
contact and a vacuum of -760 mmHg was maintained in
the furnace chamber to avoid oxide layer formation. The
MIL samples were furnace cooled after bonding to avoid
residual stresses between the Ti/Ni pairs. The bonded MILs
were cut across the bond interface using wire cut electrical
discharge machine (EDM) and the cut surface was polished
using standard metallographic procedures for further
microstructural and phase analysis. Hitachi make S3000H
scanning electron microscope (SEM) was used for
microstructural characterization i.e. to reveal the bond
interface and the various intermetallic layers formed as a
result of diffusion reaction between Ti and Ni. The layer
thickness of the individual intermetallic layers was mea-
sured from the SEM images using Image J software.
Thermo USA make energy dispersive spectroscopy (EDS)
and RIGAKU ULTIMA IV X-Ray diffraction (XRD)
facilities were used for composition and phase analysis of
the MIL samples.
The mechanical properties of the MILs were evaluated
by conducting quasi static uniaxial compression tests at
room temperature using Tinius Olsen Universal (50 kN
capacity) testing machine. As the prepared MIL samples,
did not have sufficient length to conduct other mechanical
tests such as tensile and lap joint type tests, compression
test was used for evaluating the strength of the MILs and
the results were compared with pure Ti. Also, compression
tests could be possible on two test directions i.e. parallel
and perpendicular to intermetallic layer, owing to the small
sample dimensions. For the compression tests, the MILs
were cut to dimensions 5 9 5 9 6 mm using wire EDM.
Compression tests were also conducted on commercially
pure Ti samples of 4 mm in diameter and height, for
comparison with the MILs. The compression test sample
dimensions of MILs and pure Ti were selected to have a
L/D ratio of 1 approximately. All the samples were pol-
ished properly prior to the tests for further microstructural
characterization of the fracture/failure surface using SEM.
The testing of the MILs up to failure led to delamination of
the sheets and complete deformation in parallel and per-
pendicular directions. Hence it became further difficult to
reveal the failure and crack initiation locations. So the tests
were performed to a maximum engineering strain value of
25% in order to reveal the failure locations. A constant
strain rate of 0.001/s was used for all the tests. Figure 1
shows the schematic of the MIL, Ti compression test
samples. To evaluate the variation of strength with respect
to loading direction, the MILs were tested along two dif-
ferent orientations i.e. loading direction parallel (Fig. 1a)
and perpendicular (Fig. 1b) to the intermetallic layer.
Trans Indian Inst Met (2017) 70(3):709–719
Fig. 1 Schematic of compression test samples a perpendicular
direction, b parallel direction and c Ti
3 Results and Discussion
3.1 Microstructure and Phase Analysis
Figure 2a shows the SEM micrograph taken at low mag-
nification using back scattered electron (BSE) mode, across
the interface of the Ti–Ni diffusion couple bonded at
800 °C for 4 h. It can be seen from the image that three-
different color contrast are present representing different
phases. The alternate bright and dark layers of varying
thickness represent the Ti and Ni sheets that have been
used for diffusion bonding. The thin grey colored layer in
between the Ti and Ni layers represent the product phase
that has been formed due to the diffusion of Ti and Ni
atoms across the interface of the diffusion couple. It can
also be seen from the micrograph that the interface between
Ti, Ni and product phase are found to be good and intact
and there is no crack formation due to the applied pressure.
Fig. 2 BSE mode SEM image
of MILs bonded at a 800 °C for
4 h (low magnification),
b 850 °C for 2 h (high
magnification) and c EDS
spectrum of intermetallic phases
Ti2Ni, TiNi and TiNi3
711
Figure 2b shows the high magnification SEM image taken
on the product phase in the MIL bonded at 850 °C for 2 h
bonding time. It shows that the reaction product consists of
three different layers denoting three different product
phases formed which are labelled as 1, 2 and 3
respectively.
EDS analysis has been performed on different spots on
the individual product layers to obtain the composition of
the phases formed. It is found from the point analysis that
the composition to be nearly 63.29 wt% Ti and 36.71 wt%
Ni for region 1, 43.77 wt% Ti and 56.23 wt% Ni for
region 2 and 21.07 wt% Ti and 78.93 wt% Ni for region 3.
