Journal Pre-proof

Recent Advances in Additive Manufacturing of

Refractory High Entropy Alloys: A Critical Review

Akshay Yarlapati, Y.N Aditya, Deepak Kumar,

R.J. Vikram, Mayank Yadav, Kallem Shekhar
Reddy, K.G. Prashanth

PII: S2949-9178(24)00068-3
DOI: https://doi.org/10.1016/j.jalmes.2024.100120
Reference: JALMES100120

To appear in: Journal of Alloys and Metallurgical Systems

Received date: 12 September 2024
Revised date: 8 October 2024
Accepted date: 17 October 2024
Please cite this article as: Akshay Yarlapati, Y.N Aditya, Deepak Kumar, R.J.
Vikram, Mayank Yadav, Kallem Shekhar Reddy and K.G. Prashanth, Recent
Advances in Additive Manufacturing of Refractory High Entropy Alloys: A
Critical Review, Journal of Alloys and Metallurgical Systems, (2024)
doi:https://doi.org/10.1016/j.jalmes.2024.100120
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 Recent Advances in Additive Manufacturing of Refractory High Entropy
Alloys: A Critical Review
Akshay Yarlapati a, Y.N Aditya b, Deepak Kumar c, R. J. Vikram d, Mayank Yadav e,
Kallem Shekhar Reddy f, K. G. Prashanth e, g, h*
a
Department of Metallurgical Engineering, Jawaharlal Nehru Technological University, Hyderabad-
500085, India
b
Department of Mechanical and Mechatronics Engineering, University of Waterloo, 200
UniversityAvenue West, Waterloo, ON N2L 3G1, Canada
c
School of Industrial Engineering, Purdue University, West Lafayette, IN 47907, United States
d
Department of Materials Engineering, Indian Institute of Science (IISc), Bangalore 560012,
India
e
Department of Mechanical and Industrial Engineering, Tallinn University of Technology, 19086
Tallinn, Estonia
f
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras (IIT-
M), Chennai 600 036, India

f
g
CBCMT, Vellore Institute of Technology, Vellore 632014, Tamil Nadu, India

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h
Department of Smart Manufacturing, New Age Makers Institute of Technology
(NAMTech),Gandhinagar 382355, Gujarat, India

Abstract

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Refractory High Entropy alloys (RHEAs) have evolved as a superior multicomponent material
having a unique combination of microstructures and mechanical properties. RHEAs are a
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particular grade of high entropy alloys (HEAs) known for their outstanding high-temperature
properties achieved thorough their constituent refractory elements. To date, majority of the
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RHEAs have been manufactured through several conventional methods, but are limited by
certain limitations. Additive manufacturing (AM) has the potential to revolutionize the
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manufacturing industry by providing excellent opportunities to fabricate RHEAs while

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providing opportunities for enhancing the design freedom and complex geometrical shapes.
As the field is rapidly evolving, a systematic examination of our comprehension is beneficial,
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and this article attempts to address this issue. To find the right place in industrial markets,
additively manufactured RHEAs require further advancements. The present review provides a
comprehensive overview of the additively manufactured RHEAs in terms of microstructural
characterization, mechanical behaviour and other environmental properties published so far.
This review article is presented lucidly with an aim of better understanding for the readers in
this domain. To this end, future works and current challenges are also included and discussed
briefly.

Keywords: Refractory High Entropy Alloys (RHEAs), Additive Manufacturing,

Microstructure, Mechanical Behaviour, Functional Properties

*
Corresponding author’s email: [email protected]
 Graphical Abstract

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 Nomenclature

Symbol Description
AM Additive Manufacturing
PFF Powder Fed Fusion
PBF Powder Bed Fusion
L-PFF Laser-based Powder Fed Fusion
WAAM Wire Arc Additive Manufacturing
LC Laser Cladding
EHLC Extreme High-Speed Laser Cladding

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EB-PFF Electron Beam-based Powder Fed Fusion

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CS Cold Spray
CSAM Cold Spray Additive Manufacturing

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LENS Laser Engineered Net Shaping
DLD Direct Laser Deposition
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LMD Laser Metal Deposition
LAM Laser Augmented Manufacturing
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LADRM Laser-Aided Direct Rapid Manufacturing

DLF Direct Laser Fabrication
DMLS Direct Metal laser Sintering
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SLS Selective Laser Sintering

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SHS Selective Heat Sintering

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CAD Computer Aided Design

BCC Body Centered Cubic
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FCC Face Centered Cubic

HCP Hexagonal Close Packed
SEM Scanning Electron Microscope
TEM Transmission Electron Microscope
EDS Energy Dispersive Spectroscopy
EBSD Electron Backscattered Secondary Diffraction
XRD X-Ray Diffraction
RHEA Refractory High Entropy Alloy
L-RHEA Lightweight Refractory High Entropy Alloy
HEA High Entropy Alloy
MEA Medium Entropy Alloy

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LEA Low Entropy Alloy
CET Columnar to Equiaxed Transition

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1. Introduction

1.1. High Entropy Alloys

The discovery of new metallic materials has enabled the discovery of a majority of significant

engineering developments throughout the history of humanity. Our materials have been

produced through alloying since around 5,000 years ago, or 3,000 BC [1-2]. High entropy

alloys (HEAs) or multi-component alloys are a new class of special alloys composed of

equimolar amounts of significant elements (typically five or more principal elements) [3].

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HEAs differ from traditional binary alloys of Fe-based, Al-based, Ni-based, Cu-based, and Cr-

based alloys in a way that it does not consist of a single principal or base element (Solvent), to

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which a secondary alloying addition (Solute) are made to enhance the properties. For

instance, consider stainless steels, which typically contain 60-70% Fe, 18% Cr, 8% Ni, and a
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trace addition of Mo, Mn, Si etc. The base metal (solvent) in this alloy is Fe and the solute
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elements are Cr, Ni, etc. [4]. In contrast, high entropy alloys do not fall under this

classification of a single principal element with other solutes.

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Prof. Yeh [3] and Prof. Cantor [5-9] were the first to coin the term high entropy alloys
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in 2004. Since then, high entropy alloys have gained significant importance and extensive
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research has been conducted in this field. Works on HEAs offer numerous opportunities to
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develop, ameliorate and optimize physical metallurgy knowledge.

High Entropy Alloys (HEAs) can be classified in two ways: based on composition or

based on entropy. This indicates that there may exist an alloy system which can satisfy only

one of these two definitions. The question arises whether this type of alloy can still be

considered a true HEA. While there is some controversy surrounding this issue, most scholars

agree that it is not necessary to strictly adhere to the definition of HEAs [10]. In fact, a more

extensive composition can lead to the discovery of new alloys with exceptional properties

[11-12]. The number of publications has increased rapidly over the past five years [13], which

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indicates that the field is in vogue. According to metallurgical thermodynamics (Boltzmann

Equation) [14], as the count of equiatomic alloying elements increases, so does the material's

configurational entropy, which corresponds to the principle for HEAs as highlighted by Yeh

[3].

ΔSconf = k ln w = R ln n

∆Sconf denotes the change in configurational entropy per mole, R is the gas constant (8.314

J/K.mol), K the Boltzmann's constant, w is the number of mixing possibilities, and n refers to

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the number of elements. The schematic diagram for classifying alloys based on mixing

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entropies is shown in Fig. 1 [15]. The three categories of alloy classifications namely are low

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entropy alloys [16], medium entropy alloys [17], and high entropy alloys [18]. Low entropy

alloys are conventional alloys with one or two significant elements. Medium entropy alloys
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consist of 2 to 4 major elements, while high entropy alloys typically consist of 5 or more
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principal elements. 1.61R is the boundary line between the High Entropy Alloys (HEA) and

Medium Entropy Alloys (MEA), while 1R is the division between the Medium Entropy Alloys
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(MEA) and Low Entropy Alloys (LEA). Recently, a few alloys with four principal elements
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were also termed as high entropy alloys [19].

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High Entropy Alloys

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Medium Entropy Alloys

Low Entropy Alloys

ΔSconf ≤ R

1.61 R ≥ ΔSconf ≥ 1 R

ΔSconf > 1.61 R

Fig. 1. Schematic diagram classifying HEAs based on their entropies [15]

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 Given the synergistic core effect of high entropies, namely, short ordering, cocktail

effect, lattice distortion, and slower diffusions, HEAs tend to exhibit extraordinary properties

such as high strength [20], high ductility [21], oxidation resistance [22], corrosion resistance

[23], biocompatibility [24], wear resistance [25] in addition to the ability to maintain higher

strengths at elevated [26] as well as cryogenic temperatures [27]. The disordered lattice

configuration does have a strong solid solution strengthening effect, and perhaps the high

dislocation line tension prevents crystal plane slip, resulting in high strength and toughness of

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HEAs. Higher entropies stabilize the phases, forming relatively simple phases rather than

highly complicated phases with brittle intermetallics. Ample documentation is available in

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the literature to give an in-detailed explanation of the core effects of HEAs [28]. Amongst
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various types of HEAs, RHEAs appear to be a futuristic material that could play a vital role in
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the coming years as an alternative substitute for the challenges faced in the existing high-

temperature materials. The alloy systems of HEAs can be roughly categorized into two
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categories of transition Metal-High Entropy Alloys (TMHEA) and the Refractory High

Entropy Alloys (RHEA).

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1.2. Refractory High Entropy Alloys

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With advancements in the growth of supersonic and hypersonic aircraft, there is a need

to design materials that can withstand high resistance at elevated temperatures. RHEAs are a

class of high-temperature materials consisting of multiple refractory elements with melting

temperatures exceeding 2000°C. RHEAs exhibit the crystal structures as FCC, BCC, and HCP,

in addition to the intermetallic phases, including L12, B2, C14, C15 and C36 [29-32]. To give

a brief note about intermetallic phases, B2 is the ordered BCC phase in which one type of

element occupies the body-centered place while the other occupies the corner sites. L12 is an

ordered FCC structure in which one type of element sits at the face-centered places while the

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other is at the corner sites. C14, C15 and C16 are the three classes of Laves phase. Refractory

high entropy alloys have created a growing interest because of their high melting points and

their resistance to softening at elevated temperatures. These aspects of RHEAs contribute

towards the primary criterion for high-temperature applications [33]. The densities of RHEAs

produced by additive manufacturing lie in the range of 5.6 to 13.8 g cm-3. The development of

RHEAs began due to the published report of Senkov et al. in the year 2010 [34]. Fig. 2 [3,34]

depicts the historical evolution of materials as well as the birth of RHEAs in the Ashbe

diagram. The first example of the RHEA was having a BCC structure. RHEAs are generally

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classified into generations (first and second) solely based on the nature of their chronological

formulation. Alloys that fulfil this requirement are referred to as first-generation refractory

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alloys [36]. The actual compositions of the 1st generation RHEAs were quaternary alloy
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NbMoWTa and quinary alloy NbMoVWTa, which are both BCC and consist of a single solid

solution [37]. The biggest downside of first-generation RHEAs is their high density and poor
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corrosion and oxidation resistance. Second-generation RHEAs are being developed to have a

lower density, higher ductility, and resistance to oxidation and corrosion. These are developed
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by substituting lighter elements such as Cr, Al, Ti, and Zr for heavy refractory elements such
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as W, Ta, and Mo [37-38]. The methods of producing RHEAs include smelting and castings
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[39-40], powder metallurgy [41-42], melting [34,43], and magnetron sputtering [44,45].
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Despite being manufactured through these techniques, there is a need for post-treatment to

control the grain size and adjust the microstructure. RHEAs manufactured through casting

tend to suffer from undesirable phase segregations and the inevitable formation of coarser

grains. To mitigate this challenge, accelerated solidification is needed which has a profound

effect on reducing the elemental segregations and produces refined grains [46]. It is very

difficult to obtain the desired chemical composition of RHEAs without any impurities, when

produced via smelting and powder metallurgy techniques. Magnetron sputtering is another

popular method for producing these materials, though it could generate thin coatings only

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[45]. Therefore, additive manufacturing could be a potential technique to fabricate these

special-grade alloys with complex geometries and finer microstructures. Yet, a few

challenges are associated with the additive manufacturing of RHEAs as they are susceptible

to cracking. More emphasis on this field could overcome the shortcomings and prove to be a

promising method of producing RHEAs. Putting it all together there are about nine refractory

metals that may also be combined with other lighter metals in order to lower the density and

strengthen the alloys by forming compounds. In contrast to FCC-based HEAs, there exists a

paucity of studies conducted in therealm of RHEAs owing to their difficulties because of high

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melting point and brittleness [47].

