Materials Science & Engineering A 655 (2016) 122131

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Effects of thermomechanical treatment on microstructure and shape

memory effect of Ti13V3Al lightweight shape memory alloy
Z.Y. Yang, X.H. Zheng, W. Cai n
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, Peoples Republic of China

art ic l e i nf o

a b s t r a c t

Article history:
Received 30 September 2015
Received in revised form
14 December 2015
Accepted 16 December 2015
Available online 19 December 2015

The effects of thermomechanical treatment on microstructure, mechanical properties and shape memory
effect of Ti13V3Al alloy were investigated. A dual-phase structure which consists of phase and
martensite phase forms after thermomechanical treatment. As annealing temperature increases, the
amount of phase decreases and its morphology changes. Stress plateau decreases when annealing
temperature increases and elongation shows the opposite trend. Ti13V3Al alloy annealed at 700 C has
the best comprehensive mechanical property. Recoverable strain rst increases then decreases as annealing temperature increases. Ti13V3Al alloy annealed at 700 C for 0.5 h displays a large fully recoverable strain of 7.5%. It is believed that small, uniformly distributed phase benets the shape
memory effect. With the help of phase, martensite variants become small. The variants are supposed to
have a good mobility and that reduces the chance of introducing irrecoverable strain during tensile test.
The microstructure evolution of Ti13V3Al alloy annealed at 700 C during deformation was investigated. When the pre-strain is less than 7.5%, the recoverable martensite reorientation process
contributes to the deformation. When the pre-strain exceeds 7.5%, the crossover of martensite plates
leads to the deterioration of shape memory effect.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
Ti13V3Al alloy
Lightweight shape memory alloy
Thermomechanical treatment
Microstructure
Shape memory effect

1. Introduction
As the most commercially successful shape memory alloy ever
discovered, NiTi alloy has been widely used as advanced actuators and biomedical materials [14]. But it has a relatively high
density of 6.7 g/cm3 which is not light enough for the increasing
demand of weight reduction of aircrafts in aerospace industry.
Thus, it is highly signicant to develop light weight shape
memory alloy (LWSMA).
TiVAl alloy can be a good candidate for LWSMA. First of all,
the density of TiVAl alloy is relatively low (about 4.5 g/cm3)
and close to pure titanium. It is known that almost all traditional
shape memory alloys such as NiTiX (X Pd, Pt, Hf, and Zr), Cu
AlNi, NiAl, Co-based, NiMnGa and TiTa-based alloys have a
large density ranging from 6.49.0 g/cm3 which are not light
enough for the demand of weight reduction in aerospace application just like NiTi alloy. Comparing with these shape memory
alloys, the low density TiVAl alloy is very promising. Secondly,
TiVAl alloy has an excellent cold workability. During cold
rolling, a thickness reduction of over 90% can be easily obtained.
In contrast, NiTiHf/Zr alloy has a poor cold workability [5]. Ni
n

Corresponding author.
E-mail address: weicai@hit.edu.cn (W. Cai).

http://dx.doi.org/10.1016/j.msea.2015.12.049
0921-5093/& 2015 Elsevier B.V. All rights reserved.

MnGa alloy is brittle even at relatively higher temperature [6].

NiAl alloy has almost no plasticity at room temperature [7]. Cu
AlNi alloy has large grains around 1 mm in size, high elastic
anisotropy and precipitation of brittle phase at grain boundaries, making it lack of ductility [8]. It can be seen that workability is a big issue for many shape memory alloys and that is an
important advantage of TiVAl alloy.
Wayman investigated the shape memory effect of Ti16.1V4Al
(wt%) alloy [9]. It has been reported that Ti16.1V4Al (wt%) alloy
exhibited a fully recoverable strain of 3%. When the pre-strain was
6%, it showed a recoverable strain of 4%. But the martensitic
transformation temperature of Ti16.1V4Al (wt%) alloy was below room temperature. Recently, our team has developed Ti13V
3Al (at%) alloy as a new kind of LWSMA [10]. It showed a recoverable strain of 4.2% with a pre-strain of 6%. But the shape
memory effect of Ti13V3Al (at%) alloy is still not as good as NiTi
alloy which has a fully recoverable strain of 8%. It is known that
thermomechanical treatment can improve shape memory effect
by strengthening the alloy and increasing the critical stress for slip
[11,12]. Thus, in this paper, the effects of thermomechanical
treatment on martensitic transformation and shape memory effect
of Ti13V3Al alloy were investigated. A fully recoverable strain of
7.5% was obtained in annealed Ti13V3Al alloy after cold rolling.
Moreover, reports about microstructure evolution in TiVAl alloy
have never been seen before. In order to clarify the deformation

Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

mechanism of annealed Ti13V3Al alloy after cold rolling and

explain its excellent shape memory effect, the microstructure
evolution at different deformation stages was investigated by TEM
observation.