The Ti–Ni binary phase diagram [18] reveals that these
compositions correspond to stable intermetallic (IM) pha-
ses such as, Ti2Ni, TiNi and TiNi3, which can form at the
bonding temperatures used in this study. Figure 2c shows a
typical EDS spectrum obtained from the intermetallic
phases Ti2Ni, TiNi and TiNi3 denoted by numbers 1, 2 and
3 respectively formed in the MIL bonded at 850 °C for
2 h. The difference in the count values of Ti and Ni con-
firms that the intermetallic phases formed are Ti2Ni, TiNi
and TiNi3. In addition to the formation of these inter-
metallic phases, Ni atoms also diffuse into the pure a-Ti
layer forming Ti(Ni) solid solution and also transforming it
to b-Ti as Ni being a beta eutectoid stabilizer and also
because of low solubility of Ni in a-Ti. Due to this, both a
and b Ti phases co-exists in the Ti layer up to a maximum
Ni solubility of approx. 5.66, 4.74 and 2.26 wt% at tem-
peratures 770, 800 and 850 °C respectively [18]. Figure 3
shows the co-existence of both a and b Ti in the MILs
bonded at temperatures 800 °C (Fig. 4a–c) and 850 °C
(Fig. 4d–f). It can be seen from the Fig. 3a that the a ? b
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Fig. 3 SEM images showing the presence of a ? b Ti in the MILs bonded at a, b 800 °C—4 h, c 800 °C—6 h, d, e 850 °C—0.5 h, f 850 °C—
1 h and Ti2Ni IM phase along the grain boundaries in the MILs bonded at 850 °C for g 4 h and h 6 h
Fig. 4 XRD patterns of MILs bonded at 770, 800 and 850 °C for 6 h
duration
Ti having lamellar structure are present only along the
sides of the layer and the center portion (denoted by yellow
arrow) has some untransformed equiaxed a-Ti surrounded
by b-Ti even after 4 h of bonding at 800 °C which is
shown clearly in Fig. 3b. This can be confirmed from the
fact that in a ? b Ti alloys, annealing from b-Ti phase
field causes transformation from b to a having lamellar
microstructure and annealing from a ? b Ti phase field
produces equiaxed a-Ti grains surrounded by retained b-Ti
phase. Figure 3c shows the Ti layer after bonding at
800 °C for 6 h, in which a ? b Ti are found over the
entire thickness. Thus, complete transition of a-Ti to
a ? b Ti is observed after 6 h bonding at 800 °C. Similar
kind of transition is also noticed in the MILs bonded at
770 °C. In case of MILs bonded at 850 °C, transition from
a-Ti to a ? b Ti due to Ni diffusion is seen after 0.5 h
bonding duration which is shown in Fig. 3d, e. The dif-
fusion front in Fig. 3e confirms the presence of Ti along
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Trans Indian Inst Met (2017) 70(3):709–719
the grain boundaries and complete transition is achieved
after 1 h bonding time (Fig. 3f) due to high Ni diffusivity
at the processed temperature. The formation of such
intermetallic and a ? b Ti phases are consistent with
previous studies on Ti–Ni system [14–16, 19]. With further
increase in the diffusion time i.e. after 4- and 6 h bonding
at 850 °C, Ni diffusion in the a ? b Ti reaches a saturation
limit and formation of Ti2Ni intermetallic is found near the
grain boundaries which can be seen in Fig. 3g, h. EDS
point analysis on that phase, shows a composition of nearly
63.10 wt% Ti and 36.90 wt% Ni which confirms that the
phase formed is Ti2Ni. The Ti2Ni intermetallic formed
along the grain boundaries are found connected to the
Ti2Ni layer on either side of the Ti layer which are denoted
by yellow arrows in Fig. 3g. Figure 4 shows the XRD
patterns obtained from the MILs bonded at 770, 800 and
850 °C for 6 h. Peaks corresponding to the intermetallic
phases Ti2Ni, TiNi and TiNi3 and also b-Ti are found in all
the cases which confirms the formation of these phases in
the MILs.
