Virtual and Physical Prototyping

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Achieving grain refinement and ultrahigh yield

strength in laser aided additive manufacturing of
Ti−6Al−4V alloy by trace Ni addition

Shang Sui, Youxiang Chew, Fei Weng, Chaolin Tan, Zhenglin Du & Guijun Bi

To cite this article: Shang Sui, Youxiang Chew, Fei Weng, Chaolin Tan, Zhenglin Du & Guijun
Bi (2021) Achieving grain refinement and ultrahigh yield strength in laser aided additive
manufacturing of Ti−6Al−4V alloy by trace Ni addition, Virtual and Physical Prototyping, 16:4,
417-427, DOI: 10.1080/17452759.2021.1949091

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VIRTUAL AND PHYSICAL PROTOTYPING
2021, VOL. 16, NO. 4, 417–427
https://doi.org/10.1080/17452759.2021.1949091

Achieving grain refinement and ultrahigh yield strength in laser aided additive
manufacturing of Ti−6Al−4V alloy by trace Ni addition
Shang Sui, Youxiang Chew , Fei Weng , Chaolin Tan , Zhenglin Du and Guijun Bi
Singapore Institute of Manufacturing Technology, A*STAR, Singapore, Singapore

ABSTRACT ARTICLE HISTORY

Fabricating fine equiaxed grains without undesirable secondary phases is highly challenging for Received 26 April 2021
additively manufactured Ti−6Al−4V alloy. The reference amount of Ni addition, which can Accepted 25 June 2021
achieve grain refinement without secondary phase formation, is 0.9 wt. % based on Thermo-
KEYWORDS
Calc calculation. The Ti−6Al−4V−0.9Ni alloy produced by laser-based directed energy Nickel; grain refining; laser-
deposition demonstrate refined microstructure and an ultrahigh yield strength (1309 MPa). A based directed energy
modified quantitative model is proposed to analyse the strengthening mechanism, and the deposition; titanium alloys;
results demonstrate that the yield strength increment is mainly ascribed to the refined α phase. mechanical properties
This work can contribute to the development of customised titanium alloy using additive
manufacturing.

Impact statement Obtaining fine and equiaxed grains instead of colum-

An ultrahigh yield strength of 1309 MPa was achieved by
adding 0.9 wt. % Ni into LAAM-built Ti−6Al−4V; a
strengthening model was modified to reveal the under-
lying mechanism.
1. Introduction
Titanium (Ti) alloys have been widely used in the aero-
nautic and astronautic industries, medical implants,
etc., due to their excellent specific strength, good
high-temperature stability and corrosion resistance.
Recently, the development of additive manufacturing
technologies infuse new vitality into the fabrication of
Ti alloys and bring new opportunities into tailoring the
microstructure for improving the material properties.
The prior-β columnar grain is one of the typical micro-
structure characteristics in most additively built Ti
alloys, such as Ti−6Al−4V (Zhao et al. 2017), Ti−6Al
−2Sn−2Zr−3Mo−1.5Cr−2Nb (Zhang et al. 2016c), Ti-
12Mo (Mantri and Banerjee 2018), etc., which is ascribed
to the solidification conditions conducive to epitaxial
growth and lack of nuclei in front of the solid–liquid
(S-L) interface (Bermingham et al. 2019). Consequently,
anisotropy and reduction in mechanical properties are
observed in the additively built Ti alloys (Zhang et al.
2016c, 2021a).
nar grains is one of the most effective ways to address the
abovementioned issues. Many efforts have been made to
promote grain refinement and induce equiaxed grains
formation. Todaro et al. reported that high-intensity
ultrasound can be used to refine grain structure in the
additively – built Ti−6Al−4V (Todaro et al. 2020).
Through this method, the average grain size decreased
from 500 ± 354 to 117 ± 61 μm, the yield strength
increased from 980 ± 13 MPa to 1094 ± 18 MPa, and the
elongation remained unchanged. However, this
method places high demands on the equipment and
the ultrasonic intensity will attenuate with increasing
built height away from the source at the base. In addition,
Zhang et al. indicated that increasing powder feeding
rate could also promote equiaxed grain formation due
to heterogeneous nucleation caused by partially
melted powders in the melt pool (Zhang et al. 2016b,
2021b). They achieved equiaxed grains in Ti−6Al−2Sn
−2Zr−3Mo−1.5Cr−2Nb (∼175 K under non-equilibrium
solidification condition calculated using Thermo-Calc)
(Zhang et al. 2016b) and Ti-5Al-2Sn-2Zr-4Mo-4Cr
(∼238 K) (Zhang et al. 2021b) alloys. However, this
method may not be applicable to the Ti alloys with a
small solidification range ΔT, such as Ti−6Al−4V (∼3 K).
Additives (e.g. Cu (Zhang et al. 2019), B (Bermingham
et al. 2015; Xue et al. 2019), Si (Mereddy et al. 2017),
La2O3 (Bermingham et al. 2019), Ni (Tan et al. 2018;