2. Experimental procedure
Ti13V3Al alloy was prepared by non-consuming vacuum arc
melting in a water-cooled copper crucible under Ar atmosphere.
Pure titanium, vanadium and aluminum with purity of 99.9%,
99.99% and 99.99% respectively were chosen for arc melting. Ingots
were melted for 6 times ipped over after each time to ensure the
homogeneity of composition. After arc melting, ingots were
homogenized at 900 C for 6 h in vacuum-sealed quartz tubes then
quenched into ice water. Ingots were cold rolled with a thickness
reduction of 60%. Cold rolled sheets were cut into different shapes
for different tests by wire cut electrical discharge machining.
Specimens inside sealed vacuum quarts tubes were annealed at
650, 700, 750 and 800 C for 0.5 h followed by ice water quenching. X-ray diffraction (XRD) was operated for the investigation of
phase constitution of annealed Ti13V3Al alloys at room temperature by a Cu K X-ray source. Martensitic transformation
temperatures of Ti13V3Al alloys annealed at 700 C were determined by differential scanning calorimetry (DSC) using PerkinElmer Diamond DSC, which is 295 C. Room temperature tensile
tests were processed on Instron 5569 universal mechanical testing
machine by a strain rate of 10  2 min  1. Specimens for transmission electron microscopy (TEM) observation were rst mechanical
polished to about 100 m then twinjet electropolished using a
solution containing 6% perchloric acid, 60% methyl alcohol and
34% n-butyl alcohol (by volume). The temperature during twinjet
electropolishing was  30 C.

3. Results and discussion

3.1. Phase and microstructure characterization
Fig. 1 shows the XRD patterns of Ti13V3Al alloys annealed at
different temperature after cold rolling. It can be seen that most
diffraction peaks of annealed Ti13V3Al alloys can be index as

Fig. 1. Room temperature XRD patterns of cold-rolled Ti13V3Al alloys annealed

at different temperatures.

123

orthorhombic martensite phase despite that the annealing

temperature is different. But there are diffraction peaks in every
XRD pattern that belongs to hexagonal phase, which is a kind of
equilibrium phases in titanium alloy and not seen in solution
treated alloy [10]. According to the XRD patterns, it can be seen
that relative intensity of phase when annealing temperature is
800 C decreases comparing with the situations of lower annealing
temperature, implying that the amount of phase decreases in
high annealing temperature situation.
Fig. 2 shows the bright eld TEM micrographs of Ti13V3Al
alloy annealed at different temperatures after cold rolling. It can be
seen that microstructure of the alloy consists of two phases. It can
be seen that microstructure of the alloy consists of two phases.
Combining the results of XRD and selected area diffraction pattern
inside Fig. 2a, one phase is hexagonal phase. Another is orthorhombic martensite phase. Massive TEM observation reveals
that the amount of phase decreases as annealing temperature
increases, as shown in Fig. 2ad, which is corresponding to the
result of XRD. Except for the decrease in amount, the morphology
of phase also changes as annealing temperature increases
known by massive TEM observation. When annealing temperature
is relatively low (like between 650 C and 700 C), as shown in
Fig. 2a and b, phase consists of equiaxial grains and they are
uniformly distributed in the alloy. Some of the grains become irregular and their density decreases when annealing temperature
is 750 C, as shown in Fig. 2c. phase is rare to nd when annealing temperature is 800 C and the grains become quite large,
as shown in Fig. 2d. Massive TEM observation also shows that the
average grain size of phase increases as annealing temperature
increases. It is estimated that the average grain size of phase is
about 200 nm when annealing temperature is 650 C. The grain
size increases to about 400500 nm when it comes to 700 C.
Some grains stays about 500 nm while some become unusually
large with irregular shape, as shown in Fig. 2c, when annealing
temperature is 750 C. The grains are over 1 m in Fig. 2d when
annealing temperature is 800 C. It is also indicated by massive
TEM observation that the density of remaining dislocations introduced by cold rolling decreases rapidly when annealing temperature is over 650 C.
These phenomenons can be explained by recrystallization
process during annealing. When annealing temperature is 650 C,
the recrystallization process begins. The remaining dislocations
introduced by cold rolling starts to reduce. The phase formed
during annealing displays a morphology of small equiaxial grains
and they are uniformly distributed in the alloy due to recrystallization. The remaining dislocations still keeps a certain
amount because the recrystallization process is not completed at a
relatively low temperature. When annealing temperature is
700 C, recrystallization process goes further. The density of remaining dislocations keeps dropping and the grain size of phase
increases. But phase is still uniformly distributed. When annealing temperature is 750 C, the density of remaining dislocations continues to decrease. Some grains of phase become
unusually large with strange shape and they are heterogeneously
distributed. This is thought to be a kind of unusual growing of
grains during recrystallization in high temperature. It means the
recrystallization is completed at 750 C. When annealing temperature is 800 C, both large grains of phase and large martensite variants appear.
Fig. 3 shows the phase diagram of typical titanium alloy. An
alloy with a V content of C0 is under different kinds of thermomechanical treatments. It can be seen that annealing at T1 and T2
in region leads to the formation of phase and phase
during recrystallization process. After fast cooling, phase remains unchanged and phase becomes phase through the
process of martensitic transformation. That leads to the existence

