Intermetallics 53 (2014) 56e61

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Effect of heat treatment on precipitate free zones and rollability of

V55Ti30Ni15 alloys
Yandong Yu, Peng Jiang*
School of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China

a r t i c l e i n f o a b s t r a c t

Article history: Various heat treatment processes were performed to modify the precipitate microstructures and roll-
Received 3 March 2014 ability of V55Ti30Ni15 alloys. SEM and TEM results showed that NiTi particles precipitated from V-matrix
Received in revised form and precipitate free zones (PFZs) were formed at the boundary of V-matrix grain during heat treatment.
15 April 2014
The orientation relationship between the precipitated NiTi and the V-matrix was analyzed. The PFZs
Accepted 20 April 2014
widths monotonically increased with increasing heat treatment temperature and time. The rollability of
Available online 13 May 2014
the heat treated alloy is better than that of the as-cast alloy, and PFZs played an important role in
restricting cracks extension and coordinating deformation during rolling process.
Keywords:
D. Grain boundary
Ó 2014 Elsevier Ltd. All rights reserved.
C. Heat treatment
D. Microstructure
C. Rolling

1. Introduction
Recent work on a series of alloys V85
xTixNi15 (x ¼ 0e30 at.%) has
shown that the permeability of V55Ti30Ni15 alloy
(1.05  10
7 mol m
1 s
1 Pa
0.5 at 400  C) approaches that of pure
V [1,2] which possesses a multiphase microstructure consisting of
primary BCC V-solid solution and eutectic phase containing NiTi
intermetallic compounds. Primary V-solid solution and eutectic
phase are believed to contribute to hydrogen permeation and
resistance to hydrogen embrittlement, respectively [3e5]. This
seems to be a promising alloy which may reach a good combination
of hydrogen permeability and mechanical stability in hydrogen.
Metal rolling process is most widely used for sheet fabrication and
may make multiphase VeTieNi metallic membranes thinner for
increasing hydrogen transport flux [6]. Up to now, there is little
information on their rolling workability.
Precipitate-free zones (PFZ) form during the heat treatment of
metallic alloys [7], especially Al-based alloys. The role of PFZ on
mechanical properties is clearly attested in the literature. The
presence of PFZ was found to be harmful to the mechanical
properties of AleLi alloys [8], AleMg alloys [9] and AleMgeZn
alloys [10]. Similarly, the yield strength, the ultimate tensile
strength and the plastic strain to fracture of a g0 -strengthened
* Corresponding author. Tel.: þ86 451 86391277.
E-mail address: penn.jiang@gmail.com (P. Jiang).
nickel-base superalloy have been linked to the width of the PFZ
[11]. However, some researchers thought that slip bands and
stress concentration had a priority to be released in the PFZs,
resulting in the increase of strength and ductility of the selected
alloys [12,13].
In previous work, we studied the effect of heat treatment on the
microstructure and hardness of V55Ti30Ni15 alloys and found that
the precipitation and dissolution of NiTi particles in V-matrix
resulted in the hardness variation of the alloys [14]. In the present
work, the orientation relationship between the precipitated NiTi
and the V-matrix in the heat treated V55Ti30Ni15 alloys was
analyzed by TEM, and the effect of heat treatment on the PFZs and
rollability of the alloys was discussed.
2. Experimental
2.1. Alloy preparation
High purity (99.9%) vanadium, titanium and nickel pellets were
mixed and melted on a water-cooled copper hearth using a vac-
uum/argon arc melter in the composition of 55 at.% V, 30 at.% Ti,
and 15 at.% Ni. The arc-melted ingot (total weight 100 g) was turned
over and re-melted several times to ensure compositional homo-
geneity. During melting, the chamber was evacuated to
<0.7  10
3 Pa and then backfilled with high-purity argon gas up to
a pressure of 100 kPa.

