Precipitation of second phases in aged Ni rich

NiTiRe shape memory alloy

N. El-Bagoury*1,2
This study investigated the effect of aging on the structure and precipitation of second phases of
Ni52Ti47?7Re0?3 shape memory alloys. The alloy was solutionised at 1000uC for 24 h before aging
at various temperatures ranging from 300 to 600uC for 3 h. The matrix phase in both solutionised
and aged specimens was martensite. Ti2Ni phase was also present in the microstructure of both
solutionised and aged specimens and its volume fraction decreased as the aging temperature
increased. Ni4Ti3 phase began in appearance by increasing aging temperature to 400uC. Ni4Ti3
precipitates had lenticular and non-geometry shapes. Aging at 600uC led to precipitation of Ni3Ti
phase in the microstructure. This precipitated phase formed in white blocky shapes. Ti/Ni ratio
increased and/or Ni content decreased in the matrix with increasing in aging temperature.
Keywords: Ni rich NiTiRe shape memory alloys, Aging, Martensite, Second phase precipitate, Ti/Ni ratio

Introduction
Ti50Ni to Ti55Ni (at-%) can be termed as the pioneer
of shape memory alloys (SMA) and a key system for
studying phase transformations and precipitate evolution
in shape memory alloys. Shape memory alloys are
martensitic metals that remember the original shape of
their parent modification under specific conditions of
temperature and mechanical loading/unloading. The
thermodynamics of the parent bcc-structured, ordered
austenitic B2 phase and the monoclinic martensitic B199
phase are well understood. In order to improve shape
memory and mechanical properties, SMA is usually aged
at temperatures where precipitations of second phases
from the thermodynamically stable TiNi3 phase. In
particular, Ti3Ni4 plays an important role for martensite
formation. The martensite start temperature, Ms, is
strongly influenced by changes of plastic deformation
limits associated with precipitation hardening and the
change of the matrix composition due to precipitation.18
For instance, an increase in the martensite start
temperature of approximately 30uC was reported due to
aging of Ti50?7Ni2 (at-%). Recently, the fatigue failure
of TiNi SMA was related to the occurrence of TiNi3.9
Control of transformation temperatures of shape
memory alloys has been an important research subject
to enhance the reliability and applicability of these
functional materials.1014 Factors influencing the Ms
temperature are believed to be the elastic properties of
the parent austenite crystal and certain microstructural
features such as precipitates.11,15,16

Chemistry Department, Faculty of Science, TAIF University, PO Box 888,

El-Haweyah, El-Taif, Saudi Arabia
Casting Technology Lab., Manufacturing Technology Dept., CMRDI, PO
Box 87, Helwan, Cairo, Egypt

*Corresponding author, email nader_elbagoury@yahoo.com

W. S. Maney & Son Ltd. 2014

Received 30 May 2014; accepted 5 October 2014
DOI 10.1179/1878641314Y.0000000033

There are many factors that have great influence on

the transformation behaviours, such as, the composition
of alloys, aging treatment with precipitates, mechanical
treatment (cold working), addition of a third element,
point defects, dislocations and degree of order.17 Among
these factors, aging treatment is the most simple and
effective way, and is widely used to treat the TiNi based
alloys.18,19,2022,2325
It is known that precipitates will form from the
supersaturated sample during aging; and the existence
of precipitates will greatly affect the transformation
behavior.19,21,26
The precipitation process in nickel rich NiTi shape
memory alloys is significantly influences both the
structural and functional properties of the alloy. It is
known that the precipitation sequence is as follows: bo
to b1zNi4Ti3 to b2zNi3Ti2 to b3zNi3Ti where bo, b1,
b2 and b3 indicate changes in the matrix composition.
The Ni4Ti3 particles precipitating in early stages of
ageing have a rhombohedral structure and are uniformly
distributed in the matrix.
Until now, various abnormal transformation behaviours after aging have been found and their origins
have been discussed.1012 As a result, the equilibrium
relationship between TiNi matrix and Ni4Ti3 precipitates is still subject to uncertainty.
In this present study, microstructure and precipitation
of second phases such as Ti2Ni, Ni4Ti3 and Ni3Ti of
solutionised and aged NiTiRe shape memory alloy will
be investigated.

Materials and procedures

Polycrystalline Ni51Ti48?7Re0?3 shape memory alloy was
made by melting pure elements (more than 99?99%
purity) in an induction vacuum furnace. The alloy was
melted four times to ensure homogeneity and cast into
an investment casting ceramic mould. This mould was
preheated to 1000uC before pouring process.