HEA’s

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Birth of RHEA’s
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Fig. 2. Ashbe diagram showing evolution of engineering materials along with the birth of RHEAs
[3,34] Adapted with permission from [13], Copyright 2019, Elsevier

1.3. Progress of Refractory High Entropy Alloys

Refractory high entropy alloys (RHEAs) were first introduced in 2010 and were based

on the refractory elements Ta, Mo, V, Nb, and W [34]. RHEAs are thought to present a

potentially revolutionary and disruptive class of materials that can withstand very high

temperatures and possess increased resistance to oxidation, radiation, and mechanical stress

[46]. Fig. 3 demonstrates the evolution and progress in the domain of RHEAs. Fig. 3 illustrates

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how the number of RHEA articles has increased over the years. The search for the number of

publications was taken by making use of "High entropy refractory alloy," "multi-principal

element refractory alloy," "concentrated refractory alloy," and "refractory compositionally

complex alloy" as the subject. The publication boom can be attributed to the immense potential

in application areas such as kinetic energy penetrators, nuclear materials, shaped charge liners,

and turbine blades. The best universities and research institutes dedicated to RHEA work

include the United States Department of Energy, US-AFRL, Department of Defence-United

States, MIT, League of European Researchers, Helmholtz Institutes, KIT- Germany, Belgorod

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State University, Dalian University of Science, Central South University, Beijing Institute of

Technology, Centre National de la Recherche Scientifique, Northwestern Polytechnical

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University, The University of Tennessee, Chinese Academy of Sciences, Xi'an Jiaotong
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University, and University of Science and technology-Beijing, are among the few [48]. As the

field of AM processed RHEAs is rapidly increasing, several research labs/ universities across
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the globe are working on this novel class of RHEAs and not just restricted to the research

groups from the above-mentioned institutes.

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Fig. 3. Progress of Refractory High entropy alloys with the number of publications per year

1.4. Metallic Powder fabrication of RHEAs and their challenges

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 Powder characteristics impact the overall quality and performance of AM

fabricated products. Improper powder quality can result in problems in printed products,

including porosity, fractures, inclusions, and inadequate surface roughness. RHEA powders

can be prepared processes such as mechanical alloying, atomization processes (gas or water

atomization) and Plasma rotating electrode process. Powders prepared through atomization

technique are spherical, while the powders prepared using mechanical alloying are irregular

in shape [49]. To date, mechanical alloying stands out to be the most widely used technique

for fabricating RHEA powders. Despite, carrying out the process of mechanical alloying in

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the argon atmosphere, there is still contamination of C, N, O in the RHEA powders. This is

the major drawback of the powders prepared by mechanical alloying [50]. In recent years,

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atomization has emerged as a potential process for producing pre-alloyed powders for AM.
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Apart from the impurity contamination, there are some challenges associated with the
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production of RHEA powders. Although, fundamental scientific understanding of RHEA

powder production has evolved greatly, the cost of RHEA powders remains an issue that
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must be addressed before they can be used in industry. Furthermore, several atomization-
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based powder manufacturers make metal powders at larger quantities, but researchers
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attempting to investigate this unique class of RHEAs find it extremely difficult to get

powders that meet their powder quantity requirements. A recent paper analyzed the cost of
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alloying elements in HEAs [51] and interestingly, the bulk of the elements used in RHEAs,

such as Hf, Re, Ta, Nb, W, Mo, Cr, etc., cost around (~10 - 100 USD per mole of each

element). Another obstacle associated with RHEA powders is the possibility that certain

metals will become inaccessible in the future (for ex: Hf, Re etc..). The likelihood of this

happening is determined by a variety of aspects, including the geopolitical situations, natural

abundance of the elements, replacement potential, geopolitical environment, and economic

policy [51].

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 Laser based Powder Fed Fusion (L-PFF) offers a unique advantage of directly using the

elemental powders separately and incorporate them during the time of melting, using multi-

axial feeding sources - often referred to as “in-situ alloying” [52]. In-situ alloying reduces the

lengthy and time-consuming process of RHEA powder preparation. The detrimental effects

of elemental segregations, loss of alloying elements due to vaporizations, and non-

homogeneous chemistry of the powders produced by mechanical alloying or atomization, can

be reduced by incorporating in-situ alloying [52].

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2. Additive Manufacturing

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Additive manufacturing, or 3D printing, has gained importance over the past decade owing to

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its higher degrees of freedom [53]. Metal additive manufacturing has been classified into two

major categories as per ASTM (Standard) (i) Direct Energy Deposition (DED) or Powder Fed
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Fusion (PFF) and (ii) Powder Bed Fusion (PBF). According to a 2019 report [54], DED
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accounts for about 8.3% of the market while PBF accounts for about 85%, and by 2025 [55] it

is expected that PFF accounts for 11% while the PBF market will go down to 63%. The L-
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PFF and the PBF process schematics along with their key features are depicted in Fig. 4.
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2.1. Powder Fed Fusion (PFF)

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Powder Fed Fusion (PFF) is a subset of metal additive manufacturing in which the heat source
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(laser or plasma arc) is concentrated at a point, resulting in the formation of a melt pool [56–

58]. The feedstock material (powder or wire) is introduced simultaneously with the heat source.

The interaction between the high-power heat source and the feedstock material causes the

feedstock material to melt. As the melt pool solidifies, the molten feedstock material is

deposited in the form of a clad. The cold spray technique differs from the traditional PFF

principle of melting and depositing the material. Cold Spray additive manufacturing, also

known as Kinetic Spray deposition, is a low-temperature variant solely based on high-velocity

impact, resulting in severe plastic deformation of powder particles [59]. According to recent

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studies, the Cold Spray (CS) process can be used as an additive manufacturing technique [60].

PFF processes are further subdivided into several types, including Wire Arc Additive

Manufacturing (WAAM) [61–64], Laser-based Directed Energy Deposition or Powder Fed

Fusion (L-PFF) [64], Electron beam-based PFF (EB-PFF) [65], and Cold Spray Additive

Manufacturing (CSAM). Due to its advantageous properties, such as site-specific deposition

and additive manufacturing, PFF could be a promising technique for repairing and

refurbishing damaged components [66]. When compared to the PBF technique, PFF can

deposit a broader variety of materials at higher deposition rates (10 kg/hr for WAAM [67] and

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0.5 kg/hr for L- PFF [68]). PFF is also suitable for producing large-scale components [69].

The major drawbacks associated with PFF techniques are poor component quality, moderate

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complexity, and relatively high residual stresses, when compared to other PBF techniques
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such as EBM. The L-PFF process is gaining popularity among PFF-based additive

Manufacturing techniques. L-PFF has been the most widely used deposition technique for
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depositing RHEAs to date. Sandia National Laboratories first patented the laser-based

Directed Energy Deposition process in the 1980s, and many researchers have named this
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process using their terminologies, some of which have been listed here. Laser Cladding (LC)
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[70], Laser Metal Deposition (LMD) [71-72], Laser Engineered Net Shaping (LENS),
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Directed Energy Deposition (DED) [73-74], Directed Laser Deposition (DLD) [75-76], Laser
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Forming (LF) [77], Laser Aided Direct Rapid Manufacturing (LADRM) [78], Laser aided

Additive Manufacturing (LAAM) [79-80].

2.2. Powder Bed Fusion (PBF)

Powder Bed Fusion (PBF) is one of the popular methods in metal additive manufacturing. The

PBF process uses a 3D-designed CAD model to fabricate the components in a layer-by-layer

approach. Powder bed fusion processes are categorized based on their energy sources. The

powder is spread in the form of a bed, and a high-power laser source or an electron beam scans

over the laid powder bed. After each subsequent layer, the powder is spread with a roller, and
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the scanning process is repeated, resulting in the formation of a 3D component. PBF can further

be classified, namely, Laser-based Powder Bed Fusion(L-PBF) [81–87], Electron Beam

Powder Bed Fusion (EB- PBF) [88], Direct Metal laser Sintering (DMLS) [89], and Selective

Laser Sintering (SLS) [90], and Selective Heat Sintering (SHS) [91]. Due to its advantageous

properties, such as highly complicated structures, good finish, improved manufacturing times,

and the ability to deposit a wide range of materials. Despite the numerous advantages of the

PBF technique, it has some significant disadvantages, such as higher power consumption,

longer printing time, and difficulty in powder recycling.

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Features Powder Fed Fusion Powder Bed Fusion

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Schematic
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Large-size components can be Limited to lower-sized

Size
produced components
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Complexity Low to Moderate High

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Deposition Rate High deposition rates Low deposition rates

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Powder Size 40-100µm 10-40µm

Process Cost Low High

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Repair and Can be used for repair and

Limited to a few cases
Refurbishment refurbishment

Fig. 4. Schematic illustrations of Powder Fed Fusion [92] and Powder Bed Fusion [93] processes
along with their key features

3. Refractory High Entropy Alloy Systems for Additive Manufacturing

Alloy production and processing of RHEAs is quite challenging because of their high melting

temperatures and the significant difference in the melting points of various elements. Table 1

highlights the selection of RHEAs taken from the literature. The RHEA systems and phase

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compositions have been presented, along with a summary of their work.

Table. 1: RHEAs fabricated through AM are available in the literature to date, with the
processing route, phase evolution and summary of the work done.
AM
RHEA Alloy Type Phase Remarks Ref.
The deposition was carried out by
7 different process parameters
obtained by altering the laser
MoFeCrTiWAlNb BCC+HCP+ [94]
L- PFF powers and scanning speeds.
(Nb, Ti) C
Microstructural, Phase Analysis,
Hardness, and Wear Studies
Four different powders were used

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for the deposition

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NbMoTaWx Microstructural, Phase Analysis,
(x = 0, 0.16, 0.33, L- BCC (20µm Hardness, and Compression test
[95]
PFF grain size) studies at Room Temp. along with

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0.53)
elevated temp. testing at 1000C
L- Microstructure, Phase Analysis,
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NbMoTaW PBF BCC Hardness, and Corrosion test [96]
HfNbTaWTi,
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HfNbTaWCr, Machine Learning to predict the

- - properties of RHEA [97]
HfNbTaWV
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Study on the effect of Scanning

speed on the properties of the
deposits. The deposition was
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carried out with 4 different scan

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speeds.
EB-
NbMoTaWTi PBF BCC Microstructural, Phase Analysis, [98]
Hardness, and Compression Test
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31 samples (3 sets of iteration)

were deposited by varying the
powder hopper RPM and with the
same process parameters.
L- Microstructural, Phase Analysis,
NbMoTaW PFF BCC [99]
CALPHAD Calculations for
Phase Diagram

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 The effect of Carbon
microalloying on NbMoTaW has
been studied including the
precipitation strengthening
mechanism and grain refinement.
(NbMoTaW)100-xCx Microstructural (in-detail), Phase
L-
(x = 0, 0.5 at%) PBF BCC Analysis, Phase Diagram by [100]
JMatPro Software, and
Compression test
Lightweight RHEAs were
deposited and the following
testing’s were performed
L- Microstructural, Phase Analysis,

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NbMoAlTiV PFF BCC Hardness, and Oxidation [101]

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Resistance studies
Compositionally graded
NbZrTaTi deposition was carried

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out by in-situ alloying.