http://dx.doi.org/10.1016/j.intermet.2014.04.008
0966-9795/Ó 2014 Elsevier Ltd. All rights reserved.
 Y. Yu, P. Jiang / Intermetallics 53 (2014) 56e61
Fig. 1. Optical micrograph of the initial microstructure from the arc-melted cast ingot
showing primary Vss dendrites and intermetallic compounds distributed in the
interdendritic region detailed features in the SEM inset.
Fig. 2. (a) SEM and TEM (b) images of V55Ti30Ni15 alloy heat treated at 800  C for 18 h, (c) corresponding SAED patterns of NiTi particle and V-matrix and (d) high resolution image
of the interface between NiTi particle and V-matrix in (b).
57
2.2. Heat treatment and rolling
The arc-melted ingot was sectioned to produce a batch of small
samples using electrical discharge machining (EDM). These sam-
ples were sealed in quartz tubes which were vacuumed and back-
filled with high-purity argon gas to avoid oxidation of the samples.
Subsequently, the sealed samples were heated at a temperature
range from 700 to 850  C and kept for 3e24 h. Then the sealed
samples were cooled down in air.
Approximately 1.5 mm thick samples were cut from the as-cast
and heat treated ingots with the lowest hardness. According to pre-
vious research results [14], the sample heated at 800  C for 18 h has
the lowest hardness and was chosen as the heat treated ingot to roll.
These samples were heated to different temperatures of 25e700  C in
furnace and held for 10 min, then quickly taken out for rolling process.
Rolling process was carried out on a 70-mm diameter rolling mill with
a roller speed of 0.5 m s
1. The initial roll gap was set to be 0.05 mm.
The roll gap would be increased by 0.02 mm for next sample if cracks
appeared in this selected sample, and it would be repeated until
cracks didn’t appear. The final rolling without cracks in the sample
would be valid and this reduction was the maximum reduction per
pass at this rolling temperature. On the other hand, the roll gap would
be reduced by 0.02 mm for next sample if cracks didn’t appear in this
selected sample, and it would be repeated until cracks appeared. The
58 Y. Yu, P. Jiang / Intermetallics 53 (2014) 56e61

Fig. 3. BSE-SEM images of NiTi precipitates and PFZs for V55Ti30Ni15 alloy heat treated at various temperatures for 18 h: (a) 700  C, (b) 750  C, (c) 800  C and (d) 850  C.

rolling before cracks appeared would be valid and this reduction was
the maximum reduction per pass at this rolling temperature. The
percent reduction was calculated by measuring the difference in
thickness before and after passing through the rolls and dividing it by
the original thickness.
from heat treated alloys by wire cutting to prepare TEM samples,
and then the 0.1 mm thin sample was ground to 50 mm by different
grit sandpapers. The sample was finally thinned using conventional
ion thinning at 4.4 kV of voltage and 6e8 of angle.

2.3. Microstructural analysis

An Olympus optical microscope (OM) was used to observe mi-

crostructures of the as-cast and heat treated alloys, and the samples
surfaces were etched in a mixture of hydrofluoric acid, nitric acid
and water. The possible precipitation phases of the as-cast and heat
treated alloys were examined using scanning electron microscopy
(Quanta 200 FEG-SEM, FEI Company) equipped with X-ray energy
dispersive spectroscopy (EDS). Surfaces were polished using 3 mm
and 1 mm diamond pastes without etching, and then micrographs
were recorded in back-scattered electron (BSE) mode. Qualitative
variations in Ti and Ni content in the as-cast V55Ti30Ni15 alloys were
characterized by EDS line scan. X-ray diffraction (XRD) data were
obtained with a Bruker D8 advance X-ray diffractometer employing
Cu Ka radiation with a tube voltage of 40 kV and current of 40 mA.
The sample was scanned over the 2-theta range 20e100 with a
step size of 0.02 and a count time of 4 s. Fine precipitation particles
were examined and identified by a transmission electron micro-
scope (TEM, JEM-2100, JEOL, Japan) equipped with EDS operating at Fig. 4. Relation curve of PFZs widths and temperature for V55Ti30Ni15 alloys heat
an accelerating voltage of 200 kV. 0.1 mm thin samples were cut treated for 18 h.
 Y. Yu, P. Jiang / Intermetallics 53 (2014) 56e61 59

Fig. 5. Morphologies of NiTi precipitates and PFZs for V55Ti30Ni15 alloy heat treated at 800  C and various time: (a) 3 h, (b) 6 h, (c) 12 h and (d) 24 h.

3. Results and discussion interdendritic metallic compounds, as shown in the OM image of

3.1. Initial microstructure
In the as-cast alloy, the microstructure consists of primary
dendrites of Vanadium solid solution (Vss) surrounded by
Fig. 1. These metallic compounds can be seen clearly in the SEM
image (inset of Fig. 1), and were identified as NiTi (light phase) and
NiTi2 (light-grey phase) using a combination of EDS/SEM and XRD
techniques, which are in agreement with the previously reported
multiphase microstructure [1].