CONTACT Guijun Bi gjbi@SIMTech.a-star.edu.sg Singapore Institute of Manufacturing Technology, A*STAR, 73 Nanyang Drive, 637662 Singapore,
Singapore; Youxiang Chew chewyx@SIMTech.a-star.edu.sg
Supplemental data for this article can be accessed at https://doi.org/10.1080/17452759.2021.1949091.
© 2021 Informa UK Limited, trading as Taylor & Francis Group
418 S. SUI ET AL.
Xiong et al. 2021)) have been proven to be effective for
refining grain structure and enhancing mechanical prop-
erties. Apart from Ti alloys, this method demonstrates
widespread application in steels (AlMangour, Grzesiak,
and Yang 2017), aluminium alloys (Jiang et al. 2019)
and superalloys (Zhang et al. 2016a). Bermingham
et al. indicated that the introduction of La2O3 could
reduce the grain size of Ti−3Al−8V−6Cr−4Mo−4Zr
alloy from ∼700 to ∼200 μm (Bermingham et al. 2019).
Hou et al. found that the slight increase of C, O and Fe
contents in pure titanium alloy contributed to the finer
grain size and excellent mechanical properties (Hou
et al. 2019).
However, these additives inevitably introduce unde-
sirable compounds, which deteriorate the mechanical
properties. Xiong et al. pointed out that adding 1.6
wt.% of Ni in additively manufactured pure titanium
alloy induced the formation of eutectoid Ti2Ni particles
and causes brittle failure during room-temperature
tensile process (Xiong et al. 2021). In addition, Xue
et al. illustrated that the volume fraction of TiB com-
pound increased with increasing B content, resulting
in reduced deformation compatibility and decreased
elongation (Xue et al. 2019). Furthermore, Zhang
et al. revealed that the Ti2Cu particles formed when
adding 8.5 wt.% of Cu in pure titanium alloy, lead to
low ductility of only ∼2% (Zhang et al. 2019). There-
fore, the challenge remains for fabricating equiaxed
grains in additively built Ti alloys, such as Ti−6Al−4V,
without formation of undesirable secondary phase
particles.
AM processing with in-situ alloying is a common
approach to realise good metallurgical bonding of
metals/alloys with additives (Mosallanejad et al. 2021;
Sing et al. 2021). This strategy proves to be highly
efficient in the manufacturing and verification of new
materials, shortening the development cycle (Sing
et al. 2021). Compared to the laser powder bed
fusion process, the powder-blown laser deposition
processes with in-situ alloying demonstrate more flexi-
bility in adjusting the chemical compositions of the
built part by controlling the powder feeding rates
using multiple hoppers. This advantage favours the
investigation of the microstructural evolution with
chemical composition variation, thus deepening the
understanding of phase structure formation. For
instance, Collins et al. investigated the evolution of
the α and β phases in the deposited Ti-Mo and Ti-V
alloys with changing Mo and V contents gradually
along the building direction (Collins et al. 2003). Con-
sequently, deposition with in-situ alloying is quite suit-
able for investigation on the fabrication of multi-
materials.
This work aims to use ‘Thermo-Calc prediction +
power blown laser aided additive manufacturing
(LAAM) process with in-situ alloying’ to explore a suit-
able Ni content in LAAM-built titanium alloys fabricated,
which can induce grain refinement with no undesirable
phase formation. The Ti−6Al−4V alloy was investigated
as it has the smallest solidification range amongst the
Ti alloys. Microstructure characteristics and room-temp-
erature mechanical properties were analyseed. Further-
more, the strengthening mechanism was also
proposed for quantitative analysis. The findings in this
work highlight an approach to choose appropriate addi-
tive content and can deepen the understanding of the
effect of additives on the microstructure and mechanical
properties of additively manufactured titanium alloys.
2. Thermo-calc calculation
Constitutional supercooling is essential for promoting
columnar to equiaxed transition (CET). According to
the criterion for generating constitutional supercooling
as shown below, it is easier to obtain equiaxed grains
with higher solidification range DT.
G mC0 (1 − k0 ) DT
, = (1)
R DL k0 DL
where G represents the temperature gradient, R rep-
resents the solidification velocity, m is the liquidus
slope, C0 is the initial element content, k0 is the partition
coefficient and DL is the diffusion coefficient in liquid. In
order to depict the variation in the solidification range of
Ti alloys with Ni addition more clearly, the Scheil solidifi-
cation model was used to compute the non-equilibrium
process. Thermo-calc software was used for the thermal
calculation in this work. The used Database was TCTI1:
Ti-Alloys v1.0. As shown in Figure 1(A), the variation in
the DT values for Ti−6Al−4V-xNi demonstrated two
obvious stages. In the first stage, the DT value increased
quickly and linearly with increasing Ni addition. The
slope of the first stage is 681 °C/wt. %. In the second
stage, the rate of DT value increment has reduced
slightly with the increase of Ni addition, but a clear
linear relationship could still be observed. The slope of
the second stage is 207 °C/wt. %.
Further analysis indicated that the change in slope
from stage 1 to stage 2 can be ascribed to the formation
of Laves phase as shown in Figure 1(B,C). The Thermo-
Calc calculations showed that the chemical compo-
sitions of the Laves phases contained a large amount
of Ni (∼33 wt. %). Hence, the Laves phase formation
reduces Ni content in the melt, leading to the lower
increment rate in the second stage. According to the
aforementioned analysis, no other phases, except the β