3.2 Layer Thickness and Activation Energy
Figure 5a–h shows the presence of individual intermetallic
(IM) layer in the MILs bonded at temperatures 770, 800
and 850 °C for various bonding time. The intermetallic
phases Ti2Ni, TiNi and TiNi3 in the images are marked in
green, cyan and blue color respectively. The images clearly
show the variation in the individual layer thickness with
respect to bonding temperature and time. The intermetallic
layer thickness is measured at different regions and the
average values are taken into account. The total volume
fraction of the intermetallic phases formed are calculated
from the total IM, Ti and Ni layer thickness values using
formula (1).
Trans Indian Inst Met (2017) 70(3):709–719 713

Fig. 5 SEM images of MILs bonded at a 770 °C—4 h, b 770 °C—6 h, c 800 °C—2 h, d 800 °C—4 h, e 800 °C—6 h, f 850 °C–-2 h,
g 850 °C—4 h and h 850 °C—6 h duration showing intermetallic layer thickness variation

tIM nIM increase in both bonding time and temperature. The growth
VfIM ¼ ð1Þ
tIM nIM þ tTi nTi þ tNi nNi behavior of Ti2Ni IM layer is similar in the MILs bonded at
770 and 800 °C. The growth rate is initially higher up to
where tIM, tTi and tAl denotes the total thickness (lm) of
2 h bonding time and it gets reduced beyond further
intermetallic, Ti and Al layers, nIM, nTi and nNi are layer
increase in diffusion time. Previous studies [14] suggests
count of IM, Ti and Ni respectively. Table 1 shows the
that the decrease in the growth rate of Ti2Ni IM is mainly
calculated values of individual and total intermetallic and
due to formation of b-Ti as more Ni atoms diffuse towards
metallic layer thickness. Figure 6a–c shows the variation of
Ti layer to form a ? b Ti phase. While in case of MILs
individual intermetallic layer thickness with respect to
bonded at 850 °C, the Ti2Ni growth rate increases abruptly
bonding temperature and time. It is seen from the graph
after 2 h bonding time. The growth of TiNi3 layer is similar
that the thickness of all the three IM layers increases with

Table 1 Calculated layer thickness and volume fraction of intermetallic and metallic phases after bonding
Conditions Base metal layer thickness (lm) IM layer thickness (lm) Total IM layer Total IM volume
thickness (lm) fraction VIM
f
Temperature Time Ti Ni Ti2Ni TiNi TiNi3
(K) (h)

770 °C 0.5 506.595 ± 1.16 179.725 ± 0.67 1.717 ± 0.11 3.651 ± 0.25 2.025 ± 0.26 7.393 0.0193
770 °C 1 501.382 ± 1.72 172.849 ± 0.72 2.186 ± 0.18 4.818 ± 0.48 3.118 ± 0.14 10.122 0.0267
770 °C 1.5 492.048 ± 1.06 168.736 ± 1.93 2.599 ± 0.16 5.692 ± 0.34 3.895 ± 0.18 12.186 0.0326
770 °C 2 485.302 ± 0.47 170.854 ± 0.72 2.902 ± 0.17 6.611 ± 0.10 4.339 ± 0.27 13.852 0.0372