Fig. 6. Relation curve of PFZs widths and holding time for V55Ti30Ni15 alloys heat Fig. 7. Relationship of maximum reduction per pass and rolling temperature for as-
treated at 800  C. cast and heat treated V55Ti30Ni15 alloys.
60 Y. Yu, P. Jiang / Intermetallics 53 (2014) 56e61
Fig. 8. BSE-SEM images of 70% of rolling reduction for different state alloys rolled at room temperature: (a) as-cast; (b) heat treated.
Owing to the high thermal conductivity of copper and rapid heat
extraction, this molten alloy solidifies rapidly as it comes into
contact with the water-cooled copper hearth. In this case, rapid
dendritic solidification of primary V produces a supersaturated
solid solution with much higher solute concentration than the limit
of equilibrium solid solubility at room temperature. However, so-
lute partitioning cannot be completely avoided using the cooling
rate of the arc melters water-cooled copper hearth (103 K/s), which
is much lower than other rapid solidification techniques such as
melt spinning (106 K/s) and splat quenching (108 K/s) [15,16],
resulting in only partial trapping of solute elements Ni and Ti in V.
The remaining solute atoms are segregated into the interdendrtic
regions where NiTi and NiTi2 intermetallic compounds form at the
end of solidification.
3.2. The orientation relationship between the precipitated NiTi and
the V-matrix
Figs. 2(a and b) shows SEM and TEM images of V55Ti30Ni15
alloy heat treated at 800  C for 18 h. It was observed from
Fig. 2(a) that small particles preferentially formed near the
boundaries between Vss and NiTi2/NiTi. V-matrix, NiTi phase,
NiTi2 phase and precipitated NiTi particle were identified by
analyzing the selected area electron diffraction (SAED) patterns
(in Fig. 2(c)) and marked in Fig. 2(b). Meanwhile, a PFZ formed at
the boundary of the V-matrix grain was observed. Fig. 2(c) show
SAED patterns with the ½011 zone axis taken from the precipi-
tated NiTi particle and the V-matrix in Fig. 2(a), respectively. Very
weak spots of (100) and (111) are visible in Fig. 2(c), suggesting
that the fine particle is NiTi with an ordered B2eCsCl structure. A
high resolution TEM (HRTEM) image of the interface between the
NiTi particle and the V-matrix is shown in Fig. 2(d) and corre-
sponding indices of crystal plane were marked. Through
analyzing SAED patterns and HRTEM image, the orientation
relationship between the precipitated NiTi and the V-matrix is
NiTi (011)kV (011), NiTi ½011kV ½011. Lattice parameters of these
NiTi and V are 3.019  A and 3.036  A, respectively. The misfit
parameter at the interface between the NiTi particle and the V-
matrix is 0.6%, indicating this interface is a coherent interface.
3.3. Morphologies of the NiTi precipitates and the PFZs after heat
treatment
Fig. 3 shows the morphologies of the NiTi precipitates and
the PFZs for V55Ti30Ni15 alloys heat treated at a temperature
range from 700 to 850  C for 18 h. When the alloy was heat
treated at 700  C, fine NiTi particles precipitated along the
boundary of the V-matrix grain and did not precipitate in the
center of the V-matrix grain. Meanwhile, the PFZs formed at the
boundary of the V-matrix grain (as shown in Fig. 3(a)). With
increasing temperature, more NiTi particles precipitated from
the boundary to the center of the V-matrix grain and some
particles near the PFZs started to aggregate and grow, and the
PFZs widths increased (as shown in Figs. 3(b and c)). When the
temperature increased to 850  C, the particles in the center of
the V-matrix started to disappear and the particles near the PFZs
got coarse, and the PFZs widths had no obvious variation (as
shown in Fig. 3(d)).
The relation curve of the PFZs widths and heat treatment tem-
perature is shown in Fig. 4. The PFZs widths were measured by
Image Pro-Plus software 6.0 (IPP 6.0). It can be seen that the PFZs
widths monotonically increases with temperature until 800  C and
the value increases from 147 nm at 700  C to 291 nm at 800  C.
When the temperature increases to 850  C, the PFZs widths are
almost the same with that at 800  C.
Fig. 5 shows the morphologies of the NiTi precipitates and the
PFZs for V55Ti30Ni15 alloys heat treated at 800  C for 3e24 h. When
the alloy was heat treated for 3 h, fine NiTi particles started to