Figure 1. Thermo-Calc calculation of Ti−6Al−4V alloy with Ni addition. (A) Solidification range of Ti−6Al−4V-xNi. (B and C) Scheil
solidification of Ti−6Al−4V−0.9Ni and Ti−6Al−4V-1.0Ni, respectively.
phase, will be formed under the non-equilibrium solidifi-
cation condition when the Ni content is lesser than 0.9
wt. % (as illustrated in Figure 1(B)). Although the Ti-Ni
phase diagram (Figure S1 in the Supplementary
Materials) illustrates that Ni2Ti Laves phase can be
formed during the solid-state transformation, the rapid
cooling rate during the LAAM process may suppress
the formation and maintain the microstructure charac-
teristics attained at higher temperature. Therefore, the
reference Ni content, which can promote grain refine-
ment without undesirable phase formation in the Ti
−6Al−4V alloy, should be approximately 0.9 wt. %.
3. Materials and methods
LAAM system, including a fibre laser with a maximum
output power of 1000W and a continuous coaxial
powder feeding nozzle, was used to fabricate the bulk
materials in this work. The selection of powder size is
highly dependent on the powder feeding nozzle
design and fabrication quality. The nozzle used is
capable to stably feed the fine Ti64 powders with the
size range of 20–45 μm and form a fine powder focus
about 1.5 mm in diameter with additional channel for
effective inert gas shielding. The utilised Ti−6Al−4V
powders are Grade 23, from LPW technology ltd. The
size of the Ni particles is approximately 45 μm, from
American Elements. Two powder hoppers were utilised
in this study. Hopper 1 contained Ti−6Al−4V powders
with the size range of 20–45 μm in diameter, and
Hopper 2 contained the mixture of Ti−6Al−4V and Ni
with the mass ratio of 19:1. Figure 2(A-C) depict the mor-
phologies of the pure Ti−6Al−4V powders, pure Ni
powders and mixed powders, respectively. It is evident
that the Ti−6Al−4V and Ni powders are mixed together
uniformly (Ni powders are indicated by orange arrows in
Figure 2(C)). In addition, pure Ar gas (≥99.999%) was
VIRTUAL AND PHYSICAL PROTOTYPING 419
used to deliver the powders from the hoppers to the
coaxial nozzle and shield the melt pool to avoid oxi-
dation, as shown in Figure 2(D). The fabrication of the
Ti−6Al−4V alloy (Sample 1) was achieved by using
Hopper 1, while the Ti−6Al−4V−0.9Ni alloy (Sample 2)
was manufactured by using both Hopper 1 and
Hopper 2. Furthermore, the detailed LAAM process par-
ameters are shown in Table 1.
The block size of the LAAM-built Ti−6Al−4V and Ti
−6Al−4V−0.9Ni alloys was 90 mm × 50 mm × 6 mm
(length × width × height) as shown in Figure 2(E). The
cross-sections of the as-built samples were ground by
SiC papers and etched using Kroll’s reagent for micro-
structure observation. Optical microscopy (OM) and
Image J software were used for quantitative analysis of
the grain size. The grains are considered to be elliptical
and their sizes were estimated through the defined
‘major-axis length’ and ‘minor-axis length’. At least 200
grains were analysed to ensure reliability and accuracy.
The log-normal equation given below was utilised to
fit the statistical results
⎛ ⎞
x 2
A ⎜−( ln xc ) ⎟
f (x) = f0 + √