L- PFF Microstructural and Texture

NbZrTaTi BCC [102]
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Analysis, Hardness, Phase
Analysis
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Nb addition was performed at
different molar ratios. The effect
of Nb addition and its effect on the
properties of the deposits were
NbxMoWCrTiFe1.5Al(x
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BCC + MC+ evaluated

= 1.5, 2, 2.5, 3) L- PFF [103]
Laves phase Microstructural, Phase Analysis,
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Hardness, and Wear test

Deposition of HfNbZrTaTi was
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carried out by LMD technique and

homogeneous mixing of these
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elements was made possible

HfNbZrTaTi L- PFF BCC [104]
Microstructural Characterization,
hardness
The deposition was carried out by
BCC (Cr, Zr, 8 different process parameters
Ta) + BCC obtained by altering the laser
(Mo, W, Ta) powers.
WTaZrCrMo L- PFF +C14 Laves [105]
Microstructural, Phase Analysis,
phase Hardness
Deposited clads in the as-
deposited conditions were
compared with the heat-treated
BCC+ clads.
WNbMoTiZr L- PFF precipitates of Microstructural Characterization, [106]
(β-TixW1 – x)
Heat Treatment, Hardness, and
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 Phase Analysis

Single Track Studies and

Multitrack studies of NbMoWTa
L- PFF were evaluated.
NbMoWTa - [107]
Microstructural Characterization

A fundamental understanding of

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the alloying process and melt pool
studies was carried out. The
deposited NbMoTiV clads were
observed using an in-situ high-

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speed synchrotron X-ray and IR
Imaging.
L- PFF
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NbMoTiV Temperature profile studies of [108]
Melt pool, Images of delivery
trajectories, Microstructural
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Characterization of powder

FCC+(Fe7W6)
Wx(CoCrFeMnNi)100
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Intermetallic Microstructural Characterization,

−x Phase analysis, Hardness, [109]
L- PFF phase +
(0 ≤ x ≤ 21 at%.) (W)BCC Delivery trajectory images.
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FCC+Nb
dendrites
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intermetallic
phase
1) Nbx FCC+two
CoCrFeMnNi phase Compositionally graded Nb, Ta,
2) Tax banded+ and Ti6Al4V were studied
intermetallic Microstructural characterizationand
CoCrFeMnNi
L- PFF phase hardness were studiedthroughout [110]
[TiAl6V4]x HCP+BCC+ the compositionallygraded materials
CoCrFeMnNi
intermetallic
phase

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 Microstructural Characterization,
SFE Studies, Phase Analysis, Phase
Diagrams, Room Temperature, and
NbMoTaTi0.5Ni0.5 L- PBF BCC High temperature (1000C) [111]
compressiontest.

Synthesis of Spherical Powder of

RHEA for additive manufacturing
Microstructural Characterization,
WNbZrTaMo BCC Phase Analysis, Nanoindentation, [112]
Compression Test

The deposition was carried out

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with constant laser power and with
4 different scan speeds.
Microstructural Characterization,

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WNbMoTaV L- PBF BCC Phase Analysis, Hardness, Surface [113]
Roughness, Residual Stress,
Compression test
e-
Deposition of the RHEA was
carried out by varying the
compositions of the Zr form (0.2
Pr

to 1.0). In-detailed studies on wear

AlNbTaZrx and oxidation were performed.
Microstructural Characterization,
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L- PFF BCC+HCP Phase analysis, Microhardness,

(x=0.2, 0.4, 0.6, 0.8, [114]
1.0) Wear test, Oxidation Test, XPS
n

Analysis,
Deposition of WMoCrTiFeAlNb3
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was carried out using L- PFF. Heat

Treatments were done at 750 ˚C,
850 ˚C, 950˚C, and again 950˚C
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for 4H, 6H, 8H, and 10H. The HT

results were compared to the as-
BCC+MC+La
WMoCrTiFeAlNb3 L- PFF deposited clads.
ves phase [115]
Microhardness, Wear Test, Heat
Treatment, Precipitate Studies

The clads were deposited by

BCC+(NiTi2) varying the Ta percentage.
Laves + Microstructural Characterization,
CrNiTiNbTax L- PFF (Cr2Nb) Laves Phase Analysis, XPS oxidation [116]
phase studies, Hardness, and Corrosion

18
 A new grade of
WMoTaNbVFeCoCrNi RHEA is
been developed by mixing 2
HEAs. The developed RHEA was
deposited.
EB- BCC+FCC+L
WMoTaNbVFeCoCrNi Microstructural Characterization [117]
PBF aves
(EBSD), Vickers Hardness,
Compression test
HEA coatings were deposited on
Ti6Al4V substrates using the L-
PFF technique.
1) TiZrAlNb 1) BCC Corrosion, hardness, and
TiZrAlNbCo L- PFF BCC+FCC [118]
microstructural studies were

f
carried out

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The deposition was carried out
using L- PFF. The increasing Nb
content stabilizes BCC phases and

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suppresses the ω phase.
1) BCC Phase Analysis, Microstructural
TiZrHfNbx
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L- PFF BCC+ωphase Characterization (SEM-EBSD, [119]
(x = 0.6, 0.8,1.0) EDS and TEM), Tensile test and
post-mortem studies
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C was alloyed to WMoTaNb to

suppress the cracking behaviour
Phase Analysis, Microstructural
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EB - Characterization (SEM-EDS,
WMoTaNbC PBF BCC+Nb2C EBSD, TEM), Compressive [120]
Strength, Texture
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Phase Analysis, Microstructural

Characterization (SEM-EPMA,
EBSD, TEM), Compressive
(BCC+B2)
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L- PFF
AlMo0.5NbTa0.5TiZr Strength-High Temperature 800 [121]
+HCP
and 1000C,

Phase Analysis, Microstructural

Characterization, Oxidation
behaviour
NbMoTaWV Effect of TiC on the high-
NbMoTaWV-TiC L- PBF temperature oxidation studies of [122]
NbMoTaWV

MoNbTa+W grading SEM (EBSD), Texture, EDS, and

NbTaW+Mo grading Hardness testing
MoTaW+Nb grading L- PFF High
throughp [123]
NbMoW+Ta grading ut Additive
19
 manufacturing

Phase Analysis, CALPHAD,

Microstructural Characterization
(SEM-EBSD), TEM, Tensile
testing, Hardness, Compression
testing, annealing treatment at 600
L- PBF
NbMoTiTaNi [124]
℃, 800 ℃, 1000 ℃, 1200 ℃, and
1300 ℃.

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3.1. Metallurgical Aspects - Microstructure and Phases

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The majority of the RHEAs reported to date are single-phase BCC structures while only a few

with dual phases. Senkov [46] has made a significant effort to understand the phase changes
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that occur in RHEAs, as outlined in his review. According to his findings, if RHEAs were
Pr

solely produced using transitional refractory materials, they would only have a single-phase

BCC phase. However, the second phase can only precipitate effectively when alloyed with
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non-refractory components. This highlights the importance of carefully selecting the materials
n

used in the production of RHEAs to achieve the desired properties and phase changes. There
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are several limitations that have restricted the use of refractory alloys of Nb, W, Mo, Ta, for
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high temperature applications, when used individually or in conventional refractory alloy

forms. Whereas, superalloys have become a more popular choice for high temperature

applications owing to their remarkable properties. Superalloys exhibit a microstructure

consisting of a matrix (Disordered FCC) and a precipitate (Ordered FCC-L12) [125].

Analogous to the metallurgical aspects of phases in superalloys, efforts have been made to

develop a comparable microstructure with a combination of a matrix (Disordered BCC phase)

and a precipitate (ordered BCC phase-B2) in RHEAs [126]. More information about the

phase in RHEAs can be seen in Fig. 5. It is important to note that the disordered BCC, B2

structure, Laves, HCP, FCC, and ordered L12 phases are the most prevalent phases. Given
20
that these alloys fall under the periodic table's subgroups IV, V, and VI, the dominance of the

BCC phase in the RHEAs is anticipated. The periodic table's V and VI subgroup elements

possess BCC crystal structures and have high solubilities in solid solutions. At elevated

temperatures, Group IV elements including Ti, Zr, and Hf also display BCC crystal structure.

Below the solidus line, the laves phase is remarkably stable. Several researchers suggested that

∆Sconf alone cannot govern the stability of phases [126]. In a very popular research paper

published by Guo et al. [127], they proposed a criterion for determining the phase stability in

HEAs based on the Valence Electron Concentration (VEC). The proposed that at lower VEC

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(< 6.8), BCC phase is more stable, and as the VEC increases, FCC phase becomes stable at

higher VEC (> 8).

Phases in RHEAs
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Single phase Dual Phase Multi Phase
✓ BCC ✓ BCC1+BCC2 ❑ BCC+Laves1+Laves2
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✓ FCC ✓ BCC+FCC ❑ BCC+FCC1+FCC2

✓ B2 ✓ BCC+HCP ❑ BCC1+BCC2+Intermetallic Comp.
✓ BCC+B2 ❑ BCC+FCC+Laves
✓ BCC+Laves
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✓ BCC+M-(C,B,Si,O,N)
✓ BCC+Intermetallic Comp.
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Fig. 5. Phases in RHEAs

As of date, the comparable studies of conventionally produced and Additively

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manufactured RHEAs usually possess almost same phase structures. It is still not clear, “if

the rapid cooling and the fast solidification kinetics can alter the phase formations”. Further

examinations and deeper investigations on comparable studies of RHEAs fabricated by

conventional techniques and AM route could answer this question. But there are noticeable

changes in the microstructural features of AM fabricated RHEAs. As, additive manufacturing

process involves, rapid cooling, rates, the microstructural features of melt pool boundaries

[86], grain boundaries and sub cellular boundaries [128] are evident in AM processed

RHEAs. This hierarchical microstructure found in AM processed RHEAs is quite different

21
from the microstructural features of dendritic structure in conventionally manufactured

RHEAs.

RHEAs produced via additive manufacturing techniques possess higher strength when

compared to conventionally manufactured RHEA. The evolution of higher strength in

additive-manufactured RHEAS is due to the hierarchical microstructures such as fine-grain

structures [86], solidification cells, higher dislocation densities and the formation of fine

intermetallics combined with the super-saturated solid solution achieved by rapid cooling

f
[129]. However, additively manufactured RHEA have been seen to have inferior ductility

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when compared to their conventional counterparts and such lower ductility is mainly caused

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due to process-generated defects such as porosities, cracking, residual stresses, oxide

inclusions and vaporisation of low melting point metals [110, 129].

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3.2. Relative Density
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When it comes to the samples prepared by additive manufacturing, the primary goal of the
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additive manufacturing process is to produce specimens with densities greater than 99% [130].

High porosity in the components tends to worsen the mechanical properties and cracking (Pores
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act as crack-initiating sites) [131-132]. Gou et al. [119] tried to study the processing

parameters for the TiZrHfNb specimen. The track height, depth and width tend to increase with
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the increase in the power density and decrease with the increase in the scanning speeds.

