materials
Article
Manufacturing of Ti-Nb-Cr-V-Ni-Al Refractory High-Entropy
Alloys Using Direct Energy Deposition
Ho-In Jeong 1 , Choon-Man Lee 2, *
Citation: Jeong, H.-I.; Lee, C.-M.;
Kim, D.-H. Manufacturing of
Ti-Nb-Cr-V-Ni-Al Refractory
High-Entropy Alloys Using Direct
Energy Deposition. Materials 2022, 15,
6570. https://doi.org/10.3390/
ma15196570
Academic Editor: Chao Cai
Received: 26 August 2022
Accepted: 21 September 2022
Published: 22 September 2022
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4.0/).
Materials 2022, 15, 6570. https://doi.org/10.3390/ma15196570
and Dong-Hyeon Kim 3, *
1 Mechanical Design and Manufacturing, School of Mechatronics Engineering, Changwon National University,
Changwon 51140, Korea
2 Department of Mechanical Engineering, Changwon National University, Changwon 51140, Korea
3 Mechatronics Research Center, Changwon National University, Changwon 51140, Korea
* Correspondence: cmlee@changwon.ac.kr (C.-M.L.); dkim@changwon.ac.kr (D.-H.K.)
Abstract: High-entropy alloys (HEAs) are composed of 5–35 at% of five or more elements, have high
configurational entropy, do not form intermetallic compounds, and have a single-phase face-centered
cubic structure or body-centered cubic structure. In particular, refractory HEAs (RHEAs), based on
refractory materials with excellent mechanical properties at high temperatures, have high strength
and hardness at room temperature and excellent mechanical properties at low and high temperatures.
In this study, the Ti-Nb-Cr-V-Ni-Al RHEAs were deposited using direct energy deposition (DED). In
the microstructure of Ti-Nb-Cr-V-Ni-Al, the sigma, BCC A2, and Ti2Ni phases appeared to be different
from the BCC A2, BCC B2, and Laves phases predicted in the phase diagram. This microstructure
was similar to that of the casted Ti-Nb-Cr-V-Ni-Al and had a constructed fine grain size. It was found
that the growth of these microstructures was due to the DED process, which has a fast solidification
rate. The fine grain size caused high hardness, and the microhardness of the Ti-Nb-Cr-V-Ni-Al was
measured to be about 900 HV. In addition, in order to analyze the thermal properties of Ti-Nb-Cr-V-
Ni-Al composed of the refractory material, the heat-affected zone (HAZ) was analyzed through a
preheating test. The HAZ was decreased, owing to the high thermal diffusivity of Ti-Nb-Cr-V-Ni-Al.
Keywords: additive manufacturing; direct energy deposition; high-entropy alloys; refractory material;
phase analysis
1. Introduction
High-entropy alloys (HEAs) are new materials that can overcome the limitations of the
existing physical properties, and many studies are being conducted on them intensively [1].
General alloys are composed of the main element and a small number of substituted
elements. In these alloys, as the number of constituent elements increases, intermetallic
compounds are formed, and the mechanical properties are weakened, owing to their
brittleness. HEAs are composed of 5–35 at% of five or more elements with similar atomic
radii [2]. In this case, they exhibit high configurational entropy, severe lattice distortion,
and a slow diffusion rate. In general, HEAs are defined as alloys with configurational
entropies higher than 1.5R (where R is a gas constant) [3]. The configurational entropy
equation is shown in Equation (1):
N
∆Smix = − R ∑i xi ln xi , (1)
where ∆smix is the configurational entropy, N is the number of elements, and xi is the
entropy of each element.
Owing to their high configurational entropy, HEAs do not form intermetallic com-
pounds and have a single-phase face-centered cubic (FCC) or body-centered cubic (BCC)
structure [4]. Unlike the solid solution in a general alloy system, it forms a concentrated
solid solution. Owing to their unique composition and microstructure, HEAs have not only
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Materials 2022, 15, 6570 2 of 13

high strength and hardness at room temperature but also excellent mechanical properties
at low and high temperatures [5]. In particular, refractory high-entropy alloys (RHEAs)
are the HEAs based on refractory materials such as Ti [6], V [7], Cr [8], Zr [9], Hf [10],
Nb [11], Mo [12], Ta [13], W [14], and Mn [15], which have excellent mechanical properties
at high temperatures. RHEAs have a crystal structure such as FCC, FCC+BCC, and BCC
phases, a microstructure including a precipitated phase, and intermetallic compounds such
as the BCC B2 phase and Laves phase [16]. Most research using HEAs was conducted
during evaluation of the basic properties by manufacturing ingots using arc melting and
casting [17]. The conventional casting method of manufacturing HEAs has the problem
of difficulty in forming a single-phase solid solution due to a low cooling rate. As the
size of the manufactured HEA increases, it is difficult to secure the uniformity of the mi-
crostructure because the internal cooling rate and the external cooling rate are different. The
non-uniformed microstructure causes degradation and non-uniformity of the mechanical
properties of the HEAs [18,19]. In addition, since the HEAs are challenging to process due
to their high mechanical properties, research is needed to reduce the material’s volume
and improve the substrate’s performance by coating the base material with HEAs rather
than manufacturing a large volume. Therefore, research on the manufacture of HEAs using
additive manufacturing (AM) that can be manufactured and coated in a relatively short
time is needed.
The AM process’s research and development has been actively conducted because it
has the advantages of easy design and manufacturing of complex or special shapes, and
it is used in various fields such as aerospace, automobiles, medicine, and machinery. AM
technology can be classified by processes into two types: the powder bed fusion (PBF)
process and directed energy deposition (DED) process [20]. PBF is an AM process in
which thermal energy (a laser or electron beam) selectively fuses regions of a powder bed
layer by layer [21]. PBF can create arbitrarily complex geometries by selectively melting
powder-form raw materials using a bottom-up manner with the assistance of a thermal
energy source [22], and it shows overwhelming superiority in the manufacture of objects
with geometrical complexity and high resolutions [23]. DED is an AM process in which
metal wire or powder is combined with a thermal energy source to directly deposit material
onto a build tray or an existing part. The DED method is similar to welding and can be
used to deposit material on existing products, thus being available for maintenance work.
In addition, in the DED process, since AM of multi-material objects is possible, various
alloys and composites can be manufactured using various metal materials. Therefore,
AM, which is completed in a relatively short time and manufactured using various metal
materials, is suitable for manufacturing HEAs. DED has mostly been used in research
on manufacturing HEAs using additive manufacturing [24]. Because DED has a fast
solidification rate, it is advantageous for refining grains and can prevent the segregation of
specific components [25]. In addition, because the heat source has a high energy density,
the heat-affected zone (HAZ) is narrow, and the dilution rate of the base material is low.
These features mainly reduce cracks, deformations, and metallurgical changes in the base
metal, resulting in fewer defects and better production quality than other methods [26].
In this study, a Ti-Nb-Cr-V-Ni-Al RHEA was deposited using DED. Figure 1 shows
the schematic diagram for the DED of Ti-Nb-Cr-V-Ni-Al. Prior to deposition, the phase
diagram and phase fraction of Ti-Nb-Cr-V-Ni-Al were analyzed. For the DED of Ti-Nb-
Cr-V-Ni-Al, powders of each element were mixed to prepare a mixed Ti-Nb-Cr-V-Ni-Al
powder and deposited on Ti-6Al-4V and Inconel 718 substrates. The scanning electron
microscopy (SEM), electron backscatter diffraction (EBSD) X-ray diffraction (XRD), and
energy dispersive spectrometer (EDS) analyses were conducted to verify the microstructure
of the deposited Ti-Nb-Cr-V-Ni-Al. In addition, the hardness of the deposited Ti-Nb-Cr-V-
Ni-Al was measured, and a preheating test was performed to analyze the HAZ depending
on the deposited Ti-Nb-Cr-V-Ni-Al.
Materials 2022,
Materials 2022, 15,
15, 6570
x FOR PEER REVIEW 33of
of 13
13

