Journal of Materials Processing Tech.

306 (2022) 117631

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Journal of Materials Processing Tech.

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

Microstructure and mechanical properties of Ni50.8Ti49.2 and Ni53Ti47 alloys

prepared in situ by wire-arc additive manufacturing
Jian Han a, b, Xinya Chen a, b, Guoyang Zhang a, Lianzhong Lu a, Yi Xin a, Bang Liu a,
Yangchuan Cai a, Xi Zhang c, Yinbao Tian a, b, *
a
School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China
b
Advanced materials processing and manufacturing research institute, Tianjin, China
c
Tianjin Bridge Welding Materials Group Co., Ltd., Tianjin, China

A R T I C L E I N F O A B S T R A C T

Associate Editor: Jingjing Li In this study, polycrystalline Ni50.8Ti49.2 and Ni53Ti47 single-walled components were prepared by dual-wire-arc
additive manufacturing (in-situ alloying) using TA1 and ER-Ni wires as feedstocks. The microstructural evolution
Keywords: in the building direction and the mechanical properties of the two components were also investigated. The
Wire-arc additive manufacturing phases of Ni50.8Ti49.2 and Ni53Ti47 change from NiTi + NiTi2 to NiTi + NiTi2+ Ni4Ti3 and from NiTi + NiTi2
Shape memory alloys
through NiTi + Ni3Ti to NiTi + Ni3Ti + Ni3Ti2+ Ni4Ti3, respectively, with increasing distance from the substrate.
Microstructure
The presence and absence of the NiTi(R) phase in the Ni50.8Ti49.2 and Ni53Ti47 components, respectively, were
Mechanical properties
In-situ confirmed using differential scanning calorimetry. The two components have similar fracture stress values (i.e.,
2.45 GPa); however, the fracture strain of Ni53Ti47 is 51.7% less than that of Ni50.8Ti49.2. The unrecoverable
strain of Ni50.8Ti49.2 gradually approaches 4.5%, while that of Ni53Ti47 increases linearly during a cyclic
compression test (15 load/unload cycles). This study reveals, for the first time, the phase evolution and me­
chanical properties of Ni53Ti47 components prepared using dual-wire-arc additive manufacturing and proposes a
novel method for the fabrication of a NiTi shape memory alloy with a flexible composition that meets the needs
of aerospace applications.

1. Introduction
NiTi shape memory alloys (SMAs) are intelligent materials that
possess beneficial properties such as outstanding ductility, high corro­
sion and fatigue resistance, superior damping capacity, and biocom­
patibility, as described in detail by Zhou et al. (2020). Sujith et al.
(2020), Wang et al, (2020a, b), and Varughese and El-Hacha (2020)
reported that SMAs are being increasingly applied in biomedical, aero­
space, and construction technologies, among others, owing to their
superelasticity and shape memory effect (SME). SMAs recover their
initial shapes and dimensions after deformation-at-strains exceeding
their elastic strain limits owing to the martensitic–austenitic trans­
formation. According to Patel et al. (2020) and Shariat et al. (2021), the
deformation recovery of NiTi SMAs can occur spontaneously upon
unloading (called “superelasticity”) or can be delayed until the material
is heated (called the “SME”). Shen et al. (2020) reported that the
development of NiTi alloys is an attractive research area owing to its
various application prospects.
The most common methods used to fabricate NiTi SMAs are casting
and powder metallurgy, but both methods have limitations. Casting is
performed at high temperatures, which can promote the formation of
impurities (oxides). Kai et al. (2019) investigated the vacuum induction
induced melting of the NiTi sample and deduced the following phase
transformation mechanism: (1) the dissolution of NiTi2 (with low oxy­
gen content) owing to the low energy barrier (ΔH), followed by (2) the
diffusion of oxygen in the Ni2Ti4Ox phase to increase its thermal sta­
bility. At the same time, casting is vulnerable to micro- and
macro-segregation, whereas powder metallurgy is unsuitable for the
preparation of complex parts and is prone to inducing defects like
porosity. Feng et al. (2022) revealed the effective micro-mechanism of
the laser hatch-spacing on the pore defects. Pore defects evolve from
keyholes of overlapping zones to uniformly distributed pores, and then
to unfused pores between pools or layers.
Wire-arc additive manufacturing (WAAM), which is among the most
promising, rapid manufacturing technologies, has significant advan­
tages, including high production efficiency (Zhao et al., 2020), low cost

* Correspondence to: School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China.
E-mail address: tianyinbao@email.tjut.edu.cn (Y. Tian).