However, around 4-5 process parameters yielded similar densities, selection of process

parameters in RHEAs is quite challenging. In this work, it is noticed that higher scanning

speeds lead to spattering whereas the higher powder i.e., the surplus heat paves a way for

elemental evaporation as a result of the difference in their melting points [110,119]. The

constant increase in the scanning speeds leads to the formation of humping, which resembles a

drop like pile on top of a bead [133-134]. The molten pool's hydrodynamic instability, or

Kelvin-Helmholtz (KH) instability, is what causes humping [129]. The relative density is

22
affected by two major reasons. Firstly, when the additive manufacturing processes are carried

out at very high-power densities, it may lead to splashing and deposition taking place in

keyhole mode [135]. At higher power densities, the melt poot is quite unstable and favors the

formation of balling. The entrapment of the gases in the melt pool results in the origination of

voids and hence reduces the density of the components [131,136-137]. The formed voids are

typically spherical in shape [138-139]. Secondly, at the time of the powder atomization process,

gases may get entrapped within the feedstock particles [140-141]. Additionally, the entrapment

of the shielding gases or the metal vapors inside the molten pool may result in the formation

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of gas pores.

3.3. Residual Stresses

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Processes that involve rapid solidification frequently produce residual stresses, which is the
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internal stress persisting in a component even when the external forces are removed [142]. The

large thermal gradients, thermal stresses and residual stresses emerge naturally when molten
Pr

metal is deposited over the samples that are significantly colder or over the previously

deposited layers [143-144]. As a result of the significant temperature gradient along the build
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direction causes alternating tensile residual stresses and compressive residual stresses amongst
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the underneath and the succeeding layers for components fabricated through additive
ur

manufacturing processes. The process of additive manufacturing involves repeated cycles of

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heating and cooling, which results in residual stresses. An understanding of the quantitative

evolution of thermal stresses is crucial to mitigate the problems. Since residual stresses in

RHEAs can cause distortion and cracking, it is essential to understand how they develop and

are distributed within the material. In contrast, compressive residual stresses are advantageous

as they could have a profound effect on increasing the fatigue life of the material [142,144].

X-ray diffraction and Neutron diffraction are used to determine the residual stresses in

the material. Gu et al. [113] studied the evolution of residual stresses in NbMoTaV RHEA

which was produced through the L-PBF technique. The residual stresses were measured across

23
the depth as well as the top surface of the specimen. The residual stress of NbMoTaV RHEA

was measured at different scanning speeds along the build direction as illustrated in Fig. 6a. It

is clearly evident from Fig. 6a that the bottom part of the specimen consisted of compressive

residual stresses and as it moves towards the surface the nature of residual stress tends to be

tensile in nature. This is because of the fact that the bottom layer of the specimen is closer to

the substrate, which leads to rapid heat transfer. As a result, the deposited layer at the bottom

shrinks and generates compressive residual stresses. As we approach towards the surface of the

specimen, the heat transfer reduces and heat accumulation leads to a decrease in the

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compressive residual stress and transforms into tensile residual stresses [145]. As the

scanning speed increases from 400 mm/s to 800 mm/s there is a significant decrease in the

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tensile residual stress. At lower scanning speeds, the heat dissipation is high and results in
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high tensile residual stresses. At higher scanning speeds, the heat dissipation is low and paves

the way for low tensile residual stresses [146]. Fig 6b illustrates the residual stress measured
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over the surface of the specimen in Scanning Direction (SD) i.e., σx and Transverse Direction

i.e., σy. As mentioned earlier the surface of the specimen consists of tensile residual stresses,
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and as the scanning speed increases the tensile residual stress decreases. Methods such as
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surface preheating, increasing the scanning speed and scanning in island mode are effective

strategiesto mitigate/ control residual stresses [147].

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(a) (b)

Fig. 6. Residual stresses of NbMoTaV measured (a) along the length of the specimen at different
scanning speeds, and (b) at varied scanning speeds in different directions. Reproduced with
permissions from [113], Copyright 2022, Elsevier.
24
3.4. Grain Structure and Crystallographic Texture

Regardless of the element compositions, one of the primary advantages of additive manufacturing of

RHEAs over traditional processing techniques is its higher cooling rate, which is triggered by the

localized heat input and a small amount of molten material and facilitates the fabrication of components

with a finer microstructure [130]. The two most crucial characteristics of grain structure are

solidification morphology and grain size given that they have an impact on the characteristics of

components produced using additive manufacturing [148–152]. The comprehensive understanding of

metallurgy as well as fusion welding, at which the scientific concepts of grain formation have served as

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an issue of significant research for many years, has benefited concepts of the development of grain

structure, size and its distribution when fabricated through additive manufacturing. The benefits of

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utilizing cutting-edge, potent digital tools like mechanistic modelling and machine learning, offer a

more rapid and scientific path for the development of AM than was previously possible for other
e-
manufacturing technologies [153].
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It is widely accepted that Columnar to equiaxed transition (CET) is favored when the Growth

rate (R) increases and the Temperature Gradient (G) [148]. A schematic diagram is shown in Fig. 7a
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explaining solidification in a single melt pool. The relationship between the temperature gradient and
n

the solidification growth rate (Fig. 7b) determines the grain structure. Columnar grains are more likely
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to develop when the G/R ratio is high. On top of that, the cooling rate during solidification, which
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affects the fineness of the microstructure, such as the dendrite-arm spacing or cell spacing, is

represented by the product of the temperature gradient to the solidification growth rate. In order to

achieve a particular solidification morphology and grain size, process conditions are modified to

achieve the necessary thermal gradient along with the solidification growth rate. The formation of

equiaxed grains is favored by the reduction of the temperature gradient caused by substrate preheating

and high heat input. Smaller but more elongated grains are produced by rapid cooling at a high scanning

speed [153]. As can be seen from Fig. 7a, the large temperature gradient is what causes the epitaxially

grown columnar grains to grow perpendicular to the bottom of the molten pool in a single direction

[155]. The epitaxially grown columnar grains at the molten pool's edge also have a variety of directions

25
in which temperature gradients are present, and low cooling rates in overlap areas. Equiaxed grains

make up the majority of the microstructure on the surface of the molten pool due to its extremely quick

cooling rate, crystal growth is constrained along the preferred crystal orientation. Given that the CET is

heavily reliant on the temperature gradient and the direction of the heat flux under a variety of process

parameters, the ratio of columnar to equiaxed grains could be optimized by altering the laser power and

scanning strategies as highlighted in Fig. 7b [156–160].

(a) (b)

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Fig. 7. Schematic depicting the cross-sectional microstructural characteristics in a single melt pool
during AM process [161], (b) Effect of Temperature Gradient (G) and Solidification Rate (R) on the
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microstructure [129].

When trying to maximize the mechanical properties of components at elevated temperatures,

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columnar grains oriented along the loading direction are required. At the same time, it is thought that
n

applications involving stresses in multi-direction are likely to suffer from this anisotropy in mechanical
ur

behaviour. Because of this, AM needs post-processing to suit the requirements of parts that

require isotropic mechanical characteristics [162-163]. Constitutional supercooling, which provides

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the necessary supercooling to activate particles in the vicinity for nucleation, is crucial to the

nucleation of an equiaxed grain [164]. Localized heat flow directions and competitive grain growth

affect the solidification texture [165]. In a work carried out by Li et al. [95], laser cladding of

NbMoTaWxwith varying tungsten compositions (x= 0, 0.16, 0.33, 0.53) was manufactured by

L- PFF technique. The rapid solidification during the cladding process has led to the

development of dendritic structure. NbMoTa RHEA was alloy alloyed with Ti and Ni to form

NbMoTaTi and NbMoTaNi [111]. The addition of Ti to the NbMoTa matrix induces

toughness while the addition of Ni increases the regime of the liquid phase. Fig. 8a shows the

26
TEM image of NbMoTaTi RHEA along with the SAED pattern of the matrix phase. Point 1

and Point 2 are the two distinct phases present in the alloy. The matrix phase is comprised of

BCC crystal structure (Nb2Mo3Ta3Ti2) while the Grain boundary phase as shown in Fig. 8b

has the HCP crystal structure of Ti solid solution encompassing Nb, Mo and Ta.

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Fig. 8. (a)TEM image of NbMoTaTi RHEA along with the matrix phase SAED pattern, (b) Point 1
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i.e., the Grain boundary phase along with the GB phase SAED pattern, Reproduced with permission
from [111], Copyright 2021, Elsevier.
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The addition of Ni is done in the NbMoTa matrix, which has led to the increased regime

of the liquid phase. It is of significance to mention that this alloy has high hardness owing to
n
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the presence of nickel, which promotes grain refinement. TEM images of NbMoTaNi alloy are

highlighted in Fig. 9a and 9b. Four points are selected from Fig. 9b for elemental and electron
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diffraction. Though there exists a dichotomy between point 2 and point 3 in terms of colour

contrast they both resemble the same phase. The matrix is comprised of a BCC crystal structure

(Nb2Mo3Ta4Ni0.1) and the grain boundary region is Nb2Mo0.5Ta3Ni4. The presence of

interstitial Nb3Ni3Ta4 in the Nb2Mo0.5Ta3Ni4 plus the presence of several dislocations are

indicated in Fig. 9c. Fig. 9d reveals the presence of dislocation jogs which is due to the impeded

flow of dislocations.

27
 f
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Fig. 9. HR-TEM images of NbMoTaNi RHEA (a, b) Distribution of matrix and the grain boundary
phase, (c) matrix along with its SAED pattern, (d) dislocation interaction in the grain boundary
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phase, Reprinted with permission from [111], Copyright 2021, Elsevier

3.5. Elemental distribution & Segregations

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The inequitable distribution of the elements in alloys during solidification is referred to

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as segregation. This challenge is encountered quite frequently in the AM process and has a

consequence on the phase evolution. It is a popular argument that, few elements in a HEA,
n

like as Cu and Fe, have positive mixing enthalpies, resulting in elemental segregation so as to
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minimize overall Gibb's free energy (∆G˚) [166]. The two factors which govern the elemental
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segregation in RHEAs are phase formation kinetics and cooling rates [167]. Over the past few

years, researchers have made substantial progress in understanding the phenomena of

chemical segregation in RHEAs using both thermodynamic and kinetic viewpoints, as well as

investigating innovative strategies to reduce segregation and achieve homogenisation.

RHEAs produced via AM techniques mainly comprise of single-phase BCC phase, which

results in the difference in the melting temperature between different elements therefore

paving the way for elementalsegregation. Nevertheless, the rapid cooling rate in AM processes

induces nearly instantaneous precipitation of elements with varying melting temperatures,

28
establishing the alloy with near- uniform elemental distribution with relatively small

segregation. The precipitation of specific elements in dendrites may prevent the formation of

micro cracks in RHEAs produced through AM techniques. As a rule, RHEAs fabricated via

conventional techniques such as arc melting, are more prone to elemental segregations.

Whereas, in the case of additively manufactured RHEAs, owing to its higher cooling rates,

the solute segregation, is not as severe as in the case of as-cast samples. The segregations in

the AM fabricated alloys are subtle and these chemical segregations, form along the

boundaries of the melt pools [52], grain boundaries [111] and cellular sub boundaries. In a

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recent article on TiZrNbTa RHEA, Shahryar Mooraj et al. [52], compared the additively

manufactured samples with the casting samples. They reported that the elemental segregation

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was more prominent in the case of casting samples than the additively manufactured
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TiZrNbTa RHEA (refer Fig. 10). Fig. 10a refers to the as-printed microstructure with clear

melt pool boundary as highlighted with yellow dotted lines. The as-cast microstructure with
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dendritic and interdendritic regions is illustrated in Fig. 10b. Along with the SEM images,

EDS maps have also been attached. In the case of the as-cast samples, Ta is enriched in the
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dendritic regions, while Zr and Ti are rich in the inter-dendritic regions. There are instances,
n

where intermetallic compounds have also been found during the solidification in AM.
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Authors of [119], have reported the formation of an intermetallic ω phase, which would
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deteriorate the mechanical properties such as Fracture toughness and ductility.