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Precipitation of second phases

1 Microstructure of solution treated and aged NiTiRe shape memory alloys: a solutionised at 1000uC/24 h; b aged at
300uC/3 h; c aged at 400uC/3 h; d aged at 500uC/3 h; e aged at 600uC/3 h

Specimens from this alloy were solutionised at 1000uC

for 24 h followed by quenching in iced water. The aging
process was carried out at various temperatures ranging
from 300 to 600uC for 3 h then iced water quenching.
The microstructure of both solutionised and aged
specimens was investigated by Meiji optical microscope
fitted with digital camera as well as JEOL JSM5410
scanning electron microscope (SEM). The specimens
for microstructure examination were prepared by standard metallographic procedures according to standard
ASTM: E3-11 then etched in a solution of HNO3, HF
and H2O in a ratio of 4 : 1 : 5, respectively to investigate different types of precipitates. Another etching

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solution of HNO3/HF/CH3COOH in a ratio of 4 : 4 : 2

was used to examine the martensite phase. The different phases existing in the structure were analysed
using energy dispersive X-ray spectrometry (EDS)
attached in the SEM operated at 20 kV. The phase
transformations of the solutionised and aged alloys
were measured by Netzsch CC 200 F1 differential
scanning calorimetry (DSC) with a cooling/heating
rate of 10uC min21 in the temperature range from 230
to 150uC. Moreover, X-ray diffraction (XRD) was
carried out to identify the existing different phases in
the structure by using Cu Ka radiation with a step
scanning in 2h range of 3080u.

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Precipitation of second phases

2 Precipitation of second phases in aged NiTiRe shape memory alloy at a 300uC; b 400uC; c 500uC and d 600uC for 3 h

3 Ti2Ni precipitation
NiTiRe alloy

in

microstructure

of

solutionised

4 Volume fraction of Ti2Ni phase versus aging temperature

5 Fine and coarse martensite in NiTiRe alloy aged at 300uC/3 h

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Precipitation of second phases

6 X-ray diffraction for solution treated and aged NiTiRe shape memory alloys

7 Ti2Niprecipitated phase in aged alloy at 300uC for 3 h

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Precipitation of second phases

8 Lenticular coherent (Ni4Ti3) precipitation in alloy aged

at 600uC

Results and discussion

Phase constituents and microstructure of
solutionised and aged NiTiRe alloys
The microstructures of both solutionised and aged Ni
rich NiTiRe shape memory alloys are shown in Fig. 1.
The parent phase in all of these microstructures is
the martensite phase (B19). This means that the
martensitic phase transformation temperatures for
all of these specimens are above the room temperature. Additionally, precipitates of Ti2Ni second phase is
found in the microstructure of both solutionised and
aged specimens.
Ti2Ni phase precipitated in a blocky agglomerated
non-geometric shape in the microstructure of Ni rich
NiTiRe shape memory alloys, as shown in Fig. 2.
Figure 3 shows the distribution and size of the Ti2Ni
precipitates in the microstructures of aged NiTiRe
alloys. Ti2Ni phase is well distributed in the microstructure of the aged specimens.
The size of precipitated Ti2Ni phase are differing
among microstructures according to the conditions of
the heat treatment processes, as shown in Fig. 3.
Whereas the aging temperature increases the Ti2Ni
precipitates dissolute in the NiTi matrix. Therefore, the
Ni/Ti ratio in the matrix decreases with increasing aging
temperature leading to elevates the martensitic transformation temperature.
The size of the Ti2Ni precipitates in the microstructure of NiTiRe specimen aged at 300uC (Fig. 3a),
decreases as the aging temperature elevates to 400uC as
shown in Fig. 3b. As the aging temperature increases to
500 and 600uC, in addition to the dissolution of Ti2Ni
phase, some other precipitates appeared in the microstructure of these alloys in a small size as shown in
Fig. 3c and d.
From the microstructure shown in Fig. 3, the volume
fraction was measured and the obtained values are
represented in Fig. 4. It is obvious that the volume
fraction of Ti2Ni decreases by increasing the aging
temperature. This means that the volume fraction of
Ti2Ni phase decreases as the aging temperature increase
as shown in Fig. 4.
Figure 5a and b shows the SEM image of the NiTiRe
shape memory alloy aged at 300uC for 3 h followed by
quenching in iced water. It is obvious that the microstructure of the aged alloy is dominantly constituted by

9 Bulky and non-geometry precipitates of Ni4Ti3 phase in

a aged alloy at 500uC and b aged alloy at 600uC

the martensite plates. It is also clear that the martensite

found in some areas in the microstructure consists of fine
plates structure and are uniform in size (Fig. 5a). In other
some areas the microstructure reveals a random distribution of martensite plates having fine structure (white
circles) and coarse structure (black circles) as shown in
Fig. 5b.