https://doi.org/10.1016/j.jmatprotec.2022.117631
Received 1 March 2022; Received in revised form 5 May 2022; Accepted 14 May 2022
Available online 18 May 2022
0924-0136/© 2022 Elsevier B.V. All rights reserved.
J. Han et al.
Fig. 1. (a) Diagram of the setup used for D-WAAM, (b) diagram of sampling areas of an as-built component, and (c) different areas of an as-built component.
(Wang et al., 2013), high material utilization (Rodrigues et al., 2020),
and high flexibility (Li et al., 2020a). WAAM has been used to fabricate
Al alloys, Ti alloys, and other materials. Li et al. (2020b) explored the
effect of different shielding gases on the appearance of weld beads and
on the microstructures and mechanical properties of different samples
prepared using 5356 aluminum alloy welding wire. Xie et al. (2018)
investigated the effect of the crack growth direction on the fatigue crack
growth of Ti-6Al-4V prepared using WAAM. Zeng et al. (2020) fabri­
cated a NiTi shape memory alloy wall component by WAAM using
Ni-rich (50.5 at%) NiTi wire as a feedstock, demonstrating the feasibility
of using WAAM to prepare advanced functional materials. However, the
high cost of pre-alloyed NiTi wire limits the application of WAAM in the
fabrication of NiTi components. Lu et al. (2021) and Zhang et al. (2021)
reported that dual-wire-arc additive manufacturing (D-WAAM) is su­
perior to WAAM owing to its advantages, such as lower cost and higher
deposition rate; it is also suitable for the manufacturing of advanced
materials by in-situ alloying. D-WAAM can be performed using two
different wires as feedstocks to alloy different metals in situ. The in-situ
alloying of feedstock wires has been proven to be more economical than
the use of pre-alloyed feedstock wires. Owing to its high chemical ac­
tivity, low thermal conductivity, and recoverability, NiTi SMA is diffi­
cult to machine. It is vulnerable to tool wear and burring, prone to
forming reverse-curved metal wire, and difficult to draw into welding
wire; therefore, the availability of NiTi alloy welding wire is limited.
However, the availabilities of pure Ni and Ti wires are not limited, and
their feeding speed can be controlled to adjust the composition (and
associated properties) of the resulting alloy. fabricated Ni-rich NiTi
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Journal of Materials Processing Tech. 306 (2022) 117631
alloys using D-WAAM (in-situ alloying) and pure Ti and Ni wires. Pre­
vious studies on NiTi-based composites fabricated by D-WAAM have
been focused on their processing parameters, microstructures, defor­
mation behavior, shape memory effects, superelasticity, and phase
transformations, and have demonstrated that the manufacturing of NiTi
alloys using D-WAAM (in-situ alloying) is feasible.
The Ni contents of NiTi SMAs affect their phase transformation
behavior. Khalil-Allafi et al. (2002) found that the phase transformation
temperature (PTT) of NiTi SMA decreases by about 10 ℃ for every 0.1 at
% increase in its Ni content above 50 at%. This study investigated two
NiTi SMAs, Ni50.8Ti49.2 and Ni53Ti47, where the former is the most
studied NiTi SMA composition. The performances of the D-WAAM-pre­
pared Ni50.8Ti49.2 and Ni53Ti47 components were compared with their
corresponding components prepared using other methods. Considering
that single-walled components prepared using D-WAAM suffer from
high residual stress, we also investigated another alloy composition that
ensures the mechanical integrity of the single-wall component and
prevents cracking, (i.e., Ni53Ti47). The effects of the different composi­
tions (atomic ratios) on the PTT, microstructure, and mechanical
properties of the NiTi alloy were determined by analyzing the micro­
structure and mechanical properties of Ni50.8Ti49.2 and Ni53Ti47 pre­
pared by D-WAAM (in-situ alloying) using TA1 and ER-Ni wires as
feedstocks.
2. Experimental procedures
As shown in Fig. 1, the D-WAAM system used in this study consisted
J. Han et al. Journal of Materials Processing Tech. 306 (2022) 117631

Table 1
Chemical compositions of source materials (wt%).
Material C O N V S Fe Mn P Si Al Cu Ti Ni

TA1 0.009 0.108 0.003 – – 0.021 – – – – – 99.858 –

ER-Ni 0.005 – – – 0.002 0.1 0.4 0.002 0.380 0.350 0.05 2.85 95.861
TC4 substrate 0.012 0.19 0.016 3.96 – 0.15 – – – 6.01 – 89.662 –