29
 f
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Fig. 10. SEM imaging along with EDS mapping of TiZrNbTa RHEA processed via (a) Additive
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manufacturing, (b) Casting [52].

As emphasized by the authors of [168] on WMoTaNbNiTi RHEA, they reported the elemental
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segregation of Nb, Ni, and Ti along the grain boundaries and this NbNiTi segregation at the grain

boundaries is believed to enhance the thermal shock resistance and as shown in Fig. 11. This kind of
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elemental segregations of low melting point elements along the Gb’s, while the high melting
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temperature elements such as Ta, W, and Mo as the matrix, is because of the fact that these high
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temperature elements are formed at temperatures greater than 1700°C, leading to the solidification of

these elements, thereby separating he Ni and Ti rich fluids to the Gb’s.

30
 f
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Fig. 11. Electron microscopy images of Grain Boundary Segregation of Additively manufactured
WMoTaNbNiTi RHEA along with their elemental mapping (a,b) SE and BSE mode of imaging
respectively, (c) STEM imaging of NiTi micro segregation, (d) Segregation of NiTi B19' at the grain
boundaries [168], Copyright 2024, Elsevier

Dobbelstein et al. [107] tried to investigate the deposition characteristics of the in-situ

alloyed NbMoTaW RHEAs using the L-PFF technique. The utmost disparity in the melting

points between the two elements of tungsten and niobium is 900⁰ C. In this study processing

31
variable power was chosen to be 800 W. It is an established fact that higher power leads to the

evaporation of the elements while the lower power gives a decreased deposition efficiency. In

this work, the single tracks were deposited with the process parameters of 800 W and 120 Hz

pulse frequency. The single tracks were inhomogeneous and porous, with higher elemental

segregations. To overcome these shortcomings, Dobbelstein et al. [107] employed a remelting

technique for better melting and mixing of the elements, which in turn paves the way for high-

quality welds. Remelting was carried out at 4500 W power. All the multi-tracks deposited

showed cracks close to the substrate. Cracking could be due to the difference in the thermal

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expansion coefficient and higher reactivity with oxygen (especially Mo and W). In this study,

a relation is made between the melting point and elemental concentration and is concluded that

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apart from molybdenum, the lower melting materials have higher concentrations. The
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molybdenum powder size used in the present study is comparatively smaller and could have

evaporated at high power. Another detrimental factor for the case of molybdenum powder in
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this study is its spherical shape. Spherical powders usually tend to have higher rebounds

compared to irregular powders. The final composition of clads was Mo32Nb13Ta19W35, while
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the initial composition of the powder was Mo25Nb25Ta25W25 (atomic percent). The effect of
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substrate preheating was also determined in this study. In 2019, Dobbelstein et al. [104]
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employed L- PFF to produce compositionally graded Ti25Zr50Nb0Ta25 to Ti25Zr0Nb50Ta25

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RHEAs by elemental mixing technique as shown in Fig. 12a. Both these alloys were found to

exhibit single crystal structure (BCC) and illustrated coarse grain morphology. The elemental

blending technique was used in this context as conventional melting of L- PFF cannot

be employed due to the significantly higher differences in their melting point (1350˚C

between Ti and Ta). The energy at which Ta starts to melt is way higher for the Ti, which in

turn paves theway for elemental evaporation. In order to prevent such detrimental effects, the

concept of elemental blending along with suitable remelting strategies was exercised. The

EBSD image illustrates the random orientation of grains and the grains near the substrate are

32
 very fine (~2µm) and equiaxed while the grains near the tip are coarse (~60µm) and

elongated. The tip is rich in Nb (Ti25Zr0Nb50Ta25) while the near substrate is rich in Zr

(Ti25Zr50Nb0Ta25) and can be seen in Fig. 12b. Grain size variation is more significant due to

the Ta segregation in Zr rich regions rather than cooling rate solely. It was found that the tip

region had the least hardness value (220 HV) and the highest hardness (440 HV) was

observed near the substrate which is rich in Molybdenum in another work carried out in 2021

by Zhang et al. [111].

(a)

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(b)
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Fig. 12. Cross Section EBSD of the compositionally graded TiZrNbTa over a molybdenum substrate at
right. A white box close to the Mo substrate is enlarged and shown, (b) Elemental composition of the
compositionally graded RHEA by elemental blending technique changing the composition from
Ti25Zr50Nb0Ta25 (right) to Ti25Zr0Nb50Ta25 (left), Reprinted with permission from [104], Copyright
2018, Elsevier

3.6. Post Treatment

33
Since the characteristics they possess might not be ideal for their intended use,

materials produced in the as-fabricated state usually are not directly used owing to the presence

of unstable phases, rough surfaces, non-homogeneous microstructure, and unwanted residual

stresses. The produced components must be subjected to a suitable post-processing technique

based on the area of applications. Wohlers' report from 2021 states that about 27% of the total

cost of processing metal AM is attributed to post-processing procedures. The key steps in post-

processing include heat treatment, coloring and coating, surface finishing, and removal of

support material. Heat treatment provides homogenization and enhances phase distribution and

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grain size homogeneity in an alloy. Regardless of the homogeneous grain size and phase

distribution, stable mechanical properties may be produced.

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Heat treatment prior to deformation, such as homogenization heat treatment or
e-
annealing, has been identified as an essential method of improving plastic deformation by
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controlling the microstructure. As articulated in the preceding portion of an elemental

distribution and segregations (section 3.5) there is a chance of micro segregation in RHEAs
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due to the significant discrepancy between the melting points of various elements. Therefore,

heat treatments at elevated temperatures in controlled atmospheres and cooling rates should
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be an effective strategy to mitigate the aforementioned issues of elemental segregation [169].

Kuang et al. studied laser-directed energy deposition of MoFeCrTiWAlNb3 over High-speed

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tool steels [115]. High-speed tool steels are inexpensive and have a high degree of hot

hardness up to 600˚C. An annealing treatment at three different temperatures of 750˚C, 850˚C,

and 950˚C was performed to investigate the high-temperature properties of this RHEA.

Nevertheless, they are limited by their low toughness and poor adhesion strengths. So, a

refractory eutectic high entropy alloy coating was deposited to improve the mechanical

properties of the substrate. Fig. 13 shows that the cubic MC carbide blocks are rich in (Nb +

Ti) C carbide FCC phases with minor traces of W and Mo present. The grey matrix is rich in

Fe, W, and Cr but low in Nb and Ti elements, while the white leafy structures, on the other
34
hand, are high in Fe, Ti, Nb, and Mo. The grey and white locations were identified as BCC

phase structures with Fe2M laves phase. The SEM images of MoFeCrTiWAlNb3 in as-

deposited and annealed conditions are shown in Fig 13 (a-d). When annealed at 750˚C, there

is no noticeable change in the microstructure. However, when annealed at 850˚C, the leafy

eutectic lamellar laves phase strips have been transformed into a blunt rod-like structure,

leaving behind a 0.1µm precipitate. EDS analysis revealed that the precipitate is high in Nb,

Mo, W, and Fe. Because they are formed by the dissolution of the primary laves phase, these

precipitates could be regarded as Secondary Laves

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phases. The precipitate size increased to 0.3 to 0.5µm during the subsequent heat treatment

at950˚C, while the eutectic lamellar structure disappeared. The hardness of the RHEA

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coating tends to decrease as the annealing temperature rises. Zhang et al. have studied the
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effect of heat treatment on mechanical behaviour and microstructural evolution of
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NbMoTaTiNi RHEA fabricated through the L-PBF technique [124]. In the as-built condition,

the matrix consisted of a dendritic structure and as the annealing temperature increases the
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dendrites annihilate. At 1300˚C, these dendrites are ultimately transformed into cellular

structures. The authors tried to assess the thermodynamic stability of the alloy at as-built and
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various heat treatment temperatures conditions by calculating the “Lattice disorder” and

“high entropy effect” and interestingly discerned that the alloy produces a matrix phase
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(disordered), XB phase (transitional) and B2 phase (ordered). The matrix phase's lattice

distortion steadily diminishesas the annealing temperature rises.

35
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Fig. 13. SEM images of the MoFeCrTiWAlNb3 RHEA (a) as-built, (b) annealed at 650°C. (c)
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annealed at 750°C, (d) annealed at 850°C, Reproduced with permission from [115], Copyright 2018,
Elsevier.
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4. Mechanical Properties of Additively Manufactured RHEAs

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RHEAs are viewed as futuristic materials for extreme temperature applications.

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Henceforth, during the development of AM fabricated RHEAs, it is of paramount importance

to consider the nuances of mechanical properties. It is imperative to mention that there exists
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a profound connection between the mechanical properties and composition and in turn the

microstructures [46]. The vast majority of RHEAs tend to exhibit single-phase BCC crystal

structure. It is also noticeable that the yield strength of the BCC+B2 phase is higher but

limited to poor deformability [170]. Moreover, there is a dearth of literature about the fatigue,

impact, and creep properties in the realm of additively manufactured RHEAs. In the present

section of the mechanical properties of additively manufactured RHEAs, we shed light on the

hardness, tensile, compression and high temperature compression deformation behaviour.

4.1. Hardness
36
RHEAs have significantly improved hardness primarily due to the strong effect of the solid

solution strengthening mechanism. Mostly BCC alloys have high mixing entropies owing to

their strong solid solution strengthening effect when compared to FCC phases [110,171–173].

Along with the high solid strengthening effect the next important hardening effect is refined

grains. It is also a well-known fact that, AM fabricated alloys typically exhibit higher

hardness values when compared to castings as a result of the fine microstructural features

obtained by the rapid cooling rates. Few microhardness values of AM processed RHEAs listed

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in the literature have been illustrated in Fig. 14 for easy comparison purposes. In the case of

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additive manufacturing, the hierarchical microstructural features of melt pool boundaries,

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grain boundaries and sub cellular boundaries, are believed to enhance the hardness. From the

figure, it is noticeable that few RHEAs although having same composition, exhibit a scatter
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in the hardness which is a result of different additive manufacturing processes. This higher
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solid solution strengthening in RHEAs originates due to larger lattice distortions [46]. It is

imperative to mention that AM processed RHEAs largely have microhardness values in the
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range of 400-1400 HV.

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Fig. 14. Microhardness values of AM fabricated RHEAs

37
4.2. Tensile Properties

Although, in the materials science fraternity, tensile tests have become quite popular and to

understand the mechanical behaviour of the alloys. But there are very few research articles

emphasizing on the tensile properties of AM fabricated RHEAs. Majority of the researchers

employ compression testing to understand the mechanical behaviour of AM processed

RHEAs. The reason why researchers working on AM fabricated RHEAs neglect tensile

properties, could be due to two reasons. The primary reason, being the alloy itself. It is known

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that RHEAs usually possess poor ductility owing to its BCC crystal structures. BCC-based

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alloys have analogous slip systems to FCC based materials, the smaller stacking compact of

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the slipping surfaces for BCC-based alloys compared with FCC-based materials contributes

for the poorer ductility of BCC-based metals. Stacking fault energy (SFE) is a helpful
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measure for measuring ductility levels among BCC-based materials. Higher SFE leads to
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lesser ductility in BCC-based materials [174].