X-ray diffraction for solution treated and aged

NiTiRe alloys
There are five XRD patterns; the first one related to the
solution treated alloy and the other four patters represent
the aged Ni51Ti48?7Re0?3 alloys as shown in Fig. 6. The
parent phase, which has the main diffraction peak (11), in
all solution treated and aged alloys is the martensite phase,
denoted as M. This means that the martensitic phase
transformation temperatures for these specimens are
above room temperature. In addition to the martensite
phase, the microstructure of the solution treated specimen
contains a precipitated Ti2Ni phase only. The latter
precipitated phase is a common denominator in all
microstructures of the investigated specimens with threes
peaks (110), (440) and (123) in all patterns.
The microstructure of the specimen aged at 300uC for
3 h has the same phase constitution as the solution
treated alloy, where they have identical X-ray pattern, as
shown in Fig. 6.
The XRD pattern of aged specimen at 400uC has a
new small peak for Ni4Ti3 phase, (112), as shown
in Fig. 6. By elevating aging temperature to 500 and
600uC, the Ni3Ti4 phase peak get more obvious than
that in XRD pattern of aged specimen at 400uC. The
presence of Ni3Ti phase in the microstructure of aged

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10 Ni3Ti precipitates in aged NiTiRe alloy at 600uC for 3 h

specimen at 600uC was confirmed by a new peak, (203),

appeared in its XRD pattern, as shown in Fig. 6.

Second phases precipitated in NiTiRe matrix

According to the heat treatment conditions, there are
various second phases precipitated in the microstructure
of NiTiRe shape memory alloys. These precipitated
second phases could be the equilibrium Ti2Ni and Ni3Ti
phases or metastable Ni4Ti3 phase.

In addition to the XRD pattern shown in Fig. 6, the

precipitation of Ti2Ni phase was confirmed using SEM
and EDX analysis as shown in Fig. 7. This precipitated
phase was found in the microstructures of all investigated specimens but with various volume fractions, as
shown in Fig. 4.
Surprisingly the precipitate has two phases as a
function of temperature, and one phase transforms to
the other martensitically by changing temperature. The
higher temperature phase has a tetragonal structure, the
lattice parameters being a50?3095 nm and c51?3585 nm
(at 100uC), while the low temperature phase has an
orthorhombic structure, the lattice parameters being
a50?4398 nm, b50?4370 nm and c51?3544 nm (at
20uC). See Ref. 27 for more details.
The precipitation of Ni4Ti3 phase was observed only
in the microstructures of the specimens aged at 400, 500
and 600uC. The microstructure of both solutionised and
aged specimen at 300uC was free of any precipitations of
Ni4Ti3 phase.
Figure 8 shows the precipitates of Ti2Ni and Ni4Ti3
phases in the aged alloy at 600uC. Ni4Ti3 phase
precipitated in a lenticular coherent shape as shown in
Fig. 8. The Ni4Ti3 precipitates have a rhombohedral
atomic structure with a50?670 nm, a5113?9u.28 The
composition of this precipitate was first determined by
EDS to be Ti11Ni14 by Nishida and Honma,29 and later

11 Spectrum and EDS analysis of colonies found in microstructure of aged alloy at 600uC

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12 Ti3Ni2 phase found in microstructure of aged alloy at 400uC

it was taken to be Ti3Ni4 by taking account the accuracy

of EDS.
In addition to lenticular shape, Ni4Ti3 phase precipitated in bulky non-geometric shapes as shown in
Fig. 8. This shape of Ni4Ti3 precipitates was found in
the NiTiRe alloy aged at 500uC, Fig. 9a and in alloy
aged at 600uC (Fig. 9b).
Sitepu et al. reported that precipitation of Ni4Ti3
particles occurred in a matrix of Ni rich NiTi SMA of
nominal composition Ni50?7Ti (at-%), when it was
solution annealed at 850uC for 15 min followed by water
quenching and aging at 400uC for 20 h.30
Pelton et al.31 reported dissolution of Ni4Ti3 between
500 and 600uC in Ti50?8Ni (at-%). Moreover the solvus
temperature of Ni4Ti3 phase is 560uC as estimated by
Yufeng Zheng et al.32 However in this study, Ni4Ti3
precipitates are still appeared in the microstructure of
aged specimen at 600uC for 3 h followed by iced water
quenching.
The equilibrium Ni3Ti phase precipitated only in the
microstructure of aged specimens at 600uC as shown in