exp⎜
⎝ 2 · w2 ⎠
⎟ (2)
2p · w · x
where xc and w represent the median and standard devi-
ation, respectively, in a weighted distribution. Further-
more, the mean value
x of a certain microstructure
characteristic can be expressed as (Li et al. 2018).
1 2

x = xc · exp w (3)
2
Scanning electron microscopy (SEM) was employed
for phase observation. Room-temperature tensile tests
were performed at a constant displacement rate of
1 mm/min by using the Instron 5982 test machine.
420 S. SUI ET AL.

Figure 2. Experimental details. (A-C) Morphologies and sizes of the pure Ti−6Al−4V, pure Ni and mixed powders, respectively. (D)
Schematic diagram of LAAM process with two hoppers. (E) LAAM-built Ti−6Al−4V−0.9Ni block.

Tensile coupons with a gauge size of 25 × 6× 4 mm were built Ti−6Al−4V alloy were counted and the statistical
used. result showed that the average value is 450.6 μm.
Trace Ni addition of 0.9 wt. % can significantly refine
the grain size as shown in Figure 3(B). The mean
4. Results and discussion major-axis length, minor-axis length and aspect ratio of
the grains in the LAAM-built Ti−6Al−4V−0.9Ni alloy
Figure 3 shows the microstructures of the LAAM-built Ti
were 385, 158 and 2.2 μm, respectively (Figure 3C, and
−6Al−4V and Ti−6Al−4V−0.9Ni alloys. It can be
Figure S2 in Supplementary Materials).
observed that the prior-β grains in the LAAM-built Ti
Further observation using SEM illustrated that the
−6Al−4V alloy grew epitaxially through multiple depos-
fine α laths phase appeared in both the two alloys
ited layers (Figure 3(A)), which made it difficult to accu-
(Figure 3(D,E)), which is closely related to the fast
rately measure their major-axis lengths. However, it can
cooling rate during the LAAM process. The quantitative
be inferred from Figure 3(A) that the major-axis length of
and statistical results demonstrated that the average α
the prior-β grains is larger than 1500 μm. In addition, the
lath width of the LAAM-built Ti−6Al−4V−0.9Ni alloy
minor-axis lengths of the prior-β grains in the LAAM-
(172 nm) is smaller than that of the LAAM-built Ti−6Al
−4V alloy (338 nm), suggesting that the trace Ni addition
Table 1. Detailed LAAM process parameters for fabricating the can also refine the α phase (Figure 3(F)).
Ti−6Al−4V and Ti−6Al−4V−0.9Ni alloys. Figure 4 demonstrates the TEM results of the LAAM-
Sample 1 Sample 2 built Ti−6Al−4V and Ti−6Al−4V−0.9Ni alloys. It is worth-
Laser power (W) ∼700 ∼700 while noting that the element distribution between the
Scanning velocity (mm/min) 1200 1200
Actual deposition rate (g/min) Ti−6Al−4V: 1.01 Ti−6Al−4V: 1.219 α and β phases was not uniform even though the
Ni: 0.011 cooling rate during the LAAM process was high. Specifi-
Shielding gas flow rate (L/min) 15 15
Carrier gas flow rate (L/min) 6 6 cally, the V and Ni were enriched in the β phase, while
Overlap distance (mm) 0.9 0.9 the Al was enriched in the α phase. In both the LAAM-
Layer thickness(mm) ∼0.35 ∼0.35
built Ti−6Al−4V and Ti−6Al−4V−0.9Ni alloys, the V