Moreover, not just simple BCC, but in certain cases, the presence of intermetallic phases as
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ω phase as observed by the researchers in [119], even worsens the scenario of ductility. The
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next major reason for the poor ductility in AM processed RHEAs is due to the presence of
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process induced defects such as pores, cracks, oxide inclusions, and contaminations.
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However, in the long run, we must try to understand the tensile properties of AM

fabricated RHEAs as well, because there are several engineering applications, for which

tensile properties are suitable for assessing mechanical properties. Although, a couple of

researchers tried to study the tensile behaviour of AM fabricated RHEAs. Gou et al. have

made a significant breakthrough in additive manufacturing by producing ductile refractory

high entropy alloys [119]. Specifically, they have used the L- PFF technique to create

TiZrHfNbx alloys with varying molar ratios of x=0.6, 0.8, and 1.0. The addition of Nb to the

alloy stabilizes the BCC phase and suppresses the formation of the ω phase (HCP). They have

achieved an equiaxed microstructure that increases ductility without compromising strength.

38
The increase in the tensile strength with Nb content is attributable to stabilizing the BCC

phase. The typical microstructure of additively manufactured samples consists of columnar

grains, but TiZrHfNb exhibits an equiaxed microstructure, which eventually resulted in

superior mechanical properties with a yield strength of 1034 MPa and elongation of 18.5%.

The fractured specimens’ postmortem studies of the TiZrHfNb reveal the presence of several

slip bands as shown in Fig. 15 (a-b). The highly accumulated dislocation networks are caused

by these shear bands and can be clearly manifested in Kernel Average Misorientation maps of

Fig. 15 (c-d). It is worth mentioning that few researchers have revealed that the lamellar

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structure arises from a combination of deformation twinning and slip bands [175]. However,

the misorientation line profile (Fig. 15d) revealed that there is a minor misorientation

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difference (<10˚). The possibility of a twinning deformation process is thus ruled out. These
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slip bands are the piled dislocation networks oriented on the {110} plane. XRD (Fig. 15e)

confirms the presence of a single-phase BCC structure and there is no deformation-driven

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phase transformation. Fig. 15(f-h) shows the TEM micrographs of the deformed TiZrHfNb

RHEA. Planar slip is the prevalent deformation mechanism in this material. Additionally, in
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the deformed specimen, dislocations are usually long and straight. Several researchers
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suggested that the “Glide Softening effect” results from the planar slip in BCC alloys, thereby
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deteriorating the plasticity of the alloy [176-177]. Yellow arrows show the presence of
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dislocation jogs while the red arrows show the loops on the straight long screw dislocations,

suggesting cross slip dislocations (refer Fig. 15h). Previous study suggests that these loops

occur as a result of the pinning action of chemical fluctuations [178]. As a result of the

existence of local chemical fluctuations, it has been hypothesized that as-printed TiZrHfNb

displays improved ductility.

39
 f
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Fig. 15. (a) SEM images of the post-deformed TiZrHfNb RHEA along the horizontal direction. The
presence of slip bands is demonstrated with yellow arrows in the enlarged view, (b) EBSD-IPF
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image, (c) KAM map, (d) Misorientation map along the deformation band, (e) XRD of the post-
deformed specimen indicating the presence of a single-phase BCC structure. (f-h) TEM images of the
post-deformed RHEA indicating high-density straight and long screw dislocations by white arrows
and the presence of dislocation jogs and loops as marked by yellow and red arrows respectively.
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Reproduced with permission from [119], Copyright 2023, Elsevier.

Cui et al. [179] studied the tensile properties of L-PFF processed

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Ti41V27Hf13Nb13Mo6 RHEA and reported an unprecedented yield strength of 1200 MPa, with

a ductility of ~11.3%. Another recent article [174] on Ti42Hf21Nb21V16 RHEA fabricated by

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L-PFF (in-situ alloying), reported an outstanding strength-ductility trade-off with a yield

strength of about ~1034 MPa with a remarkable ductility of 22.5%. The authors also

compared the tensile properties of the Ti42Hf21Nb21V16 RHEA prepared by casting route. The

as-cast RHEA had a yield strength of ~ 780 MPa, with a ductility of 20.2%. This clearly

suggests the potential of the AM technique for fabricating RHEAs. This composition of

Ti42Hf21Nb21V16 RHEA was selected after rigorous numerical simulations, with the intend to

possess higher ductility. The higher ductility in this AM processed RHEA was attributed to

the formation of coherent interfaces and decomposition of the BCC matrix, which hinders the

40
dislocation motion, thereby enhancing the ductility. More insights into the in-situ tensile

deformation of AM processed RHEA can be found in [174].

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 (a) (b)

(c1) (c2) (c3) (c7)

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3.5 % 8% Fractured

(c4) (c5) (c6)

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Pr
3.5 % 8% Fractured
Fractured
(d1) 3.5 % (d2) 8 % (d3)
(d5)
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Fractured

(e)
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(f)

Fig. 16. (a) True stress vs True strain curve, (b) Strain Hardening rate vs True strain, (c) EBSD IPF

42
and KAM maps of interrupted tensile tests at (c1,c4) 3.5%, (c2, c5) 8%, (c3,c6) Fractured specimen.
(c7) atomic strain maps illustrating strain heterogeneities caused by local chemical fluctuations. (d)
TEM images of the interrupted tensile tests at 3.5%, 8% and at fracture. (e,f) schematic
representation of the deformation mechanisms, dislocation interactions [180], Copyright 2024,
Elsevier.

Recently, Bing Su [180] explored the deformation mechanisms in AM fabricated

Hf10Nb12Ti40V38 RHEAs. The authors reported a tensile yield strength of about 1011 MPa and

a ductility of about 12.6% as shown in Fig. 16a. They observed a very interesting phenomena

of low strain hardening rate {Below 1GPa} (refer Fig. 16b) and a good ductility. Despite

having low strain hardening rate, there was no visible premature dropout. After careful

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investigations, they found out that multiple dislocation channels interactions along with kink

band formation were understood to be the primary deformation mechanisms that govern the

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strain hardening and softening. This Hf10Nb12Ti40V38 RHEA fabricated by AM technique

showed single phase BCC structure. Atomic scale imaging, revealed the presence of local
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chemical fluctuations, and these local chemical fluctuations are in the order of atomic scale.
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So, these cannot be considered or compared with elemental micro-segregations near the melt

pools, grain boundaries and sub cellular boundaries. The formation of these local chemical
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fluctuations, also induced local strain inhomogeneities identified from the atomic strain maps
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plotted by geometric phase analysis method, as seen in Fig. 16.c7. Interrupted tensile tests at
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true strains of 3.5%, 8% were performed to understand the deformation behaviour of this AM
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fabricated Hf10Nb12Ti40V38 RHEA. Fig. 16b demonstrates the Work Hardening rate plot, and

the curve behaviour are classified into three stages. Stage 1 (less than 4% strain) is attributed

to the dislocation slip as the strain hardening rate is decreasing. Further, as the true strain

increases (4-12%), the work hardening rate also increases. And finally stage 3 (> 12%),

fracture, leading to the drop in work hardening rate and the tensile curve. TEM and EBSD

were used to understand the deformation mechanism of the interrupted tests at true strains of

3.5%, 8% and post fracture as well (refer Fig. 16c, 16d). Finally, the higher ductility, despite

having low strain rates are due to the formation of dislocation channels, tangles, and Kink

bands and are schematically illustrated in Fig. 16e, 16f. In-detailed explorations pertaining to
43
the deformation mechanisms of the AM fabricated Hf10Nb12Ti40V38 RHEA and the

dislocation interactions can be found in the original paper [180].

Research on high temperature tensile behaviour studies of the AM fabricated RHEAs

have also begun lately. Yongyun Zhang et al. [181] studied the high temperature tensile

behaviour of the AM processed Hf-Nb-Ti-V RHEA in the temperature ranges of RT, 673K,

773K and 873. The authors have claimed that the good tensile properties even at higher

temperatures for this AM processed Hf-Nb-Ti-V RHEA was due to the local chemical

fluctuations and the atomic misfit. Similarly, few other researchers suggested the phenomena

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of local chemical fluctuations in AM processed RHEAs [178, 180-181]. The same author,

Yansong Zhang et al. [182] studied the high temperature tensile behaviour of another AM

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fabricated Al0.3NbTi3VZr1.5 light wight RHEA. They performed High temperature testing
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from 400°C to 800°C and tried to understand the governing deformation mecahnisms as well.
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4.3. Compressive Properties

Fig. 17 shows the compression properties of AM-built RHEAs. Single phase RHEAs are
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usually composed of BCC structure, and tend to display high strengths though suffer with
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poor deformability. A comparable phenomenon is also observed in the context of other BCC
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alloys. The existence of solid solutions in such alloys not only strengthens the matrix but also
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enables tuning of the stacking fault energy, which in turn impacts the generation of partial

dislocations as well as the occurrence of planar slip and double cross slip. This aids in the

creation of immobile dislocation reaction products, slip patterns, emerging complex

dislocation storage rates, and evolving complex dislocations [47]. Further, researchers

working on conventional manufacturing of RHEAs have tried to introduce reinforcement

materials into the matrix to incorporate precipitation precipitation-strengthening mechanism,

wherein the presence of precipitates in the matrix hinders the dislocation movement

[100,183]

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Fig. 17. Compressive strength vs Elongation for AM fabricated RHEAs

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Researchers expend conscientious efforts to increase the plasticity of RHEAs by
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alloying with certain elements. AM processed NbMoTaW RHEA has an impressive
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compressive strength of 1058 MPa but suffers from a poor ductility of 2.6%. In order to

enhance the plasticity and eradicate the issues of cracking, Ni and Ti into the alloy are
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introduced. The addition of nickelto the NbMoTa matrix refines the grain size. Finally, it was
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found that NbMoTaTi0.5Ni0.5 RHEA (refer Fig. 18) developed by the L-PBF technique had the
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highest compressive strength values (2277.79 MPa) with an impressive ductility of 17%
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among the class of RHEAs fabricated through AM technique. The high strength is due to the

increased formability as Ti and Ni are added thereby reducing the detrimental effects of

cracking and pore formation.

Another important reason is due to the formation of a homogeneous dendritic structure.

Though theoretically from a microstructural aspect, NbMoTaTi should exhibit high strength,

yet in practice, the prevalence of cracks diminishes its strength. In a mechanistic-based

approach of designing alloys, sequential activation of work-hardening mechanisms is vital to

glean materials with superior properties [184].

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Fig. 18. HR-TEM images of the NbMoTaTi0.5Ni0.5 RHEA (a) distribution of the Grain boundary
phase and the matrix phase, (b) an enlarged view in (a) illustrating 4 different points for elemental
and diffraction studies, (c) HR-TEM images of the GB phase, (d) SAED patterns of 4 different points
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as shown in (b). Reproduced with permission from [111], Copyright 2021, Elsevier

In his first report published in 2010, Senkov [34] investigated the NbMoTaW and
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NbMoTaV. Later in 2011, the alloy was further investigated for its mechanical behaviour and

found that NbMoTaW RHEA has a strength of about 500 MPa and could withstand its strength
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up to 1600° C [43]. When Senkov initially investigated the fracture behaviour of NbMoTaW,
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it was brittle and underwent intergranular fracture. The alloy exhibited single-phase BCC along
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with huge amounts of dendric segregations. The Lower DBTT was attributed to the NbMoTaW
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alloy pallet. Nevertheless, after several studies performed using tensile, compression, bending,

and fatigue it came out to know that the fracture mechanism was cleavage and not shear. The

fracture mode in tensile is primarily attributed to the interdendritic cracking, while the fracture

was through the slip bands and intergranular cracking in compression. A similar study

was carried out by doping carbon into NbMoTaW RHEA fabricated through the AM

technique [89]. It was discerned to exhibit excellent high-temperature properties even higher

than the Ni- based superalloys but had a brittle nature at room temperatures. Recently, Z. Wang

et al. [ studied the grain boundary engineering of NbMoTaW and inferred that the room

46
temperature brittleness of NbMoTaW was due to the segregation of elemental oxygen from

the grain boundaries, which in turn weakens the grain boundary cohesion [185]. To

overcome this problem of room temperature brittleness Li et al. alloyed Carbon in

NbMoTaW [100]. The deposition of NbMoTaWC was done using the L-PBF technique. The

deposited specimens were observed to have a density of 96.5% and superior mechanical

properties due to their refined microstructure as a result of nanometric carbide precipitates.