abrasive silicon carbide papers (150–3000 grit) and subsequently pol­

Table 2
ished carefully using a 1.5-μm diamond-polishing compound. Finally,
Processing parameters.
the obtained sample was etched using Kroll’s reagent (HF:HNO3:H2O =
Parameters Ni50.8Ti49.2 Ni53Ti47 1:3:46) for 50 s. The as-built components were characterized using op­
Marching speed 150 mm/min 150 mm/min tical microscopy, X-ray diffraction (XRD; scanning range 30–80◦ ), and
Electrode to substrate 4 mm 4 mm scanning electron microscopy (SEM) in conjunction with energy-
Nozzle to substrate 30◦ 30◦ dispersive spectroscopy (EDS). The identified secondary phase was
Between nozzles 60◦ 60◦
Ar for GTAW torch 15 L/min 15 L/min
further characterized using selected-area electron diffraction (SAED)
Ar for Trailing shield 15 L/min 15 L/min and high-resolution transmission electron microscopy (HRTEM). The
Post argon flow duration 15 s 15 s PTTs of the as-built components were determined using differential
TA1 wire 1500 mm/min 1500 mm/min scanning calorimetry (DSC), where the heating/cooling rate was 10 ◦ C/
ER-Ni wire 1045 mm/min 1146 mm/min
min. The Vickers microhardness of each as-built component was
measured at different locations along its vertical axis; the load and load
of a tungsten arc welding (GTAW) power supply, tungsten inert gas duration were 1.9 N and 15 s, respectively. Compression tests (single
(TIG) torch, shielding gas system, two wire feeders, heating plate, and and cyclic) were performed using a compression tester to evaluate the
temperature controller. TA1 and ER-Ni wires (diameter: 1.2 mm) served mechanical properties of the components.
as feedstocks, and TC4 served as a substrate; their chemical composi­
tions are listed in Table 1. The composition (EX) of the alloys was 3. Results and discussion
controlled by controlling the wire feeding speed (WFS). Wang et al.
(2019) calculated EX (mass fraction) and AX (atomic fraction) as follows: 3.1. Phase identification
∑
EX = ∑
WFSi di ρi EXi
(1) The upper, central, and lower regions of the as-built components
WFSi di ρi were analyzed using XRD (Fig. 2). Elemental Ni and Ti were not detected
among the as-built components, indicating that the Ti and Ni in the
EX /MX feedstock wires react sufficiently during in-situ alloying. The lower re­
AX = ∑ (2)
EX /MX gion of the Ni50.8Ti49.2 contained NiTi2, NiTi(B2), and NiTi(R) phases at
where i is the metal wire (1, 2), EXi (X = Ni, Ti; i = 1, 2) is the mass room temperature, while the central and upper regions contained NiTi2,
fraction of an element in the metal wire, WFSi (i = 1, 2) is the WFS in NiTi(B2), NiTi(R), and NiTi(B19’) phases (Fig. 2(a)). Based on an
mm/min, di (i = 1, 2) is the wire diameter (mm), ρi (i = 1, 2) is the wire equilibrium phase diagram, the NiTi(B2) phase forms first in the liquid-
density in g/cm3, and MX (X = Ni, Ti) is the relative atomic mass. phase alloy. As the temperature decreases, a martensitic transformation
During D-WAAM, the time between the deposition of successive occurs, in which the NiTi(B2) phase transforms to NiTi(B19’). The lower
layers was 2 min, and the substrate was heated to 400 ◦ C. In this study, region of Ni53Ti47 contained NiTi2, NiTi(B2), and NiTi(R) phases, while
the components prepared using D-WAAM consisted of 10 layers; the the central and upper regions contained Ni3Ti2, Ni4Ti3, and Ni3Ti
processing parameters are listed in Table 2. phases.
A metallographic sample was cut from each as-built component These results indicate that the matrices of both components are the
using electrical discharge machining. Its surface was ground using NiTi(B2) phase. The intensities of the (100) peaks in the XRD patterns of

Fig. 2. XRD results of as-built components: (a) Ni50.8Ti49.2 and (b) Ni53Ti47.

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J. Han et al.
Fig. 3. SEM images of Ni50.8Ti49.2: (a) area A; (b) the area within the yellow rectangle in Fig. 3(a); (c) area B; (d) the area within the yellow rectangle in Fig. 3(c); (e),
(f) area C; and (g), (h) area D.
Ni50.8Ti49.2 and Ni53Ti47 are the highest with respect to their lower and
central regions, respectively. Naji et al. (2020) found that the intensities
of the (100) peaks (corresponding to the NiTi(B2) phase) decrease with
increasing amount of precipitates, dislocations, and lattice distortions in
the corresponding NiTi alloy. The difference in the phase compositions
of Ni50.8Ti49.2 and Ni53Ti47 accounts for the different Ni contents, where
the higher Ni content of the latter results in the formation of Ni-rich
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Journal of Materials Processing Tech. 306 (2022) 117631
phases, Ni3Ti and Ni3Ti2. During cooling, Ni4Ti3 → Ni3Ti2 → Ni3Ti;
accordingly, the Ni4Ti3 in Ni53Ti47 transforms into Ni3Ti2 and Ni3Ti
during the slow cooling process associated with D-WAAM. The existence
of the NiTi(R) phase is related to the presence of precipitates in the NiTi
(B2) matrix. The Ni4Ti3 phase was not detectable in Ni50.8Ti49.2 (by
XRD), as the Ni4Ti3 content of Ni50.8Ti49.2 was too low.
J. Han et al. Journal of Materials Processing Tech. 306 (2022) 117631

Fig. 4. SEM images of Ni53Ti47:(a) area A; (b) the area within the yellow rectangle in Fig. 4(a); (c) area B; (d) the area within the yellow rectangle in Fig. 4(c); (e), (f)
area C; and (g), (h) area D.(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