Ti-Nb-Cr-V-Ni-Al.
Figure 1. Schematic diagram for DED of Ti‐Nb‐Cr‐V‐Ni‐Al.

2. Phase
2. Phase Analysis
Analysis
Table 1 lists chemical composition of Ti-Nb-Cr-V-Ni-Al. The Ti-Nb-Cr-V-Ni-Al was
Table 1 lists chemical composition of Ti‐Nb‐Cr‐V‐Ni‐Al. The Ti‐Nb‐Cr‐V‐Ni‐Al was
completely melted at above 1425 ◦ C, and the Ti-rich BCC A2 phase grew as the temperature
completely melted at above 1425 °C, and the Ti‐rich BCC A2 phase grew as the
decreased. The BCC A2 phase increased up to a complete solidification temperature of
temperature decreased. The BCC A2 phase increased up to a complete solidification
950 ◦ C and decreased rapidly with the formation of the Ti–Nb-rich BCC B2 precipitated
temperature of 950 °C and decreased rapidly with the formation of the Ti–Nb‐rich BCC
phase at 950 ◦ C. The Cr–Nb-rich C14 Laves phase as a precipitate phase appeared at 1030 ◦ C
B2 precipitated phase at 950 °C. The Cr–Nb‐rich C14 Laves phase as a precipitate phase
and gradually grew with decreasing temperature. The predicted phase fractions were BCC
appeared at 1030 °C and gradually grew with decreasing temperature. The predicted
A2 (21.6%), BCC B2 (62.2%), and BCC C14 Laves (16.2%). Figure 2 shows the phase diagram
phase fractions were BCC A2 (21.6%), BCC B2 (62.2%), and BCC C14 Laves (16.2%). Figure
of Ti-Nb-Cr-V-Ni-Al, and Figure 3 shows the phase fractions of Ti-Nb-Cr-V-Ni-Al.
2 shows the phase diagram of Ti‐Nb‐Cr‐V‐Ni‐Al, and Figure 3 shows the phase fractions
of Ti‐Nb‐Cr‐V‐Ni‐Al.
Table 1. The chemical composition of Ti-Nb-Cr-V-Ni-Al.
The growth of the BCC phase was found to be due to the beta (β) phase of titanium.
Element was encountered
Titanium
Materials 2022, 15, x FOR PEER REVIEW
Ti Nb Cr
in two crystallographic Vforms. At Niroom Al
4 of 13 temperature,
unalloyed
at % titanium has a hexagonal
34.6 20.4 close‐packed
10.0 (HCP)10.0
structure referred
15.0 to as the alpha
10.0
(α) phase. At 883 °C, titanium undergoes an allotropic transformation from HCP to the
BCC structure known as the β phase. The α phase generally has creep resistance superior
to the β phase and is preferred for high‐temperature applications. The absence of a ductile‐
to‐brittle transition, a feature of the β phase, makes the α phase suitable for cryogenic
applications. The β phase has better strength and toughness than the α phase. They also
exhibit high‐stress corrosion resistance, can be heat‐treated to high strengths, and have
excellent fatigue properties [27]. In addition, most elements constituting Ti‐Nb‐Cr‐V‐Ni‐
Al, such as Nb, Cr, V, and Cr as the transition elements, decrease the temperature of the
α‐to‐β phase transition and thus promote the development of the β phase [28].

Table 1. The chemical composition of Ti‐Nb‐Cr‐V‐Ni‐Al.

Element Ti Nb Cr V Ni Al
at % 34.6 20.4 10.0 10.0 15.0 10.0

Figure2. 2.
Figure TheThe phase
phase diagram
diagram of Ti-Nb-Cr-V-Ni-Al.
of Ti‐Nb‐Cr‐V‐Ni‐Al.
Materials 2022, 15, 6570 4 of 13
Figure 2. The phase diagram of Ti‐Nb‐Cr‐V‐Ni‐Al.

Figure
Figure3.3.The
Thephase fractions
phase of Ti‐Nb‐Cr‐V‐Ni‐Al.
fractions of Ti-Nb-Cr-V-Ni-Al.