Figure 3. Microstructure characteristics of LAAM-built Ti−6Al−4V−0.9Ni and Ti−6Al−4V alloys. (A and B) Grain characteristics of the
LAAM-built Ti−6Al−4V−0.9Ni and Ti−6Al−4V alloys, respectively. (C) Quantitative and statistical results of the minor-axis lengths of
the prior-β grains. (D to E) α laths in the LAAM-built Ti−6Al−4V−0.9Ni and Ti−6Al−4V alloys, respectively. (F) Quantitative and stat-
istical results of the α lath width.
content in the β phase was almost three times that in the
α phase, while the Al content in the former was approxi-
mately 0.4 of that in the latter according to the quanti-
tative measurements. Distinct Ni segregation was
observed in the LAAM-built Ti−6Al−4V−0.9Ni alloy, as
the β phase contained more than 20 times higher Ni
content than the α phase.
In addition, the volume fractions of the α and β
phases were measured following the Cavalieri-Hacquert
relation. Based on the SEM figures, the LAAM-built Ti
−6Al−4V alloys contained approximately 89.3 ± 1.1% α
phase and 10.7 ± 1.1% β phase, while the addition of
β-stabilising element Ni increased the volume fraction
of the β phase to 12.5 ± 1.5% and decreased the α
phase to 87.5 ± 1.5% in the LAAM-built Ti−6Al−4V
−0.9Ni alloy.
Furthermore, no secondary phase particles could be
observed in the LAAM-built Ti−6Al−4V and Ti−6Al−4V
−0.9Ni alloys (Figure 3(D,E), Figure 4(A,B)), although
the equilibrium solidification calculation indicated the
appearance of α2-AlTi3 phase during the solid–solid
phase transformation (Figure 5(A,B)). This is due to the
high cooling rate that inhibits the formation of the α2-
AlTi3 phase.
As mentioned in Section 2, Ni addition can enhance
the ability of generating constitutional supercooling
(CS) of Ti−6Al−4V alloy. Figure 6 is the schematic
diagram demonstrating the grain refinement effect of
Ni addition in Ti−6Al−4V alloy. The green and blue
VIRTUAL AND PHYSICAL PROTOTYPING 421
regions represent the CS zone of the Ti−6Al−4V and Ti
−6Al−4V−0.9Ni alloys, respectively. For pure Ti−6Al
−4V alloy, it exhibits weak ability of generating consti-
tutional supercooling, so that the degree of CS
ΔTCS_Ti64 is small, which is lower than the minimum
supercooling required for nucleation ΔTN. Consequently,
the initial grains continue to grow epitaxially, leading to
coarser columnar grains. However, when Ni is added, the
ability of generating CS is enhanced and the value of
ΔTCS_Ti64-Ni exceeds the ΔTN. Thus, new grains will form
to inhibit the epitaxial growth of the initial grains. As a
result, the final grain size will be refined.
It is interesting to note that the Ni addition can also
refine the α phase, although no secondary particles
that suppress the growth of the α phase are formed.
The possible reason is as follows: The re-distribution of
Ni element occurs during the β→α transition. As
shown in Figure 4(B), the Ni content in the β phase is
approximately 21 times of that in the α phase. The
increased Ni content stabilises the β phase, which inhi-
bits the growth of the α phase.
Figure 7(A) showed that the LAAM-built Ti−6Al−4V
−0.9Ni alloy demonstrated ultrahigh strength (yield
strength: 1309.5 ± 3.4 MPa; ultimate tensile strength:
1356.4 ± 4.5 MPa;) and a lower elongation (5.2 ± 0.3%),
compared with the LAAM-built Ti−6Al−4V alloy (yield
strength: 1034.1 ± 2.0 MPa; ultimate tensile strength:
1144.4 ± 1.6 MPa; elongation: 8.1 ± 0.9%). The decrease
in elongation may be due to that the Ni addition
422 S. SUI ET AL.