3.2. Microstructural characterization
Images of the microstructure of Ni50.8Ti49.2 are shown in Fig. 3, and
Table 2 lists the results of EDS analysis at various points. Fig. 3(a) and
(b) show the microstructure of area A (Fig. 1(c)) in Ni50.8Ti49.2, revealing
its matrix as well as the presence of an acicular phase and white particles
precipitated at the grain boundary. No obvious microcracks and pores
are present, the microstructure is fairly uniform, and no segregation is
apparent. According to the EDS analyses, the matrix is NiTi, the white
particles are NiTi2, and the acicular phase is Ni4Ti3. Wang et al. (2021)
reported that the basketweave pattern (acicular phase) is formed by
precipitates with high aspect ratios and various sizes arrayed in the
matrix. The angle between the longitudinal axes of intersecting pre­
cipitates is approximately 60◦ . This selective growth behavior is
attributed to the constraining effects of internal or external stresses. The
phase compositions of areas B and C of Ni50.8Ti49.2 are similar to that of

5
J. Han et al.
Table 3
EDS results of selected points in Fig. 3.
Position Ti Ni Possible phase
1 49.66 50.34 NiTi
2 65.09 34.91 NiTi2
3 46.67 53.33 Ni4Ti3
4 66.16 33.84 NiTi2
5 46.64 53.36 NiTi
6 50.53 49.47 NiTi
7 66.49 33.51 NiTi2
area A (Fig. 1(c)), as shown in Fig. 3(c–f). Fig. 3(g–h) show the region of
the as-built component nearest to the substrate, i.e., area D (Fig. 1(c)).
The number of NiTi precipitates in the as-built component gradually
increases from area D to area C and eventually evolves into its matrix.
The substrate of the as-built component is TC4; consequently, the Ti
contents of the first few layers (dilution-affected region) of the compo­
nent are comparatively high, and the volume fraction of NiTi is
comparatively low. During the deposition of the first layer of the
component on the TC4 substrate, the surface of the substrate melted,
increasing the Ti concentration of the NiTi molten pool. During the
deposition of the second layer, a portion of the first layer remelted,
incorporating some of the Ti from the first layer into the second layer.
The Ti content of the first layer was lower than that of the substrate, and
the Ti content of the second layer was lower than that of the first layer.
The change in Ti content of the as-built component corresponds to the
change in its NiTi2 content. Finally, the matrix of the component evolves
into NiTi. In the subsequently deposited layers, NiTi2 precipitates are
present in the NiTi matrix and at the grain boundaries. Based on cal­
culations by Laeng et al. (2007), the Gibbs free energies of formation of
the NiTi2 phase are − 74.7 KJ/mol and − 58.2 KJ/mol. Thus, the for­
mation of the NiTi2 phase is thermodynamically favored over the for­
mation of the NiTi phase. Consequently, during cooling, the NiTi2 phase
forms first and grows along the NiTi grain boundaries. Zou et al. (2021)
studied the solidification mechanism of the Ni50Ti50 alloy in detail using
electrostatic suspension technology. They found that the primary NiTi
phase develops preferentially as equiaxed dendrite, and the remaining
liquid phase forms NiTi2 and α-Ti phases at the NiTi grain boundaries.
Images of the Ni53Ti47 microstructure are shown in Fig. 4, and the
results of EDS analyses at various points are listed in Table 3. Similar to
Ni50.8Ti49.2, no microcracks and pores are visible. White needle-like
precipitates are evident in area A (Fig. 1(c)) of the component (Fig. 4
(a) and (b)). The EDS results reveal that these needle-like precipitates
are Ni3Ti2 and occur in high density in areas A and B (Fig. 1(c)). Fig. 4(c)
indicates the existence of precipitation-free zones (PFZs) at the grain
boundaries, as described by Adharapurapu et al. (2010). The massive
precipitates and needle-like precipitates near the PFZs are due to the
different morphologies of the precipitates; EDS analysis revealed that all
the precipitates were Ni3Ti. PFZs are formed via two main mechanisms,
as summarized by Maldonado and Nembach (1997): 1) the loss of excess
quenched-in vacancies from the interior of grains to the grain bound­
aries (vacancies are considered necessary for the nucleation of the pre­
cipitates), and 2) the loss of an element that is essential to the formation
of the desired precipitate from grains because the element precipitates in
the grain boundaries. The high interface energy at the grain boundaries
promotes the preferential nucleation and growth of Ni3Ti. Therefore, the
Ni3Ti at the grain boundaries form large blocks, while Ni3Ti within the
grain is mostly acicular or granular. The precipitation of Ni3Ti reduces
the Ni content of the surrounding matrix, resulting in the formation of
PFZs. Area C is composed of both NiTi and NiTi2 matrices (Fig. 4(e) and
(f)). The precipitates at the grain boundaries of NiTi are NiTi2, which
precipitates preferentially, based on the Gibbs free energy of formation
of the two phases. Fig. 4(f–h) reflect the changes in the Ti contents of the
lower layers of the Ni53Ti47 component, which manifests a corre­
sponding change in its matrix. The NiTi2 phase is gradually refined as
the distance from the substrate increases. Fig. 4(g) and (h) show the
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Journal of Materials Processing Tech. 306 (2022) 117631
Table 4
EDS results of selected points in Fig. 4.
Position Ti Ni Al Possible phase
1 42.67 57.33 – Ni4Ti3
2 35.91 64.09 – Ni3Ti2
3 26.18 73.82 – Ni3Ti
4 47.35 52.65 – NiTi
5 26.76 73.24 – Ni3Ti
6 52.18 47.82 – NiTi
7 51.01 48.99 – NiTi
8 63.20 31.97 4.83 NiTi2
9 72.64 19.04 8.31 α-Ti+NiTi2
presence of NiTi precipitates in a NiTi2 matrix. Consistent with a binary
phase diagram of NiTi, increase in the Ni content of a deposited layer is
accompanied by the formation of NiTi2, resulting in a (α-Ti + NiTi2)
region. Once the Ni content of a deposited layer exceeds 34 wt%, the
NiTi phase emerges.
The microstructures of the Ni50.8Ti49.2 and Ni53Ti47 components
differ. The phase composition and morphology of the dilution-affected
regions of the two components are similar, and although the
elemental contents of the two components above their dilution-affected
regions are similar, their precipitated phases, which are closely related
to their Ni contents, differ. Naji et al. (2020) and Liu et al. (2021) re­
ported that the phase transformation of Ni4Ti3 in Ni53Ti47 is as follows:
Ni4Ti3 → Ni3Ti2 → Ni3Ti. Ni4Ti3 and Ni3Ti2 are metastable phases that
transform into stable Ni3Ti at high temperatures or over time. According
to Nishida et al. (1986), the transformation proceeds as follows:
αo → α1 + Ni4Ti3 → α2 + Ni4Ti3 + Ni3Ti2→ α3 + Ni3Ti2 → α4 + Ni3Ti2 +
Ni3Ti → α5 + Ni3Ti，
400 ± 10 ◦ C ≤ T ≤ 650 ± 10 ◦ C
αo → α1’ + Ni3Ti2 → α2’ + Ni3Ti2 + Ni3Ti → α3’+ Ni3Ti,
700 ± 10 ◦ C ≤ T < 800 ± 10 ◦ C
αo → α1’’ + Ni3Ti,
800 ± 10 ◦ C ≤ T ≤ 1015 ± 10 ◦ C
In this experiment, the D-WAAM process itself possessed a complex
thermal history, which can be roughly considered an in-situ heat treat­
ment coupled with slow cooling after material deposition, promoting the
transformation of metastable phases. Consequently, the Ni53Ti47 con­
tained a considerable amount of Ni3Ti precipitates.Table 4.
The TEM images shown in Fig. 5(a) and (b) reveal that the
Ni50.8Ti49.2 component is mainly composed of a matrix (gray) and white
precipitates (black), where most of the precipitates are bar-like or
granular. An SAED analysis of the two phases revealed that the matrix
and precipitates are NiTi and NiTi2, respectively. The orientational re­
lationships between these two phases are (2 − 20)NiTi2//(0 − 20)NiTi and
[220]NiTi2//[011]NiTi. In addition, dislocations were observed near
NiTi2; representative locations were selected for analysis.
Fig. 6 shows the dislocations in Ni50.8Ti49.2, which are mainly
distributed in the NiTi matrix between NiTi2 phases and form disloca­
tion tangles and networks. Toprek et al. (2015) reported that the dis­
locations are caused by the difference between the thermal expansion
coefficients of NiTi2 and NiTi. The aggregation of dislocations near
precipitates reduces the crystallinity of the matrix phase, leading to a
decrease in the intensity of the (110) peak in the corresponding XRD
pattern. Therefore, the (100) peak in the XRD pattern of the lower region
is more intense than those in the XRD patterns of the central and upper
regions.
Fig. 7(a) shows the interface between a NiTi2 precipitate and the NiTi
matrix. The HRTEM analysis of the two-phase interface (Fig. 7(b))
revealed the presence of a transition layer between the matrix and
precipitated phase. The fast Fourier transforms (FFTs) of points c (Fig. 7
J. Han et al. Journal of Materials Processing Tech. 306 (2022) 117631