The growth of the BCC phase was found to be due to the beta (β) phase of titanium.
Titanium was encountered in two crystallographic forms. At room temperature, unalloyed
titanium has a hexagonal close-packed (HCP) structure referred to as the alpha (α) phase.
At 883 ◦ C, titanium undergoes an allotropic transformation from HCP to the BCC structure
known as the β phase. The α phase generally has creep resistance superior to the β phase
and is preferred for high-temperature applications. The absence of a ductile-to-brittle
transition, a feature of the β phase, makes the α phase suitable for cryogenic applications.
The β phase has better strength and toughness than the α phase. They also exhibit high-
stress corrosion resistance, can be heat-treated to high strengths, and have excellent fatigue
properties [27]. In addition, most elements constituting Ti-Nb-Cr-V-Ni-Al, such as Nb, Cr,
V, and Cr as the transition elements, decrease the temperature of the α-to-β phase transition
and thus promote the development of the β phase [28].

3. Experimental Procedure
3.1. Experimental Set-Up and Materials
To perform DED of Ti-Nb-Cr-V-Ni-Al, a hybrid machine tool for additive and sub-
tractive manufacturing was used with a high-power diode laser additive head (Laytools,
AK390) [29]. The hybrid machine tool had a travel distance of 500 × 500 × 300 mm
(X, Y, Z). A laser (Laserline, LDM 1000) with a maximum output of 1 kW, wavelength of
980 nm, focal length of 198 mm, and spot size of 3 mm was used for the laser head [30]. The
powders were mixed using a mixer for 4 h and transferred to a laser head using a rotating
twin disk-type powder feeder system (Oerlikon Metco, Twin 150). Nitrogen was used as
the carrier gas for powder feeding, and argon gas was used as the shield gas [31]. A 780-W
cooling system (Yescool, YRC-1A) was used to cool the hybrid machine tool. Figure 4
shows the experimental set-up.

Materials 2022, 15, 6570
The powder used for the DED of Ti‐Nb‐Cr‐V‐Ni‐Al was prepared by mixing Ti, Nb,
Cr, V, Ni, and Al powders manufactured by MK Corporation in the particle size range of
45–150 μm. The powder was mixed at the same ratio as in the phase analysis. The
substrates used were 15 mm wide, 15 mm thick, and 60 mm long for Ti‐6Al‐4V and Inconel
718 to prevent thermal deformation and thermal shock during DED. Table5 2of 13lists the
chemical compositions of the Ti‐6Al‐4V and Inconel 718 substrates [32,33].

Figure4.4.The
Figure Theexperimental
experimental set‐up
set-up for for
DED.DED.

The
Table powder
2. The usedcompositions
chemical for the DED of
of the
Ti-Nb-Cr-V-Ni-Al
substrates. was prepared by mixing Ti, Nb,
Cr, V, Ni, and Al powders manufactured by MK Corporation in the particle size range
of 45–150 µm. The powder was mixed at Ti‐6Al‐4V
the same ratio as in the phase analysis. The
Elementused were
substrates Ti 15 mm wide, 15Almm thick, and 60 V mm long for Ti-6Al-4V
Fe C
and Inconel
718wt
to %
prevent thermal
Bal. deformation
6.5 and thermal shock
4.3 during DED.
0.15Table 2 lists the
0.02
chemical compositions of the Ti-6Al-4V and Inconel 718 substrates [32,33].
Inconel 718
Element
Table Ni compositions
2. The chemical Cr Fesubstrates.Nb
of the Mo Ti Al Co
wt % Bal. 18.1 17.9 4.8 2.9 0.9 0.5 0.3
Ti-6Al-4V
Element Ti 3.2. DED Al
Method and ConditionsV Fe C
wt % Bal. 6.5
Ti‐Nb‐Cr‐V‐Ni‐Al 4.3
was deposited 0.15 and Inconel 7180.02
on Ti‐6Al‐4V substrates in a
rectangular shape of Inconel
10 mm718transversely (X direction) and 40 mm longitudinally (Y
Element Ni Cr direction).FeThe Ti‐Nb‐Cr‐V‐Ni‐Al
Nb was deposited
Mo in two
Ti layers to aAl
thickness ofCo
1 mm. Each
wt % Bal. 18.1 layer was deposited with
17.9 4.8 five hatches,2.9and the overlapping
0.9 efficiency
0.5 of the0.3hatch was
40%. If the efficiency was lower than 30%, internal pores may have been generated, and
the mechanical properties may have been reduced [20,34]. If the overlapping efficiency
3.2. DED Method and Conditions
was too high, deformation and internal stress would occur, owing to the reduced
Ti-Nb-Cr-V-Ni-Al was deposited on Ti-6Al-4V and Inconel 718 substrates in a rectan-
productivity and thermal overlap. Figure 5 shows the schematic diagram of the
gular shape of 10 mm transversely (X direction) and 40 mm longitudinally (Y direction).
The Ti-Nb-Cr-V-Ni-Al was deposited in two layers to a thickness of 1 mm. Each layer
was deposited with five hatches, and the overlapping efficiency of the hatch was 40%.
If the efficiency was lower than 30%, internal pores may have been generated, and the
mechanical properties may have been reduced [20,34]. If the overlapping efficiency was
too high, deformation and internal stress would occur, owing to the reduced productivity
and thermal overlap. Figure 5 shows the schematic diagram of the overlapping efficiency.
In the deposition of Ti-Nb-Cr-V-Ni-Al, the laser power, scan speed, powder feed rate, and
shield gas flow rate were used as deposition parameters. The experiment was conducted at
room temperature and in a habitual state, and the DED equipment was sealed to block the
inflow of air and prevent oxidation. Table 3 lists the deposition conditions, and Figure 6
shows the DED results of Ti-Nb-Cr-V-Ni-Al.
 overlappingefficiency.
overlapping efficiency.InInthe
thedeposition
depositionofofTi‐Nb‐Cr‐V‐Ni‐Al,
Ti‐Nb‐Cr‐V‐Ni‐Al,the thelaser
laserpower,
power,scan
scan
speed,powder
speed, powderfeed
feedrate,
rate,and
andshield
shieldgas
gasflow
flowrate
ratewere
wereused
usedasasdeposition
depositionparameters.
parameters.
Theexperiment
The experimentwaswasconducted
conductedatatroom
roomtemperature
temperatureandandininaahabitual
habitualstate,
state,and
andthe
theDED
DED
Materials 2022, 15, 6570 6 of 13
equipment was sealed to block the inflow of air and prevent oxidation. Table
equipment was sealed to block the inflow of air and prevent oxidation. Table 3 lists the 3 lists the
deposition conditions, and Figure 6 shows the DED results of Ti‐Nb‐Cr‐V‐Ni‐Al.
deposition conditions, and Figure 6 shows the DED results of Ti‐Nb‐Cr‐V‐Ni‐Al.