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Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

Fig. 2. Bright eld TEM micrographs of cold-rolled Ti13V3Al alloys annealed at different temperatures. (a) 650 C. (b) 700 C. (c) 750 C. (d) 800 C.

of phase at room temperature, as seen in Fig. 2. The V

content of phase (C1 and C2) in annealed alloy is higher than the
standard content C0. When the alloy is solution treated at T0 in
region and then quenched into water, only phase with a V
content of C0 will form through martensitic transformation. This is
the mechanism how phase forms in annealed Ti13V3Al alloys
after cold rolling while there is no phase in solution treated Ti
13V3Al alloy. When annealing temperature increases from T2 to
T1, as shown in Fig. 3, it can be inferred that the amount of phase
decreases according to phase amount calculation principle in
phase diagram. That explains the reduction of phase as annealing temperature increases which is shown by XRD and TEM.
Also, the increase of annealing temperature causes a shift of V
content in phase towards lower side (from C2 to C1), which
means a lower V content in martensite phase.

3.2. Mechanical properties

Fig. 4a shows the stressstrain curves of annealed Ti13V3Al
alloys at room temperature. It can be seen that the stressstrain
curve of Ti13V3Al alloy annealed at 650 C shows a particular
high stress plateau comparing to other annealed alloys. The stress
plateau of Ti13V3Al alloy annealed at 700 C decreases sharply
and its elongation increases to 17%. The stress-strain curve of Ti
13V3Al alloy annealed at 700 C displays a four-stage deformation
process: elastic deformation, martensite reorientation, uniform
deformation and necking. The stress plateau corresponding to
martensite reorientation starts from 1% to 3%, which is far less than
that of NiTi alloy. When annealing temperature increases to 750 C,
the height of stress plateau is close to the stress plateau when annealing temperature is 700 C and elongation increases a little bit
about 2%. But the stressstrain curve becomes a three-stage deformation curve: elastic deformation, uniform deformation and

Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

Fig. 3. Phase diagram of Ti13V3Al alloy.

900

a)

800
700

Stress (MPa)

600
500
400
300
200
100
0

10 12 14
Strain (%)