EBSD studies have revealed that the average grain size of (NbMoTaW) 99.5C0.5 is 10.6 µm,

while NbMoTaW was having an average grain size of 18.4 µm. Bright-field TEM imaging of

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(NbMoTaW)99.5C0.5 has shown that most precipitates have been dispersed at the grain

boundaries and dislocations while major traces were also present inside the grains (Fig. 19a,

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15b). SAED pattern of (NbMoTaW) 99.5C0.5 showed an additional set of diffraction spots
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which corresponded to the precipitate of NbC. The precipitates had a polygonal structure
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with a diameter of 58 µm. The formation of NbC (refer Fig. 19c, 19e) is due to its lower

formation enthalpy (-102 KJ/mol) [186]. Fig. 19f corresponds to the HR-TEM images of the
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NbMoTaW99.5C0.5 RHEA at the grain boundary. The precipitation temperature of the NbC is
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in the range of 1400-2400⁰ C and is a diffusion transformation. The addition of Carbon had
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led to a significant increase in the mechanical properties with an impressive compressive

strength of 1782 MPa with an elongation of 7.2% for the NbMoTaW99.5C0.5 RHEA (refer
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Fig. 19g, 19f). A detailed explanation regarding the precipitation and grain refinement

studies of (NbMoTaW) 99.5C0.5 could be unearthed in Xu’s [100] article.

47
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(g)

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Fig. 19. (a, b) TEM dark field images of the L-PBF fabricated RHEA along with their corresponding
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SAED patterns of NbMoTaW and NbMoTaW99.5C0.5 respectively, (c) STEM images showing the
presence of NbC precipitates along with EDS mapping, (d) HR-TEM images of the
NbMoTaW99.5C0.5 RHEA around the dislocation network along with SAED patterns, (e, f) HR-
TEM images of the NbMoTaW99.5C0.5 indicating presence of NbC precipitates and at grain
boundaries respectively, (g) Compressive stress vs strain curves for both the RHEAs and their
postmortem investigations, Reprinted with permission from [100], Copyright 2022, Elsevier.

4.4. High-temperature compressive properties

Engineering applications such as turbine blades, and aircraft engines [187] demand high-

strength materials at elevated temperatures [122]. Turbine blades are exposed to very high

temperatures (beyond 1100˚C) and are generally made up of superalloys [188]. Among the

48
class of superalloys, Ni-based superalloys are of considerable interest owing to their high-

temperature strength, oxidation, and creep resistance. However, they are restricted to a

maximum operating temperature of about 1000 ˚C [189], because of their melting points.

Hence, there is a need to develop materials that can have better properties than Ni-based

superalloys at high temperatures. Followed by the motivation to develop materials that can

withstand elevated temperatures, RHEAs were initially introduced in the year 2010 [34]. Since

then, RHEAs have gained significant attention and could be a potential candidate for such high-

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temperature applications. RHEAs can withstand their strength up to 1600˚C [43]. The high-

temperature stability of the RHEA alloys can be described using a thermodynamic concept of

Gibbs Free Energy (∆Gmix).

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∆Gmix = ∆Hmix- T∆Smix
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where ∆Hmix is the change in mixed enthalpy, ∆Smix is the change in the mixed entropy, T is

the absolute temperature (in K) and ∆Gmix is the change in the mixed free energy. At higher
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temperatures, the entropy of the system increases (i.e., chaos in the atomic arrangement) which
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tends to lower the Gibbs Free energy and henceforth stabilize the system at high temperatures.
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Precipitation Strengthening is an important strengthening mechanism at elevated temperatures,

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where the solid solution strengthening weakens. So, it is better to have multiphase structures

with stable second-phase precipitation, in order to enhance the strength at high temperatures.

Precipitation strengthening is due to the restricted flow of the motion of dislocations in a

material [190]. With the advantages offered by the AM process of producing complex

geometries, AM can be a potential manufacturing technique fabricating RHEAs. So, the high

temperature characteristics of AM processed RHEAs are very important to understand.

Interesting, in a study carried out on AM processed NbMoTaTi0.5Ni0.5 RHEA, it showed a

compressive strength of 2277.8 MPa with a ductility of 15% [111]. When NbMoTaTi0.5Ni0.5

49
RHEA was tested at higher temperatures, it was ascertained that the compressive strengths

steeply decreased with the increase in the temperatures, due to the presence of low melting

point nickel. At 600˚C, 800˚C and 1000˚C the compressive strengths were 1700 MPa, 1033

MPa and 652 MPa correspondingly [111]. There are very few papers on high-temperature

testing of RHEAs and especially on RHEAs fabricated via AM. Therefore, there is a need to

emphasize more on high-temperature testing to prove RHEAs as a prominent candidate for

high temperatures.

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5. Environmental degradation of RHEA’s

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5.1. Corrosion properties

There has only been a limited amount of research done so far on the corrosion behaviour of
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RHEAs. Furthermore, it is worth noting that, Laser based Deposition techniques such as Laser cladding
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are also being considered in this section, and are often referred to as coatings. Corrosion related failure

of a material is one of the major issues with almost all metals [191]. In general, process
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variables have a crucial influence in the corrosion characteristics of AM components because

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they effect the microstructural features. Basically, pores are the favoured locations for
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corrosion attack, particularly pitting. Being a powder-based manufacturing process, AM

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produces components with pores that might impair mechanical characteristics and corrosion

performance. The porosity and density of the component may be optimised by using the

appropriate sets of printing settings. AM components have far higher surface roughness than

other traditional manufacturing processes, and may be optimised by adjusting the processing

settings. Decreased surface roughness reduces electrochemical interactions among the surface

and the environment, resulting in both overall and localised corrosion reduction [192].

RHEAs are expected to manifest exceptional corrosion resistance as they generally belong to

a class of BCC phase alloys. Li et al. [193] emphasized the importance of BCC phase in terms

of corrosion resistance. In an experiment carried out by Li on CoCuCrFeNiAl, they pointed

50
out that HEAs with BCC phase exhibit superior corrosion properties than FCC in acidic

solutions and chloride salts. Defects play a crucial role in determining the corrosion properties

of RHEAs as they are the initiating sites for corrosion, so it is important to manufacture RHEAs

with almost negligible defects. In another study, Zhang et al. [116] studied the corrosion

properties of the TaxNiTiCrNb (x= 0.1, 0.3, 0.5, 1) RHEA processed via L-PFF. The

potentiodynamic polarization curves of TaxNiTiCrNb RHEA coatings in a 3.5 wt % NaCl

solution are displayed in Fig. 20a. These RHEA coatings showed good corrosion resistance,

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with corrosion current densities ranging from 1.08 × 10−7 A/cm2 to 3.81 × 10−7 A/cm2. Table

2 provides an overview of the pertinent electrochemical parameters determined by

polarization curves.

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All these coatings show a broad passivation zone, with Ta0.5 and
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Ta1.0 coatings showing the best pitting corrosion resistance and the emergence of the

secondary passivation phenomena. Therefore, TaxNiTiCrNb coatings possess low sensitivity

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to pitting, and by adding more Ta, the passive film's stability may be increased. XPS analysis

was done on the passive film that resulted from the polarization of NiTiCrNbTax RHEA
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coatings for 30 minutes at 500 mV. XPS intensities of the passive films created by each
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coating have comparable trends, as seen in Fig. 20b.

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(a) (b)

Fig. 20. (a) PDP curves in 3.5 wt% NaCl of the TaxNiTiCrNb coating, (b) XPS graph of the coating
after passivation. Reproduced with permission from [116], Copyright 2022, Elsevier.
51
Table. 2: Electrochemical parameters in 3.5% NaCl for the TaxNiTiCrNb (x= 0.1, 0.3, 0.5, 1)
RHEA coating [116]

RHEA Coating icorr (A/cm2) Ecorr (VSCE)

Ta0.1NiTiCrNb 1.08 × 10−7 -0.312
Ta0.3NiTiCrNb 3.81 × 10−7 -0.386
Ta0.5NiTiCrNb 2.69 × 10−7 -0.404
Ta1.0NiTiCrNb 1.63 × 10−7 -0.233

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Jiang et al. [118] have deposited TiZrAlNb and TiZrAlNbCo RHEAs by the L- PFF

technique on the Ti6Al4V substrate to overcome the shortcomings of poor corrosion resistance

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and wear resistance. The phase compositions of TiZrAlNb were revealed to be BCC with some
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intermetallic compounds of AlTi3 and AlNb3. While the Co-added TiZrAlNb had a BCC+FCC

structure with AlTi3 and AlNb2 compounds. Compared to TiZrAlNb, TiZrAlNbCo has high
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hardness and corrosion resistance, which could be attributed to the addition of Co. The Co-

addition also stabilizes the RHEA. To understand the mechanism of corrosion in TiZrAlNbCo
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RHEA processed via AM, microstructural characterization along with EDS mapping was
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carried out before and after the corrosion testing. Fig. 21a shows the SEM images with EDS
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mapping before the corrosion test, which reveals the island is of BCC phase Ti-Nb surrounded
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by a base matrix of FCC phase Al-Co-Zr. Fig. 21b indicates the EDS mapping of

TiZrAlNbCo after the corrosion test, which shows the formation of corrosion pits on the Ti-

Nb BCC phase. At the same time, a passivation layer is established on the FCC phase matrix,

thereby safeguarding the material. The partial wetting transition mechanism between the

grain boundaries and the grain boundary triple junction induces island formation in this

material. The arguments presented suggest that, the corrosion resistance of AM-fabricated

RHEAs is significantly influenced by microstructural properties like as inclusions, porosity,

surface roughness, residual stresses, chemical segregation, inclusions, phases, and grain size

52
distribution.

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Fig. 21. SEM imaging along with EDS mapping of the TiZrAlNbCo RHEA(a) prior to corrosion and
(b) post-corrosion testing. Reprinted with permission from [118], Copyright 2022, Elsevier.