Figure 4. TEM results of LAAM-built Ti−6Al−4V (A) and Ti−6Al−4V−0.9Ni (B) alloys.

enhance the resistance of Ti−6Al−4V alloy to plastic
deformation. Furthermore, to enable a clearer compari-
son between the different AM processes, the yield
strength vs. elongation to failure for Ti−6Al−4V alloys
fabricated by electron beam melting (EBM), laser
powder bed fusion (LPBF), laser-based directed energy
deposition (LAAM), (Cheng et al. 2021; Lewandowski
and Seifi 2016; Li et al. 2021; Ren et al. 2017; Xu et al.
2017; Zhao et al. 2018) and LAAM-built Ti−6Al−4V
−0.9Ni alloy were plotted in Figure 7(B). It can be seen
that the yield strength of the LAAM-built Ti−6Al−4V
−0.9Ni alloy exceeds that of the other samples by at
least 100 MPa, which demonstrates the significantly
high yield strength achieved by trace Ni addition.
The yield strength of the LAAM-built Ti−6Al−4V
−0.9Ni alloy is increased by 275.4 MPa compared to
that of the LAAM-built Ti−6Al−4V alloy. The improved
yield strength can be ascribed to the following three
contributors: (i) prior-β grain size; (ii) refined α lath; (iii)
solid solution strengthening caused by trace Ni addition.
(i) Hall-Petch relation is commonly used to describe the
grain boundary strengthening, which can be
expressed as:
DsGB = kd−1/2 (4)
where d is the grain size, k is the Hall-Petch coeffi-
cient. Then, the yield strength increment caused by

Figure 5. Equilibrium solidification calculation results of the LAAM-built Ti−6Al−4V alloy (A) and Ti−6Al−4V−0.9Ni alloy (B).
 VIRTUAL AND PHYSICAL PROTOTYPING 423

Figure 6. Schematic diagram of the grain refinement effect of Ni addition in LAAM-built Ti−6Al−4V alloy.

difference in grain size can be computed as: expressed as

−1/2 −1/2 1/nb 1/na

Dsb = kb (dTi64−09Ni − dTi64 ) (5) n
DsSSS = fb Bbb, i Xb,i +fa Bnaa, i Xa,i
2 i i
where kb is 191.7 MPa/μm (Bhattacharjee et al.
(8)
2006). After calculation, the value of Dsb is equal to
6.2 MPa. where fa and fb represent the volume fractions of
(ii) Many prior investigations indicate that the depen- the α and β phases, respectively. Then, the yield
dence of yield strength on the α laths can also be strength increment between Ti−6Al−4V and Ti
computed using the Hall-Petch relation (Chong −6Al−4V−0.9Ni alloys caused by SSS can be formu-
et al. 2019; Zhang et al. 2018). Thus, the increase of lated as
the yield strength caused by the difference in α
1
lath size can be expressed as:
n nb
−1/2 −1/2
DsYS−SSS = fb, Ti64−09Ni Bbb, i Xb,Ti64−09Ni,i
Dsa = ka (wTi64−09Ni − wTi64 ) (6) i