Figure 5.5.The
Figure5. schematic
Theschematic diagram
schematicdiagram ofofthe
diagramof overlapping
theoverlapping efficiency.
overlappingefficiency.
efficiency.
Figure The the

Table
Table 3.3.The
Table3. TheDED
The DEDconditions.
DED conditions.
conditions.

Laser Power
ScanningSpeed
Scanning
Scanning Speed
Speed PowderFeed
Powder
Powder FeedRate
Feed Rate
Rate ShieldGas
Shield
Shield GasFlow
Gas Flow
Flow
Laser Power(W)
LaserPower (W)
(W) (mm/s) (g/min) Rate (L/min)
(mm/s)
(mm/s) (g/min)
(g/min) Rate(L/min)
Rate (L/min)
1000
1000
1000 888 13
13
13 15
1515

Figure6.
Figure
Figure 6.6.The results
Theresults for
resultsfor Ti‐Nb‐Cr‐V‐Ni‐Al:
forTi‐Nb‐Cr‐V‐Ni‐Al:
Ti-Nb-Cr-V-Ni-Al: (a)
(a) Ti‐Nb‐Cr‐V‐Ni‐Al
(a) deposited
Ti-Nb-Cr-V-Ni-Al
Ti‐Nb‐Cr‐V‐Ni‐Al onTi‐6Al‐4V
deposited
deposited on Ti‐6Al‐4V
on and
Ti-6Al-4V
and (b)
and
(b)
Ti‐Nb‐Cr‐V‐Ni‐Al
(b) Ti-Nb-Cr-V-Ni-Al
Ti‐Nb‐Cr‐V‐Ni‐Al deposited
deposited
deposited on Inconel
on on 718.
Inconel
Inconel 718.718.