770 °C 4 479.829 ± 0.84 161.455 ± 0.57 3.743 ± 0.18 8.789 ± 0.13 4.951 ± 0.17 17.483 0.0475
770 °C 6 473.472 ± 1.97 156.198 ± 0.98 3.896 ± 0.32 13.865 ± 0.17 5.215 ± 0.16 22.976 0.0625
800 °C 0.5 515.595 ± 0.35 180.603 ± 2.62 2.144 ± 0.14 5.012 ± 0.41 2.512 ± 0.28 9.668 0.0242
800 °C 1 512.951 ± 1.51 171.302 ± 1.29 2.758 ± 0.44 7.502 ± 0.22 3.588 ± 0.39 13.848 0.0355
800 °C 1.5 510.671 ± 2.25 156.410 ± 0.89 3.168 ± 0.20 9.211 ± 0.22 4.109 ± 0.39 16.488 0.0432
800 °C 2 512.868 ± 1.22 147.785 ± 2.06 3.557 ± 0.24 10.322 ± 0.33 4.535 ± 0.26 18.414 0.0484
800 °C 4 511.774 ± 0.59 140.450 ± 1.60 4.247 ± 0.20 13.964 ± 0.85 5.469 ± 0.26 23.680 0.0646
800 °C 6 507.034 ± 1.49 137.374 ± 2.36 4.851 ± 0.31 20.405 ± 0.48 6.234 ± 0.32 31.490 0.0858
850 °C 0.5 522.393 ± 0.79 156.178 ± 1.92 3.896 ± 0.41 7.807 ± 0.23 3.364 ± 0.19 15.067 0.0389
850 °C 1 520.337 ± 1.96 152.039 ± 1.89 5.368 ± 0.60 11.708 ± 0.34 4.450 ± 0.40 21.526 0.0552
850 °C 1.5 513.303 ± 1.82 140.441 ± 0.72 6.146 ± 0.71 13.704 ± 0.26 5.918 ± 0.28 25.768 0.0669
850 °C 2 515.771 ± 2.52 137.561 ± 2.05 6.446 ± 0.24 15.251 ± 0.32 6.681 ± 0.14 28.378 0.0733
850 °C 4 501.529 ± 1.93 132.084 ± 1.87 8.658 ± 0.49 24.114 ± 0.81 7.174 ± 0.51 39.946 0.1024
850 °C 6 473.007 ± 0.71 129.134 ± 1.21 11.659 ± 0.58 36.146 ± 0.90 7.659 ± 0.38 55.464 0.1431

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Fig. 6 Change in intermetallic layer thickness with respect to bonding time in MILs bonded at a 770 °C, b 800 °C and c 850 °C
in all the processed temperatures with considerable
decrease in the growth rate after 2 h bonding time. The
TiNi IM contributes more to the total IM layer thickness in
all the processed conditions and the growth of which
increases for the entire bonding time.
The rate constants of each IM layer has been calculated
based on Wagner approach [20] which is given by the
Eq. (2).
Dx2 ¼ kt
where Dx represents the intermetallic layer thickness, k is
the rate constant of first kind and t the diffusion time. The
intrinsic rate constants cannot be calculated for the tem-
peratures used in this study because of the high diffusion of
Ni in Ti as it violates the assumptions involved [20]. The
rate constants (first kind) of the intermetallic phases can be
obtained from a plot between squared IM layer thickness
and diffusion time assuming parabolic growth. Figure 7a–c
show such graphs plotted for the intermetallics Ti2Ni, TiNi
and TiNi3 respectively. The IM thickness data are fitted
using linear regression model and the slope of the fitted line
represents the rate constant. It is observed from the plot
that the growth constants of the IM phases are not constant
and it varies with the diffusion time.