1
Where wTi64 and wTi64−09Ni represent the α lath
na
width of the LAAM-built Ti−6Al−4V and Ti−6Al−4V +fa,Ti64−09Ni Bnaa, i Xa,Ti64−09Ni,i
−0.9Ni alloys respectively, and ka can be selected i
as 330 MPa/μm2 (Luo, Hu, and Wu 2016). The calcu- 1 1
lation result shows that the value Dsa is equal to n nb na
228.1 Mpa. −fb, Ti64 Bbb, i Xb,Ti64,i −fa,Ti64 Bnaa, i Xa,Ti64,i
i i
(iii) Solid solution strengthening (SSS) effect in a multi-
component system can be formulated by the fol- (9)
lowing equation (Zhao et al. 2019):
1/n
Due to the small size of the α and β phases (Figure 3),
it is difficult to measure the elemental content in these
DsSSS = Bni Xi (7)
i phases accurately through EDS. Considering the high
cooling rate in the LAAM process, the elements are
where Bi is the SSS coefficient for solute i, Xi is the assumed to be more uniformly distributed in these
atom concentration of solute i and n is a constant. two phases. The required parameters for calculation
The value of Bi is closely related to the value of n. are given in Table S1. It should be noted that the value
For Ti−6Al−4V alloy containing two phases, consid- of Ba,Ni cannot be found in the literature. However,
ering that the same solute has different SSS effect Sasano et al. indicated that the Ba,Ni is linearly related
on different phases, the Equation (7) can be to the atomic size misfit (Sasano and Kimura 1980).
424 S. SUI ET AL.
Figure 7. Room-temperature tensile properties of LAAM-built Ti−6Al−4V−0.9Ni and Ti−6Al−4V alloys. (A) Engineering stress-engin-
eering strain curves. (B) Comparison of the room-temperature tensile properties of different AM-built Ti−6Al−4V alloys.
The radius of the Ni atom (empirical value of 135 pm) is
the same as that of the V atom (empirical value of 135
pm). Thus, it is reasonable to use the following relation-
Ba,Ni = Ba,V . The calculation result demonstrates that
the value of DsYS−SSS is 34.4 MPa.
It should be noted that the yield strength increments
caused by the prior-β grains and the α laths cannot be
added together since they both reflect Hall-Petch contri-
bution. For the α+β type Ti alloys, numerous investi-
gations had indicated that the α lath was the main
contributor and the strengthening effect of the prior-β
grains was ignored (Chong et al. 2019; Zhang et al.
2018). In this work, it is also found that the strengthening
effect of the α laths was remarkably higher than that of
the prior-β grains (Table S2 in Supplementary Materials).
Therefore, the total increment in yield strength should
be calculated using contribution from the refined α
laths and the solid solutes, which is 262.5 MPa. This
shows a good agreement with the experimental result
(275.4 MPa increase in yield strength for Ti−6Al−4V
−0.9Ni), indicating that the model used in this work is
reasonable. Furthermore, it is evident from the quanti-
tative analysis that the contribution of the refined α
lath phase (228.1 MPa) on the yield strength increment
far, exceeds that of the prior-β grain (6.2 MPa) and SSS
(34.4 MPa).
The reduction in ductility after adding Ni may be
ascribed to the following reasons: (i) Although trace Ni
addition can slightly increase the volume fraction of β
phase (from 10.7 to 12.5 vol.%), it also bring about
higher deformation resistance due to its hindering
effect on dislocation movement, especially with Ni
enrichment in the β phase as shown in Figure 4(B). As
a result, dislocation pile-up is more likely to occur in
the β phase, which results in a decrease in ductility. (ii)
In both the LAAM-built Ti−6Al−4V and Ti−6Al−4V
−0.9Ni alloys, the α/β phase boundary dominates. In
the LAAM-built Ti−6Al−4V−0.9Ni alloy, the width of
the α phase is smaller than that in the LAAM-built Ti
−6Al−4V alloy, leading to smaller dislocation slip dis-
tance. Therefore, it is much easier for the dislocations
in the LAAM-built Ti−6Al−4V−0.9Ni alloy to accumulate
at the α/β phase boundary and form stress concen-
tration. On one hand, the HCP-α phase has fewer slip
systems, and it is more difficult to start these slip
systems, compared to the BCC-β phase. Thus, it is hard
to alleviate stress concentration by activating multiple
slip systems. On the other hand, the small width of the
α phase in the LAAM-built Ti−6Al−4V−0.9Ni limits the
formation of twins, which is also an effective approach
to relieve stress concentration. Under the combined
effects of these factors, the ductility of the LAAM-built
Ti−6Al−4V−0.9Ni alloy is lower than that of the LAAM-
built Ti−6Al−4V alloy.
5. Conclusion
This work demonstrates that using Ni addition of ∼0.9
wt. % can significantly promote grain refinement
without inducing the formation of undesirable interme-
tallic phases in LAAM-built Ti−6Al−4V alloy. The refer-
ence Ni addition was determined using Thermo-Calc
calculation and supported by microstructure examin-
ation of the LAAM-built Ti−6Al−4V−0.9Ni alloy. The
experimental results showed that the trace Ni addition
of 0.9 wt. % promote the formation of equiaxed grain,
reducing the minor-axis length (width) of the prior-β
grains from 450.6 μm to 158 μm, compared with
LAAM-built Ti−6Al−4V using the same process par-
ameters. The superior yield strength of the LAAM-built