4. Results
4.4.Results
Results
4.1. Microstructure
4.1.Microstructure
4.1. Microstructure
To investigate the microstructure of the deposited Ti-Nb-Cr-V-Ni-Al, SEM images and
Toinvestigate
investigatethe
themicrostructure
microstructureofofthe thedeposited
depositedTi‐Nb‐Cr‐V‐Ni‐Al,
Ti‐Nb‐Cr‐V‐Ni‐Al, SEMimages images
EBSDToanalyses were performed. To fabricate the SEM and EBSD specimens, 5 SEM × 5 × 5 mm
and
and EBSD analyses
EBSD analyses were
were performed.
performed. To fabricate the SEM and EBSD specimens, 5
××55××55
Ti-Nb-Cr-V-Ni-Al was deposited on a To fabricate
Ti-6Al-4V the SEMTo
substrate. and EBSD the
prevent specimens,
inflow of5compo-
mmmm Ti‐Nb‐Cr‐V‐Ni‐Alwas wasdeposited
depositedon on aTi‐6Al‐4V
Ti‐6Al‐4Vsubstrate.
substrate. Toprevent
preventthe theinflow
inflowofof
nentsTi‐Nb‐Cr‐V‐Ni‐Al
of the substrate through the meltingapool, a 3 × 3 × 3 mm To specimen was fabricated
componentsofofthe
components thesubstrate
substratethrough
throughthethemelting
meltingpool,
pool,aa33××33××33mm mmspecimen
specimenwas was
by cutting the deposited Ti-Nb-Cr-V-Ni-Al with a wire, and the deposited specimens were
fabricated
fabricated by cutting
bymechanical the deposited
cutting thepolishing
deposited Ti‐Nb‐Cr‐V‐Ni‐Al with a wire, and the deposited
subjected to forTi‐Nb‐Cr‐V‐Ni‐Al
analysis. From thewith phasea analysis,
wire, andit was
the deposited
predicted
specimenswere
specimens weresubjected
subjected tomechanical
mechanicalpolishing
polishingforforanalysis.
analysis.From
Fromthe thephase
phaseanalysis,
analysis,
that the BCC B2 phase wasto 62.2%, the BCC A2 phase was 21.6%, and the C14 Laves phase
itit was
was predicted
predicted that
that the
the BCC
BCC B2B2 phase
phase was
was 62.2%,
62.2%, the
the BCC
BCC A2
A2 phase
phase was
was
was 16.2% (Figure 3). However, the sigma(σ) and Ti2 Ni phases appeared in the deposited
21.6%,
21.6%, and
and the
the
C14Laves
C14 Lavesphase
Ti-Nb-Cr-V-Ni-Alphasewas
was16.2%
16.2%
[35,36]. (Figure3).
(Figure 3).However,
Microstructure However, thesigma(σ)
analysisthe sigma(σ)
revealed and
thatand
theTiσTi 2Niphases
2Ni
phasephases appeared
appeared
appeared in a
inin the
the deposited
deposited Ti‐Nb‐Cr‐V‐Ni‐Al
Ti‐Nb‐Cr‐V‐Ni‐Al [35,36].
[35,36]. Microstructure
Microstructure analysis
analysis revealed
revealed
form surrounding the BCC A2 phase, and the Ti2 Ni phase appeared in a fine form inside that
that theσσ
the
the σ and BCC A2 phases [6,37]. The microstructure of Ti-Nb-Cr-V-Ni-Al showed that the
BCC A2 phase, which grew first at high temperatures, grew first, and then the σ phase grew
rapidly before the Ti2 Ni precipitated phase grew [38,39]. Figure 7 shows the SEM image of
Ti-Nb-Cr-V-Ni-Al. EBSD analysis revealed that the fraction of the BCC A2 phase was 28.2%,
that of the σ phase was 64.2%, and that of the Ti2 Ni phase was 7.6%. Figure 8a shows the
IPF map of Ti-Nb-Cr-V-Ni-Al, and Figure 8b shows the phase map of Ti-Nb-Cr-V-Ni-Al.
 in a fine
phase form inside
appeared in a the
form σ surrounding
and BCC A2 the phases
BCC[6,37]. The microstructure
A2 phase, and the Ti2Ni phase of Ti‐Nb‐Cr‐V‐
appeared
Ni‐Al showed
in a fine that the
form inside theBCCσ and A2 BCC
phase, A2which
phases grew first
[6,37]. at microstructure
The high temperatures, grew first,
of Ti‐Nb‐Cr‐V‐
and
Ni‐Althen the σ phase
showed that thegrew
BCC rapidly before
A2 phase, the Tigrew
which 2Ni precipitated
first at highphase grew [38,39].
temperatures, grew Figure
first,
7and
shows
thenthe theSEM
σ phaseimagegrewof rapidly
Ti‐Nb‐Cr‐V‐Ni‐Al.
before the TiEBSD analysis revealed
2Ni precipitated phase grewthat the fraction
[38,39]. of
Figure
the BCC the
7 shows A2 phase
SEM image was 28.2%, that of the σ phase
of Ti‐Nb‐Cr‐V‐Ni‐Al. EBSD was 64.2%, revealed
analysis and that thatof the
theTifraction
2Ni phase of
Materials 2022, 15, 6570 7 of 13
was 7.6%.A2
the BCC Figure
phase8awas shows
28.2%, thethat
IPFof mapthe of Ti‐Nb‐Cr‐V‐Ni‐Al,
σ phase was 64.2%, and andthat
Figure
of the8bTishows
2Ni phasethe
phase mapFigure
was 7.6%. of Ti‐Nb‐Cr‐V‐Ni‐Al.
8a shows the IPF Themap microstructure of the deposited
of Ti‐Nb‐Cr‐V‐Ni‐Al, and FigureTi‐Nb‐Cr‐V‐Ni‐Al
8b shows the
contained
phase mapthe of σTi‐Nb‐Cr‐V‐Ni‐Al.
phase, which was The not predicted
microstructureby theofphase analysis. The
the deposited reason for the
Ti‐Nb‐Cr‐V‐Ni‐Al
The microstructure
appearance
contained the σ phase,of the
of unexpected which deposited
phases notTi-Nb-Cr-V-Ni-Al
wasfrom the phase by
predicted analysis contained
is that
the phase thethe phase,
σThe
accuracy
analysis. ofwhich
thefor
reason was
phase
the
not predicted
analysis is by
highly the phase
dependent analysis.
on the The reason
thermodynamic for the appearance
database
appearance of unexpected phases from the phase analysis is that the accuracy of the phase of
used, unexpected
and a phases
complete
from theisphase
thermodynamic
analysis highly analysis
analysis isofthat
dependent eachthebinary
on accuracy
the andofternary
the phase
thermodynamic analysis
phase
database is highly
diagram
used, anddependent
belonging to the
a complete on
the thermodynamic
multicomponent
thermodynamic analysis database
system was used, and
not performed
of each a complete
binary andforternary thermodynamic
accurate calculations
phase analysis
diagram[40–42]. of
belongingeach binary
However,
to the
andmicrostructure
the ternary phase
multicomponent diagram
was
system wasbelonging
similar that to
nottoperformed ofthe multicomponent
Ti‐Nb‐Cr‐V‐Ni‐Al
for system
that
accurate calculations was was not performed
heat‐treated
[40–42]. However,after
for microstructure
the accurate
casting [6]. It calculations
was found [40–42].
that
was similar However,
thetogrowth the microstructure
microstructure
that ofofTi‐Nb‐Cr‐V‐Ni‐Al
this that was
waswas similar
because to
of that
heat‐treated of Ti-
the high
after
Nb-Cr-V-Ni-Al
energy
casting density
[6]. It wasofthat
the wasthat
laser
found heat-treated
used theduring
growth after
DED,of casting
which
this [6]. It was
rapidly
microstructure found
increased thattemperature
the
was because theofgrowth
the high toof
this
aenergymicrostructure
high density
temperature was
of theand because
laserthen
usedshowedof the high
during DED, energy
the heat which density
treatment of the laser
effect because
rapidly increased used during
of the rapid
the temperature DED,to
awhich
high rapidly
cooling. temperatureincreased
Rapid temperature and thethen temperature
changes
showed alsothe to aheat
highthe
affected temperature
grain size.
treatment and
effect then
grainshowed
Thebecause size of the
of the the heat
Ti‐
rapid
treatment
Nb‐Cr‐V‐Ni‐Al
cooling. effecttemperature
Rapid because
was 1–35 ofμm, the rapidwas
which
changes cooling.
also finer Rapid
thanthe
affected temperature
the 45–150
grain changes
μmThe
size. grainalso
powder sizeaffected
size used.
of the Ti‐the
grain size. The grain size of the Ti-Nb-Cr-V-Ni-Al was 1–35 µm, which was finer than the
Nb‐Cr‐V‐Ni‐Al was 1–35 μm, which was finer than the 45–150 μm powder size used.
45–150 µm powder size used.

Figure 7. The SEM image of the Ti‐Nb‐Cr‐V‐Ni‐Al: (a) ×1000 magnification and (b) ×5000
magnification.
Figure 7. The
Figure 7. TheSEM
SEM image
image of theofTi-Nb-Cr-V-Ni-Al:
the Ti‐Nb‐Cr‐V‐Ni‐Al:
(a) ×1000(a) ×1000 magnification
magnification and
and (b) ×5000 (b) ×5000
magnification.
magnification.