Figure 7a shows the fitted model for the Ti2Ni IM
formed in the MILs bonded at temperatures 770, 800 and
850 °C. The growth of the Ti2Ni IM phase initially is found
Fig. 7 Squared layer thickness versus bonding time plots for the intermetallic phases a Ti2Ni, b TiNi and c TiNi3 showing variation in rate
constants with different bonding temperature
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Trans Indian Inst Met (2017) 70(3):709–719
to be rapid with higher rate constant followed by a gradual
decrease in the growth with lower rate constant at the
processed temperatures 770 and 800 °C. Similar kind of
two stage growth of Ti2Ni is observed in the work of Bastin
et al. [14], in which the increase and decrease in the growth
was attributed mainly due to the transition from grain
boundary to volume diffusion. In this case, it can be noted
that the decrease in the rate constant was observed at the
ð2Þ diffusion time in which high solubility of Ni in b-Ti started
to take place. It can be further explained in a way that in
case of MILs bonded at 800 °C, the a ? b Ti was formed
locally along the sides of the Ti layer up to 2 h bonding
duration providing less space for Ni diffusion and initially
increasing the Ti2Ni growth rate. At the end of 2 h bonding
time, almost 3/4th of the Ti layer was already transformed
to a ? b Ti which increases the Ni mobility in those layers
and reducing the Ti2Ni growth rate. Thus, high diffusion of
Ni towards Ti to form b-Ti hinders the growth of Ti2Ni IM
phase. This is exactly opposite in case of MILs bonded at
850 °C, in which Ti2Ni growth constant is higher after 3 h
bonding time. It can be seen from the Fig. 3g, h that Ti2Ni
phase started to form along the a ? b Ti grain boundaries
due to the saturation in the solubility of Ni in b-Ti, which
in turn leaves behind more Ni for the Ti2Ni layer formation
thus increasing the growth rate. It can be noted from
Fig. 7a that there is a slight decrease in the rate constant of
Ti2Ni after 1 h bonding time in the MILs bonded at
Trans Indian Inst Met (2017) 70(3):709–719
850 °C. It denotes that there is a decrease in the growth rate
of Ti2Ni after 1 h bonding time and it continues to grow at
the same rate up to 3 h bonding duration due to high dif-
fusion of Ni in b-Ti. Thus, the initial stage high growth
constant in case of MILs bonded at 850 °C is limited to 1 h
bonding time. The fitted line (shown by blue colored dotted
lines) of this initial stage growth is extended up to 6 h
bonding time for comparison. After 3 h bonding time, the
layer growth takes place approximately with same rate
constant of initial stage which can be seen in the graph
(Fig. 7a) that both the fitted lines are almost parallel to
each other. Thus, in the MILs bonded at 850 °C, the growth
of Ti2Ni takes places in three stages denoted by 1, 2 and 3
respectively. While in MILs bonded at 770 and 800 °C, the
Ti2Ni growth takes place in two stages because the third
stage Ti2Ni layer growth has not started yet.
Figure 7b shows the TiNi phase, rate constant variation
over the bonding time for the different bonding temper-
atures. It is observed from the figure that the rate constant
increased after 4- and 3.5 h in the MILs bonded at tem-
peratures 770, 800 and 850 °C. The high growth rate of
TiNi can be due to the slightly wide composition range
involved at the processed temperatures when compared to
the other two IM phases. And as the growth rate of Ti2Ni
increased beyond 2 h diffusion time when processed at
850 °C, the growth rate of TiNi also increased abruptly
increasing the rate constants (Table 1). Figure 7c shows
the decrease in the rate constant for the TiNi3 phase
beyond 2 h diffusion time in all the processed tempera-
tures. The decrease in the rate constant is mainly due to
the long-range diffusion of Ti toward the phase as Ti has
much less diffusivity at the temperatures used. This can
be observed from Table 1 that the difference in the layer
thickness between 6 h and 2 h bonding time is hardly
1 lm for all the processed condition. Bastin et al. [14]
reported that the initial high growth rate is due to the
grain boundary diffusion followed by volume diffusion
due to the increased grain growth which reducing the rate
constants.
The activation energy for the growth of these inter-
metallic phases were calculated from the initial stage rate
constants by plotting between ln k versus 1/T as both are
related by Arrhenius type Eq. (3).
Q
k ¼ k0 eQ=RT or ln k ¼ ln k0  ð3Þ
RT
where k is the rate constant, k0 the pre-exponential growth
constant, Q is the activation energy for the phase forma-
tion, R is the gas constant and T is the temperature
involved. Figure 8 shows the plots between ln k and 1/T for
the individual intermetallic phase and the activation energy
can be calculated from the slope of the fitted line. The
calculated values of the rate constants and activation
715
Fig. 8 Plot of ln k versus 1/T of the intermetallic phases Ti2Ni, TiNi
and TiNi3 for activation energy calculation
energy for the various phases formed are shown in Table 2.
In the work of Bastin et al. [14], there is a sharp discon-
tinuity in the log k versus 1/T plot between the tempera-
tures 760 and 800 °C which may be due to the formation of
b-Ti at 770 °C. In this study too, discontinuity in the ln k
versus 1/T is seen between the temperatures 770 and
800 °C. Taking this into account, the activation energy of
Ti2Ni is obtained by fitting the rate constant data points
corresponding to the temperatures 800 and 850 °C. The
activation energy of TiNi3 is found to be the lowest among
the three IM phases.