Fig. 10. This phase precipitated in the microstructure as

bulky white shape. The TiNi3 phase has the hexagonal
DO24 type ordered structure. The lattice constants are
a50?5101 nm, c50?8306 nm and c/a51?6284.33
Moreover, in Fig. 11, and according to EDS analysis
there are some colonies in the microstructure classified
as a matrix phase.
From the above results, it can be concluded that the
optimum aging treatment conditions are ranging from
450 to 550uC for 3 h. Where the preferred Ni4Ti3 phase
that elevating martensite transformation temperature
above the room temperature,33 is precipitated in the
microstructure of Ni rich NiTiRe shape memory alloy
after aging at 450uC for 3 h. However, the precipitation
of undesirable Ni3Ti phase that affects the fatigue life
negatively33 in the microstructure of Ni rich NiTiRe
shape memory alloy starts with aging at 600uC for 3 h.
There are some other strange precipitates found in the
microstructures of the investigated alloy specimen. For
instance in the aged alloy at 400uC, the microstructure
contains some precipitates other than the recognised

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13 Ti4Ni3 phase found in microstructure of aged alloy at 400uC

ones such as Ti2Ni, Ni3Ti2, Ni4Ti3 and Ni3Ti that appear

in the binary NiTi phase diagram.33
According to the EDS analysis and atomic percentages, it was found precipitates of Ti3Ni2 and Ti4Ni3, as
shown in Figs. 12 and 13 respectively. The precipitation
of these phases and its conditions need more work in the
near future to be investigated.

Table 1 summarises the precipitated phases found

in different microstructures of solutionised and aged
NiTiRe shape memory alloy specimen.
The precipitation of the second phase formed at
different aging temperatures alter the Ti/Ni ratio or Ni
concentration in B19 matrix as shown in Fig. 14. As the
aging temperature increases the Ti/Ni ratio in B19
increases due to the dissolution of the second phase
Ti2Ni in the B19 matrix. In the same direction, the
precipitation of both Ni4Ti3 and NiTi3 phases at higher
temperature of aging process, 400 to 600uC, supports the
decreasing of Ni concentration or increasing Ti/Ni ratio
in the B19 matrix, as shown in Fig. 14.
As a result of the precipitation of Ni4Ti3 phase in the
microstructure of aged alloys at 400, 500 and 600uC
in addition to the precipitation of Ni3Ti phase in the
Table 1 Existence of precipitated phases in investigated
alloys

14 Ti/Ni ratio in matrix of NiTiRe alloy versus aging temperature

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Phase

B19 Ti2Ni Ni4Ti3 Ni3Ti Ti4Ni3 Ti3Ni2

Sol. treated alloy

Aged at 300uC
Aged at 400uC
Aged at 500uC
Aged at 600uC

!
!
!
!
!

!
!
!
!
!

6
6
!
!
!

6
6
6
6
!

6
6
!
6
6

6
6
!
6
6

El-Bagoury

microstructure of aged alloy at 600uC, the Ti/Ni ratio

increases while Ni content in the matrix decreases.34
Therefore, this changing in the chemical composition of
the matrix may affect the martensite transformation
temperature, which increases as the ageing temperature
increases.35

Conclusions
1. Martensite and Ti2Ni phases are the common
denominator in the microstructure of all investigated
alloy specimens. Ti2Ni phase dissolves in the matrix as
the aging temperature increase.
2. Ni4Ti3 phase starts in formation slightly in lenticular
as well as non-geometry shapes in the microstructure of
Ni52Ti47?7Re0?3 alloys with aging at 400uC and obviously
at 500 and 600uC for 3 h.
3. The precipitates of Ni3Ti phase appeared as white
blocky shapes in the microstructure of Ni52Ti47?7Re0?3
alloy after aging at 600uC for 3 h.
4. The optimum aging temperature for Ni52Ti47?7Re0?3
shape memory alloy is above 450uC to precipitate the
preferred Ti4Ni3 phase and below 550uC to avoid the
undesired Ni3Ti phase.
5. Ti/Ni ratio and/or Ti content in the matrix of
Ni52Ti47?7Re0?3 alloy increases as the aging temperature
increase.

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