Ti−6Al−4V−0.9Ni alloy (∼1309.5 MPa) is ∼275 MPa
higher than that of the LAAM-built Ti−6Al−4V alloy
(∼1034.1 MPa). A modified quantitative model is pro-
posed for assessing the strengthening effects caused
by prior-β grains, α laths phase and solid solute atoms.
The results demonstrate that the refined α laths phase
in the Ti−6Al−4V−0.9Ni alloy is the dominant strength-
ening contributor. This work opens up new methods for
the development of titanium alloys using additive man-
ufacturing. In the future work, systematic investigation
on the effect of different Ni content on the microstruc-
tural evolution and mechanical properties will be per-
formed. The effect of process parameters and
deposition size on the solidification conditions and
resulting microstructure will also be studied for Ti−6Al
−4V with the same Ni content.
Disclosure statement
No potential conflict of interest was reported by the author(s).
Funding
This research was supported by Agency for Science, Technol-
ogy and Research (A*Star), Republic of Singapore, under the
IAF-PP program “Integrated large format hybrid manufacturing
using wire-fed and powder-blown technology for LAAM
process” [grant number A1893a0031].
Notes on contributors
Dr Shang Sui is a Research Scientist in Sin-
gapore Institute of Manufacturing Tech-
nology. He received his B.S. degree in
Materials Forming and Control Engineer-
ing in 2013 as an outstanding graduate,
his Ph.D. in Materials Processing Engin-
eering in 2019, all from Northwestern
Polytechnical University of China. He has
been engaged in Laser Additive Manufacturing (LAM) technol-
ogy for 6 years since 2013 when he was a bachelor student at
Northwestern Polytechnical University. His research is focused
on the microstructural optimization and mechanical perform-
ance enhancement of LAM-built nickel-based superalloy
Inconel 718.
Dr Youxiang Chew is a Research Scientist
and deputy group manager in Singapore
Institute of Manufacturing Technology
(SIMTech). He joined SIMTech in 2015
and obtained his PhD in Mechanical
Engineering from Nanyang Technological
University (Singapore). He has over 8
years of experience in Laser directed
energy deposition (LDED) technology, focusing on process,
residual stress modelling and integration of machine learning
with FEM to optimize laser deposition toolpaths. His other
research interest includes the development of high entropy
VIRTUAL AND PHYSICAL PROTOTYPING 425
alloy and bulk spatially patterned heterostructured multi-
materials parts using LDED.
Dr Fei Weng is a Research Scientist in Sin-
gapore Institute of Manufacturing Tech-
nology (SIMTech). He received his PhD
degree in Materials Science and Engineer-
ing from Shandong University, China. His
current research interest is in laser aided
additive manufacturing of Ti-6Al-4V
alloys, nickel-based alloys, high/medium
entropy alloys, and other novel high-performance alloys. The
emphasis is on microstructure evolution and property evalu-
ation. Dr. Weng also has experience in repair and surface medi-
cation of metal components by laser cladding.
Dr Chaolin Tan is a Research Scientist in
Singapore Institute of Manufacturing Tech-
nology (SIMTech). He received his PhD
degree in Materials Processing Engineering
from South China University of Technology
in conjunction with University of Birming-
ham (UK) in 2019. His research experience
on laser additive manufacturing (LAM)
has been over 7 years, with rich research experiences in LAM
of advanced high strength steels since 2013. His research inter-
ests include LAM new materials and heterostructured materials.
Dr Zhenglin Du is a scientist in the Agency
for Science, Technology and Research
(A*STAR). He graduate from Nanyang
technological University during 2018
with a Doctor of Philosophy (PhD) in
Mechanical Engineering with Honors. He
specialises in additive manufacturing,
process optimisation and metallurgy.
Dr Guijun Bi is a Senior Scientist and Group
Manager with the Joining & Machining
Group in Singapore Institute of Manufac-
turing Technology. He also holds the
adjunct professorship with the National
University of Singapore. Dr Bi received his
PhD in laser material processing from
Fraunhofer Institute for Laser Technology
and RWTH Aachen University, Germany. His research focuses
on additive manufacturing for surface modification, repair and
3D printing, development of new materials using additive man-
ufacturing, hybrid technologies combined additive and subtrac-
tive manufacturing, process monitoring and control, modelling
and simulation of additive manufacturing and joining processes.
ORCID
Youxiang Chew http://orcid.org/0000-0002-2930-2614
Fei Weng http://orcid.org/0000-0003-3195-8329
Chaolin Tan http://orcid.org/0000-0003-2029-4600
Guijun Bi http://orcid.org/0000-0002-3931-4301
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