3.3 Compression Strength and Failure Analysis
Figure 9a–f show the plots between engineering stress and
engineering strain for the MILs tested along parallel and
perpendicular direction. The stress–strain plot of the
commercially pure Ti is also shown for comparison. The
deformation behavior is completely elastic–plastic for all
the MILs and no delamination of the sheets is observed
during the test. All the MILs continue to deform up to the
total applied strain value (25%). It is observed that the
strength of the MILs along the perpendicular direction is
slightly higher than in the parallel tested samples in all the
conditions. This confirms that the MILs exhibit anisotropic
property with respect to the loading direction. Only the
MILs bonded at 770 °C up to 2 h bonding time is found to
be having lower strength than the commercially pure Ti
which may be due to the lower intermetallic content. Fig-
ure 10a, b show the change in the yield strength (YS) and
ultimate compressive strength (UCS) with respect to the
bonding time and temperature along parallel (Fig. 10a) and
perpendicular direction (Fig. 10b). Both the YS and UCS
of the MILs bonded at different temperatures are found to
be increasing with respect to the diffusion time in both the
test directions. This is mainly due to the increase in the
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716 Trans Indian Inst Met (2017) 70(3):709–719

Table 2 Calculated growth rate constants and activation energies of the intermetallic phases
IM phases Rate constant (910-12 cm2/s) Activation energy (kJ mol-1)
Initial stage Later stage
1043 K 1073 K 1123 K 1043 K 1073 K 1123 K

Ti2Ni 8.689 14.776 72.547 1.614 7.553 84.701 318.8

TiNi 50.640 132.119 314.267 159.713 307.463 1007.158 174.4
TiNi3 27.577 24.952 63.980 5.812 9.339 9.748 78.8

Fig. 9 Compression engineering stress–strain curve of MILs bonded at 770, 800 and 850 °C for a 0.5 h, b 1 h, c 1.5 h, d 2 h, e 4 h and f 6 h
duration and tested in parallel and perpendicular direction

intermetallic phase fraction in the MILs. The difference in
the strength values in both the test directions is slightly
higher between the MILs bonded at 770 and 800/850 °C
than between 800 and 850 °C which can be seen in the
stress–strain graphs. The stress–strain curve of the MILs
bonded at 800 and 850 °C are mostly close to each other in
both the test directions denoting lesser strength improve-
ment along the temperature range.
Figure 11a–h show the cracks formed in the MILs
(bonded using different conditions) when tested along the
parallel direction. The white colored arrows on the top and
bottom of the images show the test loading direction. In all
the MILs tested in parallel direction, only localized
debonding is observed between the interfaces of different
phases and there are no complete delamination of the Ti
and Ni sheets. The cracks and localized debonding are
present only in the Ti–Ti2Ni and TiNi3–Ni interfaces which
are denoted by yellow and red colored arrows in the images
respectively. Figure 11a shows the localized debonding
along the Ti–Ti2Ni interface in the MIL bonded at 770 °C
for 4 h, which is shown in high magnification in the inset.
From the inset, it is clear that cracks are formed in the
Ti2Ni IM phase which appears to be brittle. While in case
of MILs bonded at 770 °C for 6 h duration (Fig. 11b),
debonding along both Ti–Ti2Ni and TiNi3–Ni interfaces
are observed clearly. Similar kind of localized debonding is
also seen in the MILs bonded at 800 and 850 °C for dif-
ferent bonding duration which are shown in Fig. 11c–h. It
is seen from the Fig. 11d that the TiNi IM phase exhibits
certain amount of plastic deformation when compared to
Ti2Ni and TiNi3. Also the debonding in the Ti–Ti2Ni
interface is mainly due to the britlle crack formation in the
Ti2Ni IM phase which can be seen clearly in the Fig. 11g,
h.