16

18

20

22

b)
18
16
Elongation(%)

necking. The plateau corresponding to martensite reorientation

cannot be found. When annealing temperature rises to 800 C, the
stressstrain curve does not change very much comparing to that of
700 C: it shows similar stress plateau, elongation and three-stage
deformation characteristic.
Fig. 4b shows the relationship between annealing temperature
and elongation. It can be seen that the elongation increases as
annealing temperature increases. When annealing temperature
increases from 650 C to 700 C, the elongation increases sharply
from 9.5% to 16.8%. After that the elongation increases smoothly
from 16.8% to 18.4% with the increase of annealing temperature
from 700 C to 800 C, which is considered a small change.
High stress plateau of Ti13V3Al alloy annealed at 650 C is
due to the combination effect of large amount of remaining defects
and hard phase introduced by low temperature annealing which
is relatively small and uniformly distributed. The morphology and
distribution of phase make it effective in strengthening materials. When annealing temperature increases from 650 C to
700 C, the recrystallization process proceeds which causes the
annihilation of remaining defects and growing of phase. It makes
strengthening effect weaken and that is why the stress plateau
decreases and elongation increases sharply. When annealing
temperature is over 750 C, remaining defects almost disappears
completely and the grains of phase grows larger and irregular,
which lead to further increase in elongation. But the effect is not
obvious so the change in elongation is less than 2%.
There is an interesting phenomenon in the stressstrain curves
of annealed Ti13V3Al alloys: obvious stress plateau corresponding to martensite reorientation can only be seen when annealing temperature is 700 C. We assume that proper strength of
the alloy makes the martensite reorientation process clear in a
stressstrain curve. If the density of remaining defects is too high,
like in the situation when annealing temperature is 650 C, martensite reorientation is covered by overcoming the obstacles to
deformation. If the strength of alloy is not high enough, it is easy
to introduce plastic deformation during tensile test and martensite
reorientation occurs simultaneously, like situations when annealing temperature is above 750 C. That is why the stress plateau
corresponding to martensite reorientation cannot be seen. With
proper strength, like the situation when annealing temperature is
700 C, martensite reorientation can happened before plastic deformation, which makes the stress plateau obvious to see.
3.3. Shape memory effect

20

14
12
10
8

125

650

700

750

800

Temperature ( C)
Fig. 4. (a) Stressstrain curves of cold-rolled Ti13V3Al alloys annealed at different temperatures. (b) Elongations of cold-rolled Ti13V3Al alloys annealed at
different temperatures with 6% pre-strain.

Fig. 5a shows the loadingunloading curves of annealed Ti

13V3Al alloys with 6% pre-strain at room temperature. The curving arrows represent shape recovery after heating above Af for
1 min. Ti13V3Al alloy annealed at 650 C exhibits a recoverable
strain of 5%. When annealing temperature rises to 700 C, recoverable strain increases to 6% which means fully recovered.
Recoverable strain decreases to 4.5% when annealing temperature
is 750 C. Further increase of annealing temperature to 800 C
leads to a slight decrease to 4.2% in recoverable strain. Fig. 5b
shows the relationship between recovery rate and annealing
temperature with 6% pre-strain. It can be seen that recoverable
strain rst increases then decreases as annealing temperature increases. The recovery rate increases from 83% to 100% as annealing
temperature increases from 650 C to 700 C, then recovery rate
decreases to 75% when annealing temperature is 750 C. Further
increase in annealing temperature to 800 C leads to a small drop
in recovery rate, which is 70%.
Ti13V3Al alloy annealed at 650 C contains the largest
amount of remaining defects and hard phase. Even it has the
highest strength, excess defects and phase hinder the shape
recovery in a certain extent. But when annealing temperature is

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Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

900

As Fig. 6ab display, the deformation can be fully recovered after

heating above Af temperature when the pre-strain is not more
than 7.5%. This is the highest value of fully recoverable strain ever
obtained in polycrystalline HTSMAs. When pre-strain is 8%, there
is a residue strain of 0.4% after heating, as Fig. 6c shows. It can be
implied that excess pre-strain causes plastic deformation. When
pre-strain is 10%, as Fig. 6d shows, the residue strain after heating
rapidly increases to 3.9%. It means irrecoverable deformation increases sharply as the pre-strain increases further.
Fig. 7 shows the relationship between recovery rate and prestrain in Ti13V3Al alloy annealed at 700 C. The recovery rate
stays 100% when pre-strain is not exceeding 7.5%. When pre-strain
is 8%, recovery rate slightly decreases to 95%. The recovery rate
decreases rapidly to 61% with a pre-strain of 10%.

a)

800

Stress (MPa)

700
600
500
400
300
200
100
0

100

3.4. Microstructure evolution during deformation

0

3
4
Strain (%)

b)

95

Recovery rate (%)