Fig. 5. (a–c) TEM bright-field images of Ni50.8Ti49.2 and corresponding (d–f) SAED patterns.

Fig. 6. TEM images of NiTi2 and NiTi in the Ni50.8Ti49.2 component. Dislocations are typically distributed in the NiTi matrix.

(c)) and d (Fig. 7(d)), inverse FFTs, and lattice spacings of the phases (D-
spacings, insets of Fig. 7(c) and (d)) confirmed that the matrix is NiTi
and the precipitate is NiTi2; the lattice spacings of NiTi and NiTi2 are
0.2115 and 0.2823 nm, respectively.
The upper region of Ni53Ti47 was observed using TEM; Fig. 8(a–e)
show the microstructure and Fig. 8(f–i) show the corresponding SAED
images of various selected points. Two different precipitated phases are
visible in Fig. 8(a) and (b): acicular and spherical. Fig. 8(c) shows the
morphologies of these two phases under a high-powered microscope.
Several dislocations are apparent near the precipitated phases, and
stacking faults are present in the acicular phase. A large spherical grain
(Fig. 8(c)) was analyzed using SEM-EDS and was determined to be
Ni3Ti2. The Ni3Ti2 grain grows over time, as shown in Fig. 8(d). Fig. 8(f)
shows a TEM image of the Ni4Ti3 phase; a typical superlattice reflection
is observable in addition to the NiTi reflection, which subdivides the
reciprocal space of (321) NiTi(B2) into seven intervals. Two types of
Ni3Ti can be found in the Ni-rich NiTi alloy; one is a stable DO24 η-Ni3Ti
(hexagonal) phase and the other is a metastable L12 γ′ -Ni3Ti (FCC)
phase. Based on the high-resolution image (Fig. 8e) and SAED pattern
(Fig. 8g), the Ni3Ti phase in the Ni53Ti47 component is the DO24 η-Ni3Ti
phase, not the L12 γ′ -Ni3Ti phase. The SAED pattern shown in Fig. 8(g)
confirms that the matrix of Ni53Ti47 is NiTi(B2); the orientational