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Figure 12a–h show the cracks formed in the MILs
(bonded using different bonding parameters) when tested in
the perpendicular direction. The white colored arrows on
both sides of the images show the loading direction. In the
MILs tested in perpendicular direction, cracks are observed
Fig. 10 Variation of compressive strength with respect to bonding
duration along the a parallel and b perpendicular direction in the
MILs (YS—yield strength and UCS—ultimate compressive strength)
Fig. 11 SEM micrographs showing de-bonding and crack formation in the MILs bonded at a, b 770 °C—4 and 6 h, c–e 800 °C—2, 4 and 6 h,
f–h 850 °C—2, 4 and 6 h duration and tested along parallel test direction
717
to form only parallel to the loading direction and there are
no localized debonding or complete delamination of the
sheets. It can be seen that the cracks are formed only in the
Ti2Ni and TiNi3 IM phases and are denoted by yellow and
red colored arrows. Figure 12a, b show the fracture
locations in the MILs bonded at 770 °C for 4- and 6 h
duration. The cracks are formed in the brittle Ti2Ni and
TiNi3 phases and oriented along the loading direction. The
Ni layer is found to get squeezed between the Ti layers and
exhibits good ductility. The Ti layers also deform plasti-
cally while loading adding strength to the MILs. Similar
kind of mechanical response and crack formation is
observed in the MILs bonded at 800 °C (Fig. 12c–e) and
850 °C (Fig. 12f–h). The TiNi IM phase exhibits good
ductility than other two IM phases as it gets deformed
plastically between Ti2Ni and TiNi3. The cracks are con-
fined only among the Ti2Ni and TiNi3 phases and there are
no propagation in both TiNi IM phase and the metallic
layers. In addition to this, in the MILs bonded at 850 °C for
4- and 6 h duration and tested in perpendicular direction,
cracks are formed in the Ti2Ni phase formed in the grain
boundaries of the a ? b Ti which are shown clearly in
Fig. 13a, b. The cracks formed are also parallel to the
loading direction which are shown clearly in the inset in
Fig. 13b.
4 Conclusion
1. Ti/Ni MILs were prepared successfully through dif-
fusion bonding at temperatures 770, 800 and 850 °C
for various bonding duration. The Ti2Ni, TiNi and
TiNi3 were the intermetallic phases formed as a result
of diffusion reaction between Ti and Ni atoms and the
IM layer thickness varied with respect to bonding
duration. In addition to the formation of these IM
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Fig. 12 SEM micrographs showing crack formation in the MILs bonded at a, b 770 °C—4 and 6 h, c–e 800 °C—2, 4 and 6 h, f–h 850 °C—2, 4
and 6 h duration and tested along perpendicular test direction
Fig. 13 SEM images showing crack formation along the grain
boundaries in the MILs bonded at 850 °C for a 4 h and b 6 h duration
when tested in perpendicular test direction
phases, b Ti was also formed in the Ti layer due to the
initial high diffusion of Ni atoms.
2. The rate constants and activation energies of the
Intermetallic phases were calculated from squared IM
layer thickness versus diffusion time and ln k versus
1/T plots. The activation energy for Ti2Ni, TiNi and
TiNi3 IM phases were calculated to be 140.4, 174.4
and 78.8 kJ/mol respectively.
3. The compressive strength of the MILs was found to be
increased with increase in intermetallic layer thickness
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Trans Indian Inst Met (2017) 70(3):709–719
in both parallel and perpendicular direction. Also, the
MILs exhibited anisotropic property with higher
strength along the perpendicular direction than in
parallel direction.
4. The failure analysis revealed that there were only
localized debonding along the Ti–Ti2Ni and TiNi3–Ni
interface and no complete delamination in the MILs
tested in parallel direction. In the MILs tested in
perpendicular direction, cracks were formed in the
Ti2Ni and TiNi3 IM phases and plastic deformation in
TiNi, Ti and Ni layers was observed. The cracks
formed in the MILs were oriented parallel to the
loading direction.
Acknowledgements This work was funded by Defence Research and
Development Organization (DRDO) of India under Project Sanction
No. ERIP/ER/1006013/M/01/1374.
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