precipitate along the boundary of the V-matrix grain and no pre-
cipitate was found in the center of the V-matrix grain. In addition,
the PFZs started to form at the boundary of the V-matrix grain (as
shown in Fig. 5(a)). This phenomenon is similar to that of the alloy
heat treated at 700  C for 18 h. When holding time extended to 6 h,
more NiTi particles precipitated and precipitate positions extended
from the boundary to the center of the V-matrix grain, and the PFZs
widths had little change (as shown in Fig. 5(b)). With holding time
increasing, the NiTi particles were found in the whole V-matrix,
some particles near the PFZs started to aggregate and grow, and the
widths of PFZs got larger (as shown in Fig. 5(c)). When holding time
increased further to 24 h, the area where the particles aggregated
and grew started to extend to the center of V-matrix, and the PFZs
widths increased further (as shown in Fig. 5(d)).
The relation curve of the PFZs widths and heat treatment time is
shown in Fig. 6. It can be noted that the PFZs widths increases with
increasing time. In addition, at the initial stage of heat treatment
(3e6 h), the slope of the curve is small and the PFZs widths in-
creases inconspicuously. When holding time increases from 6 h to
18 h, the slope of the curve gets larger and the PFZs widths in-
creases rapidly which reaches 291 nm at 18 h. When holding time
extends to 24 h, the PFZs widths increases slightly.
 Y. Yu, P. Jiang / Intermetallics 53 (2014) 56e61
3.4. Rollability
Fig. 7 shows the comparison of maximum reduction per pass
for as-cast and heat treated V55Ti30Ni15 alloys at various rolling
temperatures. It should be noticed that the rollability of heat
treated alloy is better than that of as-cast alloy, and the reduction
per pass increases about 30% at every rolling temperature. Fig. 8
shows the microstructures of the as-cast and heat treated alloys
rolled at room temperature with reduction of 70%. It is obvious
from Fig. 8 that the hard and brittle NiTi2 phases in the as-cast
alloy cracked seriously (as shown in Fig. 8(a)) during the roll-
ing, but a few NiTi2 phases cracked in the heat treated alloy (as
shown in Fig. 8(b)).
The V-matrix in the as-cast alloy has high harness and low
plastic due to the high cooling rate during the alloy solidification
[14]. During rolling deformation, the deformation of the interface
between the V-matrix and NiTi2 phase is difficult to coordinate,
therefore the cracks are easy to form at the interface because the
stress concentration occurred at the interface after dislocations
movement was obstructed. After the alloy was heat treated at
800  C for 18 h, the plastic of the V-matrix increased because the
NiTi particles precipitated in the V-matrix resulting in the
decrease of the hardness [14], improving the formability of the V-
matrix. Therefore, the force applied on NiTi2 phases decreased
and the fragment degree of NiTi2 phases decreased greatly. In
addition, the PFZ appeared at the boundary of the V-matrix grain
after heat treatment, which has a better plastic [12,13], and made
up for the bad deformability of NiTi2 phases, because the PFZs
and NiTi phases can provide necessary dislocations for the
deformation. Therefore the cracks occurred on NiTi2 phases were
restricted and can’t extend to the V-matrix to form macroscopic
cracks when the rolling reduction per pass is large enough. The
PFZs played an important role in restricting cracks extension and
coordinating deformation.
61
4. Conclusions
NiTi particles precipitated from V-matrix and the PFZs were
formed at the boundary of V-matrix grain in V55Ti30Ni15 alloys
during heat treated at a temperature range from 700 to 850  C and
kept for 3e24 h. The orientation relationship between the precipi-
tated NiTi and the V-matrix is NiTi (011)kV (011), NiTi ½011kV ½011.
The PFZs widths increased with increasing heat treatment time and
temperature. The PFZs played an important role in restricting cracks
extension and coordinating deformation during rolling process.
Acknowledgment
The authors are grateful to the reviewers who evaluated this
manuscript and gave valuable suggestions to improve the manuscript.
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