Figure
Figure8.8.The
TheEBSD
EBSDresults
resultsofofthe
theTi‐Nb‐Cr‐V‐Ni‐Al:
Ti-Nb-Cr-V-Ni-Al:(a)
(a)IPF
IPFmap
mapand
and(b)
(b)phase
phasemap
map(red
(red==BCC
BCCA2,
A2,
green
green==8.
Figure σ,σ,and
The yellow
EBSD
and ==TiTi
results
yellow 2Ni).
2of the Ti‐Nb‐Cr‐V‐Ni‐Al: (a) IPF map and (b) phase map (red = BCC A2,
Ni).
green = σ, and yellow = Ti2Ni).
4.2. XRD and EDS Analyses
The XRD and EDS analyses were performed to verify the phase and components of
Ti-Nb-Cr-V-Ni-Al. Figure 9 shows the results of the XRD analysis. In the results of the
XRD analysis, the σ phase peak was higher than those of the BCC A2 and Ti2 Ni phases.
As a result of the XRD analysis, the peaks for the three phases occurred as shown in the
phase map, where the intensity of the σ phase peak was the highest and the intensity of
the Ti2 Ni phase peak was the lowest. Additionally, a lot of noise was generated as a result
of the XRD analysis. It was found that the noise was caused by not melting the powder
inside the deposited Ti-Nb-Cr-V-Ni-Al. In order to reduce this noise, it was confirmed
 completely melted.
The EDS analysis was analyzed through SEM imaging (Figure 7b). For component
analysis of Ti‐Nb‐Cr‐V‐Ni‐Al and each phase, component analysis of the entire area and
each phase point was conducted. Table 4 shows the chemical compositions of the structure
constituents for Ti‐Nb‐Cr‐V‐Ni‐Al. As a result of EDS analysis, the BCC A2 phase showed
Materials 2022, 15, 6570 a Ti‐Nb‐rich composition, as in the phase analysis results. The σ phase, which did 8 of not
13
appear as a result of the previous phase analysis, showed a Ti‐Ni‐rich composition, as in
the BCC B2 phase. The Ti2Ni phase showed the highest Ti composition and showed the
Ti
that2Ni
theratio composition.
deposit should be The composition
performed of Ti‐Nb‐Cr‐V‐Ni‐Al
at a higher wasthe
temperature so that similar to the
powder design
could be
composition,
completely but the composition of Nb was measured to be slightly lower.
melted.

Figure9.9.The
Figure Theresults
resultsofofXRD
XRDanalysis
analysisofofTi-Nb-Cr-V-Ni-Al.
Ti‐Nb‐Cr‐V‐Ni‐Al.

Table 4. The
The EDSchemical
analysiscompositions of the
was analyzed structure
through SEMconstituents
imagingfor Ti‐Nb‐Cr‐V‐Ni‐Al.
(Figure 7b). For component
analysis of Ti-Nb-Cr-V-Ni-Al and each phase, component analysis of the entire area and
Element (at %) Ti Nb Cr V Ni Al
each phase point was conducted. Table 4 shows the chemical compositions of the structure
Constituents
constituents for Ti-Nb-Cr-V-Ni-Al. As a result of EDS analysis, the BCC A2 phase showed a
BCC composition,
Ti-Nb-rich A2 phase 38.4
as in the phase28.7 9.0 The σ10.1
analysis results. phase, which6.0did not appear
7.8
as a resultσ of
phase 32.3 analysis,
the previous phase 15.1 showed 13.9
a Ti-Ni-rich9.0composition,
21.1 as in the8.6
BCC
Ti Ni phase 46.2 8.2 7.0 8.8 23.8
B2 phase. The Ti2 Ni phase showed the highest Ti composition and showed the Ti2 Ni ratio
2 6.0
Ti‐Nb‐Cr‐V‐Ni‐Al
composition. 37.5of Ti-Nb-Cr-V-Ni-Al
The composition 13.2 8.8was similar
14.5to the design
16.7 composition,
9.3
Nominal
but composition
the composition 34.6 measured
of Nb was 20.4 to be slightly
10.0 lower. 10.0 15.0 10.0

Table 4. The chemical compositions of the structure constituents for Ti-Nb-Cr-V-Ni-Al.

4.3. Microhardness
Element (at %) Ti Nb Cr V Ni Al
Constituents
BCC A2 phase 38.4 28.7 9.0 10.1 6.0 7.8
σ phase 32.3 15.1 13.9 9.0 21.1 8.6
Ti2 Ni phase 46.2 8.2 7.0 8.8 23.8 6.0
Ti-Nb-Cr-V-Ni-Al 37.5 13.2 8.8 14.5 16.7 9.3
Nominal composition 34.6 20.4 10.0 10.0 15.0 10.0