90
85
80
75
70
65
650

700
750
o
Temperature ( C)

800

Fig. 5. (a) Loadingunloading curves of cold-rolled Ti13V3Al alloys annealed at

different temperatures. (b) Recovery rate of cold-rolled Ti13V3Al alloys annealed
at different temperatures with 6% pre-strain.

above 750 C, remaining defects disappear with the proceeding of

recrystallization. The amount of phase decreases and they become unusually large and irregular. This kind of phases morphology and low density of remaining defects are not effective on
strengthening the alloy. That leads to a low critical stress for slip
and makes it easy to introduce plastic deformation during tensile
test, damaging the shape memory effect. Ti13V3Al alloy annealed at 700 C has the best comprehensive mechanical property.
Recrystallization process eliminates excess remaining defects and
keeps them at a proper amount. It is known that the proper
amount of dislocations is good for shape memory effect [1315].
Also, the small and uniformly distributed phase has a good
ability of strengthening the alloy [16]. Proper strength of the alloy
annealed at 700 C will prevent the occurrence of plastic strain
during deformation without hindering the shape recovery like the
situation when annealing temperature is 650 C. That is the reason
why Ti13V3Al alloy annealed at 700 C has the best shape
memory property.
Fig. 6ad show the loadingunloading curves of Ti13V3Al
alloy annealed at 700 C with different pre-strain. The curving
arrows represent shape recovery after heating above Af for 1 min.

3.4.1. Before deformation

Fig. 8 shows the bright eld TEM micrographs of Ti13V3Al
alloy annealed at 700 C with 0% pre-strain. It can be seen in
Fig. 9a that martensite variants in annealed Ti13V3Al alloy are
much thinner and smaller than that of solution treated alloy [10].
These martensite variants are randomly oriented which is called
self-accommodation morphology. The average width of twins
plates is about 40 nm and their length is almost no more than
1 m. Region A, B, C and D in Fig. 8a represent martensite variants
in three different orientations and circle 1, 2 and 3 represent three
grains of equiaxial phase. It can be seen that the growth of
martensite variant A is blocked by phase grain 1 and 2. This
interaction stops variant A from growing to a large variant like
variants in solution treated alloy and may assists the formation of
variant B and C with different orientations. Variant B and C are also
impeded by phase grain 2 and 3. Something similar can be seen
in Fig. 8b. Martensite variants D, E and F with three different orientations forms around phase grain 4. It can be inferred that
phase grain 4 has a similar inuence on the growth of variants D, E
and F like the situation in Fig. 8a.
It can be concluded that the small, equiaxial and randomly
distributed phase has a great inuence on the morphology of
martensite variants. They limit the scale of martensite variants by
stopping their growth and changing their orientations, similar
with the situation that occurs in TiNiHfCu alloy ribbons containing (Ti,Hf)2Ni precipitates [17]. That makes the formation of
small martensite variants with random orientations, which have a
different morphology compared to that of solution treated alloys.
3.4.2. 4% Deformation strain
Fig. 9 shows the bright eld TEM micrographs of Ti13V3Al
alloy annealed at 700 C with 4% pre-strain. It can be seen in
Fig. 9a that martensite reorientation has occurred in some area.
Martensite variant A shown by the dotted line is a large variant
compared to the situation of 0% pre-strain. It ranges over a few
micrometers in the direction perpendicular to martensite plates.
Even there is a grain of phase inside variant A, as the circle
1 shows, the orientation of martensite variant is not affected,
unlike the former situation with 0% pre-strain. It is believed that
such a large variant comes from martensite reorientation process.
The width of twins plates in variant A comes to a differentiation:
half of twins become thinner which is about 20 nm wide and the
other half becomes wider which is nearly 200 nm. This is the
process called de-twinning: half of the twins shrinks and vanishes
in the end, becoming one coarse martensite plate. The area below
variant A is almost de-twinned. The variant B shown by the dotted
line almost vanishes and it has a similar orientation with variant A.
It might be assumed that de-twinning process proceeds from
variant B towards variant A. The boundary between variant A and

Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

500

500

400

400

300

300

200

200

100

100

b)

600

a)

Stress(MPa)

Stress(MPa)

600

4
Strain(%)

127

4
5
Strain(%)

700

700

c)

d)

600

600
500

Stress(MPa)

Stress(MPa)

500
400
300
200

300
200

100
0

400

100
0

Strain(%)

10

Strain(%)

Fig. 6. Loadingunloading curves of cold-rolled Ti13V3Al alloy annealed at 700 C for 0.5 h with different pre-strain. (a) 7%. (b) 7.5%. (c) 8%. (d) 10%.