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J. Han et al.
Fig. 7. HRTEM analysis of Ni50.8Ti49.2: (a) two-phase interface selected for HRTEM; (b) HRTEM image of the area within the yellow square in (a); FFTs of (c) NiTi2
and (d) NiTi phases (insets: corresponding inverse FFTs and lattice spacings).
relationships between the Ni3Ti and NiTi phases are (0 − 20)Ni3Ti//
(111)NiTi and [100]Ni3Ti//[0 − 11]NiTi. Fig. 8(h) shows the orientational
relationships between the NiTi and Ni3Ti2 phases, viz. (111)Ni3Ti2//
(111)NiTi and [0 − 11]Ni3Ti2//[01 − 1]NiTi. Fig. 8(f) shows the SAED
pattern of a point at which all three phases exist, where the diffraction
spots of Ni3Ti indicate stacking faults.
Three points in the Ni53Ti47 component were selected, and the in­
terfaces between the phases were investigated using HRTEM (Fig. 9
(b–d)). According to the FFT results (Fig. 9(e)), the interface shown in
Fig. 9(b) separates the NiTi and Ni3Ti2 phases. The corresponding in­
verse FFTs show that the lattice spacings (D-spacings) of NiTi and Ni3Ti2
are 0.2065 and 0.2122 nm (Fig. 9(h) and (k)), respectively. Similar
analyses reveal that the lattice spacings of the Ni3Ti2 and Ni3Ti phases
shown in Fig. 9(f) and (g) are 0.2078 and 0.2236 nm (Fig. 9(i) and (l)),
respectively, and 0.2111 and 0.2245 nm (Fig. 9(k) and (m)),
respectively.
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Journal of Materials Processing Tech. 306 (2022) 117631
3.3. Phase transformation behavior
Fig. 10 shows the DSC curves of the two components; their PTTs were
determined from these curves. The DSC curve of Ni50.8Ti49.2 (Fig. 10(a))
shows its phase transformation from the initial to final temperatures (Rs
= 12.1 ◦ C, Af = 53.6 ◦ C, Ms = 32.5 ◦ C, and Mf = − 49 ◦ C). The phase-
transition peaks in the DSC curve of Ni50.8Ti49.2 are broad. Moreover,
a shoulder peak representing the NiTi(R) phase transition arises, which
corresponds to the thermoelastic transformation of the rhombohedral
NiTi(R) phase to austenitic NiTi(B2) phase. Jiang et al. (2015) reported
that this transformation occurs before the formation of NiTi(B19′ ) dur­
ing cooling owing to the presence of crystal defects (such as dislocations)
or Ni4Ti3 precipitates. According to the DSC curve of Ni50.8Ti49.2, the
temperature of the room (25 ◦ C) is higher than that corresponding to the
onset of the NiTi(R) phase transformation (Rs = 12.1 ◦ C) but lower than
the final temperature at which this transformation is complete. Thus,
Ni50.8Ti49.2 contains the NiTi(R) phase, which is consistent with the XRD
results. It should be noted that the formation of the NiTi(R) phase is
J. Han et al.
Fig. 8. (a–f) TEM bright-field images of Ni53Ti47 and (g–i) corresponding SAED patterns.
generally caused by stress fields around coherent Ni4Ti3 precipitates.
Thus, the presence of the NiTi(R) phase indirectly confirms the presence
of the Ni4Ti3 phase in the Ni50.8Ti49.2 component. These results are
consistent with the SEM results. The discontinuity of the Ni50.8Ti49.2
matrix, which is segmented by Ni4Ti3 precipitates, is responsible for
inhibiting the martensitic transformation and thus yields a more gradual
transformation process. In addition, the initial temperature of the
martensitic transformation during cooling is higher than the room
temperature. Therefore, Ni50.8Ti49.2 contains both martensite and
austenite; this uneven composition impairs the superelasticity of
Ni50.8Ti49.2. No phase-transition peaks appear in the DSC curve of the
Ni53Ti47 component owing to the inhibition of the martensitic trans­
formation. This phenomenon is mainly attributed to 1) the high Ni
content (53 at%) of Ni50.8Ti49.2, resulting in a Ni-rich matrix (the PTT
9
Journal of Materials Processing Tech. 306 (2022) 117631
decreases with increasing Ni content of the NiTi matrix according to
Khalil-Allafi et al. (2002)); and 2) the presence of abundant Ni3Ti and
Ni3Ti2 precipitates (Wasilewski, 1971). There is a certain lattice
mismatch between the precipitates of intermetallic compounds and the
austenite matrix; the pinning effect of the nonconformal phase bound­
aries inhibits martensitic transformation.
3.4. Microhardness
The microhardness of the as-built components along their vertical
axes was measured, and the results are plotted in Fig. 11. The hardness
of the Ni50.8Ti49.2 component (blue curve) initially increases along its
vertical axis with increasing distance from the substrate before
decreasing and then stabilizing. This initial increase in hardness is due to
J. Han et al. Journal of Materials Processing Tech. 306 (2022) 117631