4.3. Microhardness
The microhardness measurements were performed for Ti-Nb-Cr-V-Ni-Al deposited
by DED. To measure the microhardness as shown in Figure 10, two Ti-Nb-Cr-V-Ni-Al
specimens deposited on Ti-6Al-4V and Inconel 718 were divided into three sections: a
deposition area, a substrate area, and a bonding layer for a total of six Vickers hardness
(Hv) areas measured. The microhardness measurement was performed nine times for each
area to consider the non-uniformity of the hardness according to the deposition height,
and the average value was used as the result. The microhardness of the Ti-Nb-Cr-V-Ni-Al
deposited area was measured to be approximately 900 HV. The microhardness of Ti-6Al-4V
and Inconel 718 used by the substrates increased by 17–19% compared with that of the
 depositiondeposited
specimens area, a substrate area, and
on Ti‐6Al‐4V and aInconel
bonding 718layer
werefordivided
a total into
of sixthree
Vickers hardness
sections: a
deposition area, a substrate area, and a bonding layer for a total of six Vickers hardnessfor
(Hv) areas measured. The microhardness measurement was performed nine times
eachareas
(Hv) area measured.
to considerThe themicrohardness
non‐uniformitymeasurement
of the hardness was according
performed to thetimes
nine deposition
for
height,
each areaandto the average
consider thevalue was used asofthe
non‐uniformity result.
the The microhardness
hardness according to the of the Ti‐Nb‐Cr‐
deposition
V‐Ni‐Al
height, and deposited
the average areavalue
was was
measured
used astothe beresult.
approximately 900 HV. The
The microhardness microhardness
of the Ti‐Nb‐Cr‐
Materials 2022, 15, 6570 9 of 13
of Ti‐6Al‐4V
V‐Ni‐Al and Inconel
deposited area was 718 used by to
measured thebesubstrates increased
approximately 900 by
HV.17–19% compared with
The microhardness
ofthat of the wrought
Ti‐6Al‐4V and Inconel material (340by
718 used Hv),
the and the microhardness
substrates of the bonding
increased by 17–19% compared layer
with was
measured to be an intermediate value between the microhardness
that of the wrought material (340 Hv), and the microhardness of the bonding layer was of the deposition area
wrought
and the material
measured to be an(340
substrate area Hv), and the
[43,44].
intermediate microhardness
Figure
value 11 shows
between ofmicrohardness
the
the the bonding layer
microhardness was measured
of distribution.
the deposition The tohigh
area be
an intermediate
microhardness
and the substrateofvalue between
Ti‐Nb‐Cr‐V‐Ni‐Al
area the microhardness
[43,44]. Figure 11was related
shows of the deposition
to the high volume
the microhardness area and the
fraction
distribution. substrate
Theofhighthe σ
area
phase.[43,44].
The σ
microhardness Figure
phase 11is shows
knownthe
of Ti‐Nb‐Cr‐V‐Ni‐Al microhardness
to exhibit relateddistribution.
wasbrittleness toand
thehigh The highfraction
highhardness.
volume microhardness
Therefore, σof
of the high
Ti-Nb-Cr-V-Ni-Al
volume
phase. Thefraction
σ phase ofwas related
the σ to
is known to
phasethe
exhibit high volume
forbrittleness fraction
Ti‐Nb‐Cr‐V‐Ni‐Al of the σ phase.
increased
and high hardness. The σ
the hardness
Therefore, phase
the high is
and
known
decreased
volume to exhibit brittleness
the ductility.
fraction of the σThe and high
causefor
phase hardness. Therefore,
of Ti‐Nb‐Cr‐V‐Ni‐Al the
the increased microhardness high volume
increased theof the fraction
substrate
hardness of
andthe
was
σ phase
decreased for
found to be Ti-Nb-Cr-V-Ni-Al
theheat
ductility.
treatment, increased
The owing
cause of the
to the hardness
the increased and decreased
microhardness
rapid temperature the ductility.
changeofoccurring The
the substrate cause
in thewasDED.
of the increased
found to be heat microhardness
treatment, owing of to
thethesubstrate was found change
rapid temperature to be heat treatment,
occurring owing
in the DED.to
the rapid temperature change occurring in the DED.

Figure 10. The measure point for the microhardness of Ti‐Nb‐Cr‐V‐Ni‐Al deposited on the
Figure
Figure 10. The
10.
substrates.The measure point for
measure point for the
the microhardness
microhardness of
of Ti-Nb-Cr-V-Ni-Al
Ti‐Nb‐Cr‐V‐Ni‐Aldeposited
depositedon
onthe
thesubstrates.
substrates.

Figure 11. The microhardness distributions of Ti-Nb-Cr-V-Ni-Al deposited on the substrates.

4.4. Heat-Affected Zone

To analyze the thermal properties and thermal shielding effect of Ti-Nb-Cr-V-Ni-Al
composed of the refractory material, the HAZ was analyzed through a preheating test.
For HAZ measurement, the surface of the specimen was preheated with a laser with a
500-W output and 15 L/min shield gas (Ar) for 3 s [45]. Preheating tests were performed
on four specimens of conventional Ti-6Al-4V and Inconel 718 as well as Ti-6Al-4V and
Inconel 718 deposited with Ti-Nb-Cr-V-Ni-Al. Figure 12 shows the measurement results
for the HAZ depth for each specimen. The HAZ depth of the conventional Ti-6Al-4V was
4.021 mm (Figure 12a), and the HAZ depth of the Ti-Nb-Cr-V-Ni-Al-deposited Ti-6Al-4V
 composed of the refractory material, the HAZ was analyzed through a preheating test.
For HAZ measurement, the surface of the specimen was preheated with a laser with a
500‐W output and 15 L/min shield gas (Ar) for 3 s [45]. Preheating tests were performed
on four specimens of conventional Ti‐6Al‐4V and Inconel 718 as well as Ti‐6Al‐4V and
Materials 2022, 15, 6570 Inconel 718 deposited with Ti‐Nb‐Cr‐V‐Ni‐Al. Figure 12 shows the measurement 10 results
of 13
for the HAZ depth for each specimen. The HAZ depth of the conventional Ti‐6Al‐4V was
4.021 mm (Figure 12a), and the HAZ depth of the Ti‐Nb‐Cr‐V‐Ni‐Al‐deposited Ti‐6Al‐4V
was 3.375 mm (Figure 12c). The HAZ depth of the conventional Inconel 718 was 3.523 mm
was 3.375 mm (Figure 12c). The HAZ depth of the conventional Inconel 718 was 3.523 mm
(Figure 12b), and the HAZ depth of the Inconel 718 deposited with Ti‐Nb‐Cr‐V‐Ni‐Al was
(Figure 12b), and the HAZ depth of the Inconel 718 deposited with Ti-Nb-Cr-V-Ni-Al
3.015 mm (Figure 12d). The HAZ size was determined by the thermal diffusivity of each
was 3.015 mm (Figure 12d). The HAZ size was determined by the thermal diffusivity
material. The thermal diffusivity of the Inconel 718 was higher than that of the Ti‐6Al‐4V,
of each material. The thermal diffusivity of the Inconel 718 was higher than that of the
and the HAZ was smaller in the Inconel 718 [46,47]. The HAZ depths of the Ti‐6Al‐4V and
Ti-6Al-4V, and the HAZ was smaller in the Inconel 718 [46,47]. The HAZ depths of the
Inconel 718 were reduced by 16.07% and 14.42%, respectively, according to the Ti‐Nb‐Cr‐
Ti-6Al-4V and Inconel 718 were reduced by 16.07% and 14.42%, respectively, according to
V‐Ni‐Al deposition. As a result of the HAZ measurement, it was found that the Ti‐Nb‐Cr‐
the Ti-Nb-Cr-V-Ni-Al deposition. As a result of the HAZ measurement, it was found that
V‐Ni‐Al had a higher thermal diffusivity than the Inconel 718 and that the thermal
the Ti-Nb-Cr-V-Ni-Al had a higher thermal diffusivity than the Inconel 718 and that the
shielding
thermal effect could
shielding effectbecould
obtained throughthrough
be obtained the deposition of Ti‐Nb‐Cr‐V‐Ni‐Al.
the deposition of Ti-Nb-Cr-V-Ni-Al.