But martensite reorientation process and de-twinning process

are both not completed. It can be seen that there are still martensite variants in different orientation, as Fig. 9b shows. Variant D
shown by the dotted line is conducting martensite reorientation
process. Bottom part of variant D has formed a large martensite
plate while the upper part is blocked by a grain of phase which is
marked as circle 3. Variant E is in a different orientation compared
to variant D and they are almost mutually perpendicular.

100

Recovery rate (%)

90

80

70

60
7.0

7.5

8.0

8.5
9.0
Strain (%)

9.5

10.0

Fig. 7. Recovery rate of cold-rolled Ti13V3Al alloy annealed at 700 C for 0.5 h
with different pre-strain.

its bottom area is curving, which suggests that de-twinning process does not proceed homogeneously. Similar situation occurs in
deformed TiNiCu thin lms [18].

3.4.3. 8% Deformation strain

Fig. 10 shows the bright eld TEM micrographs of Ti13V3Al
alloy annealed at 700 C with 8% pre-strain. It can be seen that
martensite reorientation process is almost completed. Martensite
variants in Fig. 10a are nearly in one direction. Randomly distributed phase cannot impede the reorientation process in the
situation with 8% pre-strain. A small amount of martensite plates
cross with other plates, as shown in Fig. 10b. A coarse martensite
vairant crosses with other variants that have the same orientation,
as highlighted by dotted circle. But this is a minority phenomenon
in the situation with 8% pre-strain.
3.4.4. 10% Deformation strain
Fig. 11 shows the bright eld TEM micrographs of Ti13V3Al
alloy annealed at 700 C with 10% pre-strain. It can be seen that
the occurrence of crossover of martensite plates becomes much

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Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

2
B

1
D

200nm

F
E
D

2
D

200nm

200 nm

Fig. 8. (a,b) Bright eld TEM micrographs of cold-rolled Ti13V3Al alloy annealed
at 700 C for 0.5 h before deformation.

Fig. 9. (a,b) Bright eld TEM micrographs of cold-rolled Ti13V3Al alloy annealed
at 700 C for 0.5 h with 4% pre-strain.

more frequent. As Fig. 11a shows, large martensite plates cross

with each other in the position highlighted by dotted circle. Similar situation occurs in other area, as shown by Fig. 11b. The
martensite reorientation process which is almost completed
when pre-strain is 8% has been broken in the situation with 10%
pre-strain.

(1) Before deformation. During this stage, the small martensite

variants form as self-accommodation morphology. Randomly
distributed phase limit the growing of martensite variants
and change their orientations.
(2) 4% deformation strain. During this stage, martensite reorientation process and de-twinning process take place.
(3) 8% deformation strain. During this stage, martensite reorientation process is completed. A small number of martensite
plates starts to cross with other plates.
(4) 10% deformation strain. During this stage, a large number of
martensite plates cross with other plates. The martensite reorientation process is damaged.

3.5. Correlations between microstructure evolution and stressstrain

curve
The microstructure of Ti13V3Al alloy annealed at 700 C was
observed by TEM at different deformation stages. Fig. 12 shows the
combination of microstructure evolution and the stressstrain curve
with 10% pre-strain.

This relationship between deformation strain and microstructure evolution might provide an explanation for the excellent

Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

129

200 nm

200 nm
Fig. 10. (a,b) Bright eld TEM micrographs of cold-rolled Ti13V3Al alloy annealed at 700 C for 0.5 h with 8% pre-strain.

7.5% fully recoverable strain obtained in Ti13V3Al alloy annealed

at 700 C. We believe that comparing to the large martensite
variants in solution treated alloy, the mobility of small variants is
much higher and the deformation strain is easier to be accommodated elastically, which makes them easier to conduct a reorientation process without introducing irrecoverable deformation,
just like what occurs in FeMnSi based shape memory alloy [19].
Also, the strengthening effect of uniformly distributed phase
contributes a lot to the great shape memory effect. When the prestrain is 8%, which surpasses the fully recoverable strain of 7.5%,
the crossover of a small amount of martensite plates leads to a
small irrecoverable strain of 0.4%. The recovery rate decreases
sharply when the pre-strain is 10%. Obviously it is due to the
massive crossover of martensite plates which hinders the recoverable movement of martensite variants during shape recovery.