Fig. 9. HRTEM images of phase interfaces in the Ni53Ti47 component: (a) interfaces selected for HRTEM; and HRTEM images of (b) NiTi/Ni3Ti2, (c) Ni3Ti2/Ni3Ti, and
(d) NiTi/Ni3Ti interfaces. FFTs of (e) Fig. 9(b); (f) Fig. 9(c); (g) Fig. 9(d); and (h–m) corresponding inverse FFTs (lattice spacings).

10
J. Han et al. Journal of Materials Processing Tech. 306 (2022) 117631

Fig. 10. DSC curves of (a) Ni50.8Ti49.2 and (b) Ni53Ti47 components.

the dilution effect of the substrate, which leads to abundant formation of

the NiTi2 phase and increases the hardness of the matrix. The maximum
hardness of this area of the Ni50.8Ti49.2 component is 575.9 HV0.2. As the
dilution effect fades, the matrix transforms into NiTi(B2) and stabilizes;
the hardness similarly stabilizes at ~278 HV0.2. The slight fluctuation in
the hardness is related to the volume fraction of NiTi2 precipitates. As
the distance from the substrate increases, the hardness of the Ni53Ti47
component (red curve in Fig. 11) sharply increases, decreases, and then
increases again before stabilizing. The microstructural analysis and
phase diagram of the Ni–Ti alloy system indicate that the component
consists of a mixture (NiTi2 + α-Ti) near the substrate; the presence of
NiTi2 improves the hardness of the Ni53Ti47 component. The sharp
decrease in the hardness of the component is attributed to the change of
its matrix from NiTi2 to TiNi(B2), resulting in an overall decrease in its
hardness to 266 HV0.2. The phase composition of the component be­
comes uniform with increasing distance from the substrate. The micro­
structural analysis indicates that this area of the component consists of a
NiTi matrix and a small amount of NiTi2 precipitates. The hardness of
the Ni53Ti47 component increases again before stabilizing owing to the
Fig. 11. Microhardness of components along their vertical axes.
formation of Ni3Ti precipitates, which has a pinning effect that prevents
the migration of dislocations and enhances the hardness of the material.
Moreover, Ni3Ti is very hard; according to Li et al. (2017), the hardness

Fig. 12. (a) Stress–strain curves of (a) Ni50.8Ti49.2 and (b) Ni53Ti47 components prepared using D-WAAM.