Figure12.
Figure 12.The
Themeasurement
measurementresults
resultsofofthe
theHAZ:
HAZ:(a)
(a)Ti-6Al-4V,
Ti‐6Al‐4V,(b)(b) Inconel
Inconel 718,
718, (c)(c) Ti‐Nb‐Cr‐V‐Ni‐
Ti-Nb-Cr-V-Ni-Al
Al deposited on Ti‐6Al‐4V, and (d) Ti‐Nb‐Cr‐V‐Ni‐Al deposited on Inconel
deposited on Ti-6Al-4V, and (d) Ti-Nb-Cr-V-Ni-Al deposited on Inconel 718. 718.

5.
5. Conclusions
Conclusions
In
Inthis
thisstudy, a Ti-Nb-Cr-V-Ni-Al
study, a Ti‐Nb‐Cr‐V‐Ni‐AlRHEA was deposited
RHEA using DED.
was deposited usingThe phase
DED. diagram
The phase
and phaseand
diagram fraction
phaseoffraction
Ti-Nb-Cr-V-Ni-Al were analyzed
of Ti‐Nb‐Cr‐V‐Ni‐Al werefor deposition
analyzed for on Ti-Nb-Cr-V-Ni-Al.
deposition on Ti‐Nb‐
For the deposited
Cr‐V‐Ni‐Al. Ti-Nb-Cr-V-Ni-Al,
For the powders of powders
deposited Ti‐Nb‐Cr‐V‐Ni‐Al, each element were
of each mixedwere
element to prepare a
mixed to
mixed Ti-Nb-Cr-V-Ni-Al powder and deposited on Ti-6Al-4V and Inconel 718
prepare a mixed Ti‐Nb‐Cr‐V‐Ni‐Al powder and deposited on Ti‐6Al‐4V and Inconel 718 substrates.
The microstructure
substrates. and hardnessand
The microstructure of the deposited
hardness Ti-Nb-Cr-V-Ni-Al
of the were measured.
deposited Ti‐Nb‐Cr‐V‐Ni‐Al In
were
addition, HAZ and thermal shielding analyses were performed on the deposited Ti-Nb-Cr-
V-Ni-Al. The primary findings of this study are as follows:
• SEM images and EBSD analysis were used to investigate the microstructure of the
deposited Ti-Nb-Cr-V-Ni-Al. Phase analysis predicted that the BCC B2 phase was
62.2%, the BCC A2 phase was 21.6%, and C14 Laves phase was 16.2%. However, the σ
phase was 64.2%, the BCC A2 phase was 28.2%, and the Ti2 Ni phase was 7.6% in the
deposited Ti-Nb-Cr-V-Ni-Al.
• The microstructure of the deposited Ti-Nb-Cr-V-Ni-Al consisted of a phase not pre-
dicted by the phase analysis but showed a microstructure similar to that of Ti-Nb-Cr-
V-Ni-Al annealed after casting. In addition, the deposited Ti-Nb-Cr-V-Ni-Al exhibited
a fine grain size of 1–35 µm. The growth of this microstructure was attributed to the
Materials 2022, 15, 6570 11 of 13

high energy density of the laser used in DED, which showed the heat treatment effect
by rapid cooling after rapidly increasing the temperature to a high temperature.
• The microhardness of the deposited Ti-Nb-Cr-V-Ni-Al was investigated. The micro-
hardness of the Ti-Nb-Cr-V-Ni-Al deposited area was measured to be approximately
900 HV. The microhardness of the Ti-6Al-4V and Inconel 718 used by the substrates in-
creased by 17–19% compared with that of the wrought material, and the microhardness
of the bonding layer was measured to be an intermediate value of the microhardness
of the deposition area and the substrate. The cause of the increased microhardness of
the substrate was analyzed as heat treatment, owing to the rapid temperature change
occurring in the DED.
• A preheat test was performed for the HAZ measurement of the Ti-Nb-Cr-V-Ni-Al
deposited by DED. The HAZ depths of the Ti-6Al-4V and Inconel 718 were reduced
by 16.07% and 14.42%, respectively, according to the Ti-Nb-Cr-V-Ni-Al deposition.
The HAZ decreased owing to the high thermal diffusivity of Ti-Nb-Cr-V-Ni-Al. In
addition, the deposited Ti-Nb-Cr-V-Ni-Al exhibited a heat-shielding effect.
The RHEAs had excellent mechanical properties at high temperatures, so their use-
fulness is high. However, it is necessary to study the manufacturing method because the
design of the material is difficult due to the correlation between the constituent materials.
In particular, since additive manufacturing of RHEAs has many process variables and rapid
temperature changes occur, it is necessary to analyze the effect of each process variable
on phase formation. In this study, it was found that an unexpected phase occurred in the
preparation of RHEAs using DED. In future research, we will analyze the effect of each
process variable on phase formation and find suitable manufacturing conditions for RHEAs
by controlling the process variables. This study on the manufacturing of RHEAs with a
Ti-Nb-Cr-V-Ni-Al composition using DED can be used as a novel RHEA manufacturing
method and can be used as basic data for future research of RHEA phase analysis according
to additive manufacturing conditions.

Author Contributions: Conceptualization, H.-I.J. and D.-H.K.; methodology, H.-I.J.; software, H.-I.J.;
validation, H.-I.J.; formal analysis, H.-I.J.; investigation, H.-I.J.; resources, H.-I.J.; data curation, H.-I.J.;
writing—original draft preparation, H.-I.J. and D.-H.K.; visualization, H.-I.J.; writing—review and
editing, D.-H.K. and C.-M.L.; supervision, D.-H.K. and C.-M.L.; project administration, H.-I.J., D.-H.K.
and C.-M.L.; funding acquisition, C.-M.L. All authors have read and agreed to the published version
of the manuscript.
Funding: This research was supported by the National Research Foundation of Korea (NRF) grant
funded by the Korea government (MSIT) (No. 2019R1A5A8083201 and No. 2022R1A2B5B03001884).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data presented in this article are available upon request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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