Fig. 11. (a,b) Bright eld TEM micrographs of cold-rolled Ti13V3Al alloy annealed
at 700 C for 0.5 h with 10% pre-strain.

3.6. The effects of

phase on enhancing shape memory effect

The effects of phase on the shape memory effect of Ti13V

3Al alloy annealed at 700 C can be summarized as below:
(1) Strengthening effect. Hexagonal phase is a kind of hard
phases comparing to martensite phase. It has the ability of
strengthening the alloy with proper morphology. Small, uniformly distributed phase in the alloy is good for the
strengthening of the matrix and that leads to an enhancement
of shape memory effect.
(2) Segmentation of martensite variants. Unlike the large martensite variants in solution treated alloy, small martensite variants with good mobility forms due to the existence of

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Z.Y. Yang et al. / Materials Science & Engineering A 655 (2016) 122131

(2)

(3)

(4)

Fig. 12. Correlations between microstructure evolution and stressstrain curve.

uniformly distributed phase. They have a better ability of

accommodating deformation strain elastically and preventing
the occurrence of irrecoverable strain. That also helps improving shape memory effect.
3.7. The effect of V content in the matrix (as well as in
martensite reorientation stress and recoverable strain

phase) on

Effect of changes in V content on martensite reorientation

stress and recoverable strain can be explained from the points of
both phase and martensite phase. The change of V content in
phase does not have an obvious inuence on the reorientation
stress and recoverable strain due to that phase is a hard phase in
all kind of V content, without obvious plastic deformation during
tensile test. The change of V content in martensite phase,
however, has a potential inuence on its shape memory behavior.
Martensite reorientation stress of shape memory alloy becomes
lower and recoverable strain is larger when deformation temperature is closer to martensitic transformation (Ms) temperature.
At lower annealing temperature, the V content in martensite phase
is higher compared to specimens annealed at higher temperatures.
So the Ms temperature is lower due to higher V content and much
closer to deformation temperature which is room temperature.
That leads to a lower reorientation stress and a larger recoverable
strain, theoretically. Combining the strengthening effect of phase
and work hardening, lower annealing temperature leads to better
shape memory behavior. But it is really difcult to distinguish the
effect of V content from strengthening effect. The alloy annealing
at 650 C shows a smaller recoverable strain compared to that of
700 C due to the large amount of remaining defects.

4. Conclusions
In summary, thermomechanical treatment has a great inuence
on microstructure, mechanical property and shape memory effect
of annealed Ti13V3Al alloy. The following conclusions can be
obtained.
(1) A dual-phase structure forms after thermomechanical treatment. They are hexagonal phase and orthorhombic
martensite phase. With the increase of annealing temperature,

(5)

the amount of phase decreases and its small, uniformly

distributed morphology changes to coarse, concentrated distributed morphology and the martensite variants become
larger.
The stress plateau decreases with increase of annealing temperature and the elongation follows an opposite trend. The
obvious stress plateau corresponding to martensite reorientation can only be seen when annealing temperature is
700 C. It is believed that the alloy has the best comprehensive
mechanical property when annealing temperature is 700 C.
Shape memory effect is rst improved then worsened with the
increase of annealing temperature. Ti13V3Al alloy annealed
at 700 C for 0.5 h exhibits the largest fully recoverable strain
of 7.5%.
The microstructure evolution during deformation provides an
explanation to the excellent shape memory effect. The small,
self-accommodated martensite variants have a good mobility
and that reduces the chance of introducing irrecoverable deformation during tensile test. When the pre-strain exceeds
7.5%, the crossover of martensite plates leads to the deterioration of shape memory effect.
The effects of phase on the improving of shape memory
effect of Ti13V3Al alloy annealed at 700 C can be summarized as strengthening effect and segmentation of martensite variants.

Acknowledgment
This work is supported by National Natural Science Foundation
of China (No. 51271065 and 51371069), Major State Basic Research
Development Program of China (973 Program) (No. 2012CB619403).

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