11
J. Han et al.
Fig. 13. Cyclic compression test of components prepared using D-WAAM: (a) cyclic stress–strain curves of Ni50.8Ti49.2; (b) accumulated residual strain of Ni50.8Ti49.2;
(c) cyclic stress–strain curves of Ni53Ti47; and (d) accumulated residual strain of Ni53Ti47.
of Ni3Ti is ~1071 HV. These factors account for the high hardness of the
Ni53Ti47 component.
3.5. Compression test
In order to evaluate the mechanical properties of the two compo­
nents, the specimens were subjected to a compression test in which they
were compressed until failure. The representative stress–strain curves
are given in Fig. 12. Liu et al. (1998) reported that the deformation of
NiTi SMA involves four main stages, viz. the elastic deformation stage of
austenite, the stress-induced martensitic transformation stage, the
martensitic deformation stage, and the fracture stage. The stress–strain
curve of the Ni50.8Ti49.2 component (Fig. 12(a)) reflects these four stages
and indicates a fracture stress of 2.42 GPa with a corresponding fracture
strain of 28.6%. The component undergoes an austenitic elastic defor­
mation up to a strain of 3.7%, stress-induced martensite transformation
between a strain of 3.7 (stress 0.63 GPa) and 15.7%, and martensitic
deformation between a strain of 15.7% and 28.6%. In the martensitic
deformation stage, martensite starts to plastically deform and fractures
at a strain of ~13.8% with a corresponding fracture stress of ~2.47 GPa.
The expected four deformation stages are not observed in the stress–­
strain curve of the Ni53Ti47 component. Moreover, the fracture strain of
the Ni53Ti47 component is less than that of the Ni50.8Ti49.2 component.
Based on the microstructural analyses, the matrices of both components
are NiTi(B2); the components differ only in terms of their precipitated
12
Journal of Materials Processing Tech. 306 (2022) 117631
phases. The precipitated phase in Ni53Ti47 is small and mainly composed
of Ni3Ti, appearing not only at grain boundaries but also within the
grains. During significant plastic deformation, the interfaces between
the NiTi(B2) and Ni3Ti phases hinder the slip of dislocations, resist
dislocation line movement, and increase slip resistance, thereby
increasing the strength and hardness of the Ni53Ti47 component and
reducing its plasticity and toughness. The presence of Ni3Ti precipitates
also has a pinning effect on the matrix, which inhibits martensitic
transformation.
3.6. Superelasticity
Cyclic compression tests were performed to evaluate the super­
elasticity of the components; the results are shown in Fig. 13. A total of
15 loading/unloading cycles were performed during each test, at the
same strain rate. Superelasticity is related to the stress-induced
martensitic transformation and its inverse strain. The cyclic compres­
sion test of Ni50.8Ti49.2 was performed under loads up to 12 kN, corre­
sponding to the maximum stress of the stress-induced martensite
transformation stage in the compression test. The cyclic stress–strain
curves of Ni50.8Ti49.2 show superelastic deformation behavior, i.e., a
stress plateau (Fig. 13(a)). During the cyclic compression test (load:
20 kN) of the Ni53Ti47 component, no stress plateaus were observed in
the obtained stress–strain curves (Fig. 13(c)). The unrecoverable (re­
sidual) strain of the Ni50.8Ti49.2 component gradually stabilizes (Fig. 13
J. Han et al.
(b)), while that of Ni53Ti47 continues to increase (Fig. 13(d)). Wasilewski
(1971) reported several factors that affect the superelasticity of mate­
rials, including the test temperature, strain rate, heat treatment or me­
chanical treatment, and grain size. In this study, the applied strain rate
was identical and the components were not heat treated. Therefore, the
loss of superelasticity can be analyzed in terms of test temperature,
phase composition, and grain size. Additive manufacturing is charac­
terized by a non-equilibrium crystallization process; accordingly, the
components consist of single microstructures that are non-uniform along
their vertical axes; these regions of columnar and equiaxed crystals
affect the local mechanical properties of the components. Zeng et al.
(2020) reported that regions with coarse grains deform more easily than
those containing finer grains; the difference in superelasticity of these
regions is related to martensitic stability. The different microstructures,
i.e., the columnar crystals at the bottom of a compressed sample and
equiaxed crystals at the top, can account for the unrecoverable strain of
the Ni53Ti47 component, and the degree of deformation of a compressed
sample can reveal whether uneven deformation occurs. In addition, the
XRD results revealed that Ni53Ti47 does not consist entirely of austenite
at the test temperature (~25 ◦ C). Therefore, some unrecoverable strain
can also be attributed to the presence of martensite before any stress is
applied. Since the cyclic compression test was carried out at room
temperature, which did not exceed the final temperature of austenite
transformation, the component could not completely recover during the
cyclic compression test; thus, its recoverable strain is lower than that of
NiTi SMA prepared using conventional methods.
4. Conclusion
(1) Two pore-free and crack-free NiTi-based SMAs with different
compositions, Ni50.8Ti49.2 and Ni53Ti47, were fabricated using D-WAAM
and pure Ti and Ni wires as feedstocks. The phases of the Ni50.8Ti49.2 and
Ni53Ti47 components changed in the building direction from NiTi
+ NiTi2 to NiTi + NiTi2 + Ni4Ti3 and from NiTi + NiTi2 through NiTi
+ Ni3Ti to NiTi + Ni3Ti + Ni3Ti2 + Ni4Ti3, respectively.
(2) In the homogeneous regions of the two single-walled compo­
nents, the hardnesses of Ni50.8Ti49.2 and Ni53Ti47 were 278 and 596
HV0.2, respectively. This difference arises from their different precipi­
tated phases. In Ni50.8Ti49.2, NiTi2 precipitated at the grain boundaries,
and the NiTi2 content of Ni50.8Ti49.2 was low; in Ni53Ti47, Ni3Ti
precipitated inside the grains, strengthening the matrix.
(3) The unrecoverable strain of Ni50.8Ti49.2 gradually approached
4.5%, and its superelasticity was significantly lower than that of the
corresponding component prepared using conventional methods. This is
related to the processing conditions characteristic of D-WAAM. The
complex heat accumulation produced a heterogeneous microstructure
along the building direction, and the internal stress induced by this heat
accumulation led to heterogeneity in the phase composition of
Ni50.8Ti49.2 at room temperature.
(4) The unrecoverable strain of the Ni53Ti47 component increased
linearly, indicating negligible superelasticity. Although it possessed a
NiTi matrix, acicular Ni3Ti precipitated in the grain segments of the
matrix and inhibited martensitic transformation.
CRediT authorship contribution statement
Jian Han: Supervision, Methodology, Writing – review & editing.
Xinya Chen: Data curation, Formal analysis, Writing – original draft.
Guoyang Zhang: Formal analysis, Resources, Methodology. Lianzhong
Lu: Resources, Investigation. Yi Xin: Resources, Investigation. Xi
Zhang: Resources. Yangchuan Cai: Methodology, Investigation. Yin­
bao Tian: Methodology, Conceptualization, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
13
Journal of Materials Processing Tech. 306 (2022) 117631
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
We would like to thank Editage (www.editage.cn) for English lan­
guage editing.
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