5.2. Wear

Wear resistance of AM processed RHEAs is another important property that RHEAs are

expected to exhibit. In general, AM processed RHEAs showcase exceptional hardness, which

implies that they could possess goodwear properties. High wear resistance helps in preventing
53
the damage of material under harsh environments and rubbing actions [194]. The wear

properties of AM processed RHEAs are comparable to that of conventional superalloys and

refractory alloys. J. Luo et al. [195] tried to develop high wear resistant TiTaZrHfNb RHEA

by surface remelting to produce heterogeneously gradient nanostructure. They tried to employ

laser-based surface remelting in order to produce a heterogeneous gradient structure. It was

evident that the initial single-phase coarse-grained BCC were decomposed into TiNb and

TaNB rich BCC phase, Zr-Hf rich HCP phase along with TiZrHf rich FCC phase. Apparently,

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nanograined homogenous structures significantly have more grain boundaries showcasing no

enhanced wear properties. This is attributed to the mechanical instability caused due to the

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restricted motion of the motion and multiplication of dislocations [196-197]. In another study
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by Zhao [114], they tried to deposit AlNbTaZrx RHEA as a coating to enhance its wear

properties. The Zr percent was been changed from 0.2,0.4, 0.6, 0.8 and 1.0 wt%. Compared
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with different variants of Zr additions in this RHEA, 0.8% Zr possess higher wear resistance

with the lowest wear track depth. It is worth mentioning that in the context of 1% Zr the wear
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mechanism was a combination of micro-cutting and oxidation. This synergistic effect

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aggravated brittle debonding. A list of a few wear properties has been showcased in Fig.22.
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Fig. 22. Wear properties of various RHEAs fabricated via AM
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Wang et al. [103] deposited MoFe1.5CrTiWAlNbx (x = 1.5, 2, 2.5, 3) RHEA coating

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through laser cladding in order to obtain hard and wear-resistant coating for high-performance
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cutting tools. Fig. 23(a-e) illustrates the SEM image of the worn surface for the substrate and
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the RHEA coatings. The worn morphology of Nb1.5 is shown in Fig. 23a, where tearing

deformation is clearly visible. There is no evidence of an oxidation process, and a narrow, tiny
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furrow forms. Nb increases cause the furrows to get smaller (Fig. 23(b–d)). According to EDS

in these locations, the worn surface is mostly formed of two areas: dark grey (oxidised regions)

and grey (non-oxidized regions). The extent of oxidised areas steadily shrank as the Nb

concentration rose. It is worth mentioning that, the increase in the Niobium content led to a

decrease in the wear volume loss (refer Fig. 22). The higher Nb content leads to the

55
stabilization of the MC and C-14 Laves phases. These phases enhance the microhardness and

wear resistance, as they hinder the dislocation movement. The wear mechanism is primarily

abrasive wear. Fig. 23e shows the worn morphologies of the substrate (M2 tool steel), which

has deep furrows and the mechanism is also abrasive wear. In general, AM processed RHEAs

with single phase BCC structure, showed smoother surface deformation, with oxygen

enrichment and finer debris, suggesting the fact that oxidative wear. It is also worth

mentioning, that wear resistance doesn’t just directly depend on the hardness values, but on

several competing factors including complex microstructures, chemical segregations, BCC

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phase volume fraction, morphology, wear behaviour, surface roughness and the

manufacturing process [198]. In order to obtain superior wear properties of the AM fabricated

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RHEAs, proper process variables are essential, as improper process conditions can lead to
e-
rough surface and several other defects. Surface roughness and residual stresses in AM

fabricated RHEAs can increase the wear volume loss and reduce the component lifespan.
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56
 (a) (b)
Furrow
Deformation
Oxidized region

Non-Oxidized region

(c) (d)

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(e)
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Furrow
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Fig. 23. (a-d) Wear morphologies of the MoFe1.5CrTiWAlNbx RHEA coating with Nb1.5, Nb2,
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Nb2.5, Nb3 respectively and (e) wear morphology of the substrate i.e., M2 tool steel. Adapted with
permission from [105], Copyright 2019, Elsevier.

5.3. Oxidation Properties

Oxidation studies of RHEAs fabricated through AM are crucial, as these alloys are potential

candidates for high-temperature applications where oxidation is a major concern. One of the

significant drawbacks of refractory metals is that they possess poor elevated temperature

oxidation resistance under oxidizing environments. There is substantial disagreement among

researchers over the true values of oxidation kinetics, highlighting the need for more research. Nonetheless,

57
AM fabricated RHEAs outperform commercial refractory alloys in terms of oxidation resistance by at least

one order of magnitude. Complex oxidation kinetics therefore result from the superposition of

positive contributions from solid scale development and negative contributions from

volatilization, evaporation, or spallation. [199]. In general, the oxidation behaviour of

refractory metals could be improved by adding Al, Si and Cr. These elements form a

protective oxide scale of Al2O3, SiO2, and Cr2O3 respectively. The addition of these elements

such as Al, Cr, and Si not just enhances the oxidation resistance, but also reduces the density

of the RHEAs. However, very limited works on the oxidation studies of RHEAs fabricated

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through AM have been carried out to date.

The effect of TiC on the elevated temperature oxidation mechanism of NbMoTaWV

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fabricated through the L-PBF technique was investigated (Fig 24a, 24b). In their study, it was
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found that cracks were the major source of defects in NbMoTaWV RHEA, which could be
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mitigated by process parameter optimization. In addition, TiC particles could also suppress the

crack formation in this RHEAs [122]. P. Zhao et al. [114] studied the oxidation behaviour of
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AlNbTaZrx by varying the Zr contents (x=0.2, 0.4, 0.6, 0.8 and 1.0 wt%) at 1000oC for 50h.

LMD fabricated AlNbTaZrx RHEA is applied over Ti6Al4V substrate in order to enhance its
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wear and elevated temperature properties. Compared to the substrate RHEA coating possessed

good oxidation resistance (60%-87%) with a mass gain of 2.6 mg/cm2 [24% of substrate - 10.78
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mg/cm2]. Pesting behaviour in RHEAs is the breakdown of the metallic substrate as a result of

intergranular oxidation [200].

The authors have observed that the increase in Zr content led to a significant increase

in the oxidation resistance. In order to understand the oxidation products of the surface, XPS

was performed and understood that the oxide layer consisted of TiO2, ZrO2, 2Al2O3, 2Nb2O5,

2Ta2O5. Fig. 24c illustrates an Ellingham diagram of various oxides formed in the oxide layer.

The thermodynamic stability of the oxides is a function of the negative value of Gibbs Free

58
Energy (-∆Go). It is the saying that the formation of oxides of Ta, Nb and Al occurs prior to

the oxides of Zr and Ti. Though ZrO2 has a relatively positive enthalpy, the oxidation resistance

has been enhanced by increasing the Zr content. This is attributed to the stability of the oxides.

The stability of oxides depends on the volumetric change in the material during the process of

oxidation. The stability of oxides is calculated by Pilling–Bedworth ratio) PBR. The value of

Zr is low compared to all other values of Ta, Ti, Al, Nb. So, change in Zr content can influence

the oxidation resistance despite its relatively positive free energy.

In another study, NbMoAlTiV Lightweight Refractory High Entropy alloy (L-RHEA)

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was deposited onto a Ti6Al4V substrate in order to increase its surface hardness and elevated

temperature oxidation resistance [99]. The high temperature oxidation studies were carried out

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at 800 oC for 120h, and noticed that the coatings mass gain is 4.94 mg/cm2, which is 9.45 times
e-
less than the mass gain of the substrate (46.7 mg/cm2). The oxide layers thus formed was Al2O3
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followed by TiO2.
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(c)

Fig. 24. (a, b) Schematic diagram indicating the high temperature oxidation mechanism of
WMoTaNbV and TiC/WMoTaNbV respectively. Reproduced with permission from [122], Copyright
2022, Elsevier, (c) Ellingham diagram showing several oxides formed on the oxide layers in

59
AlNbTaZrx RHEA. Adapted with permission from [114], Copyright 2021, Elsevier.

Recently, Zhe Li et al. [201] studied the oxidation behaviour of the AM fabricated

TiNbMoAlSi RHEA by performing cyclic oxidation tests up to 60 hrs @1000°C and isothermal

oxidation kinetics for 1000°C/8hrs (refer Fig. 25). These RHEAs were fabricated by Electron Beam

Additive Manufacturing technique. As discussed earlier, AM fabricated RHEAs usually do not

possess excellent oxidation resistance. In view of this, and with the aim to enhance the oxidation

resistance of the AM fabricated RHEAs, new strategies of remelting and Al-deposition have been

employed in this study to enhance the oxidation resistance. High temperature cyclic oxidation carried

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at 1000°C after 60 hrs showed that the overall mass gain decreased by 17.5% for remelted samples,

and about 30.5% for the Al-deposited samples when compared to the As-cast samples. The

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enhancements in oxidation resistance for remelted samples was attributed to the formation of finer
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Short-Range Ordering (SRO) structures, while in case of Al-deposited RHEAs, it was attributed to

the formation of intermetallic and silicide phases. Post oxidation microstructural analysis of the
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surface morphologies have also been studied and are illustrated in Fig. 25g, 25h, 25i. At 1000 °C, the

oxides appear to develop sequentially with varying the Al concentration, as shown in Fig. 25j. The
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evolution of oxides are as follows: TiNb2O7 → TiO2 + TiNb2O7 → TiO2 + AlNbO4 → TiO2 + Al2O3 +
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AlNbO4. The authors [201] found that the higher oxidation resistance for this AM fabricated RHEA
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is believed to a result of the multilayer oxides comprising of TiO2, SiO2 Al2O3 along AlNbO4 with as

obtained by performing EDS, EPMA imaging and XRD.

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60
 (a) (b) (g) (A) (B)

(C) (g1) (g2)

(c) (d)
(g3)

(e) (f) (h1) (h2)

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(i) (j)

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Fig. 25. (a,b) Isothermal oxidation kinetics of both the remelted and Al-deposited TiNbMoAlSi
RHEAs at 1000°C/8hrs, (c,d) Cyclic oxidation of the remelted, Al-deposited and As-cast RHEA for
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reference. (e,f) Total mass gain for unannealed, annealed, remelted and Al-deposited samples after 60
hrs. (g) SEM surface oxide morphology after isothermal oxidation of Al-deposited samples. (g1, g2,
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g3) refer to the high magnification images of the regions of boxed regions of A,B,C respectively in
fig. g. (h1,h2) SEM surface oxide morphology after isothermal oxidation, for the remelted samples.
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(i) SEM cross section images illustrating the surface oxide morphology of the cyclic oxidation
samples of remelted and Al-deposited. (j) Schematic representation of oxide evolution by varying the
Al content [201]. Copyright 2024, Elsevier.
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6. Recent status and challenges

Hitherto, only a few studies on additive manufacturing of RHEAs have been explored.

Nevertheless, there are still some challenges associated with this field, such as cracking

susceptibility and high residual stresses, low dimensional accuracy, poor surface finish,

chemical inhomogeneity, mechanical anisotropy and so on. As a result, more work should be

done to broaden our understanding of this new family of metallic materials using AM

techniques. Therefore, this section will present a couple of ideas to suggest some potential

61
research lines for AM RHEA innovation and enhancement.

1. There is a need for the development of design theory for these materials. As of date,

there is no fixed composition for the RHEA.

2. More emphasis should also be made on the innovation of novel RHEA materials, which

could lead to significant developments for high-temperature materials with superior

properties.

3. Generally, As-built additively manufactured builds suffer from anisotropy and are

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prone to cracking, so the builds need post-heat-treatment. More efforts must be made

to get an in-detailed understanding of the precipitation mechanisms in RHEAs.

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4. The presence of defects such as pores and cracks could drastically affect the build's
e-
properties. To prevent the formation of pores, cracks, and other detrimental effects such

as balling and so on, process parameter optimization of RHEAs should be carried out
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to produce high-quality defect-free builds. As additive manufacturing is costly, the trial-

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and-error method of testing for deciding the process parameters would lead to

significant wastage of cost and time. Therefore, machine learning can play a crucial
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62
 role in determining the process parameters of additively manufactured builds which is

a time-saving and cost-effective technique.

5. Significant research has to be carried out on high temperatures stability, creep, and

fatigue testing of the additive manufactured samples to understand the properties better

and find themselves suitable for high-temperature applications beyond the traditional

superalloys. Creep studies of RHEAs would also reveal the diffusion and creep

mechanisms at elevated temperatures.

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6. However, studies on post-treatments of the AM builds are also required to assess the

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quality of the build surface, as AM builds usually suffer from rough surfaces.

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The broad acceptance of these materials across a range of sectors depends on resolving
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problems with material homogeneity, post-processing, high temperatures, process

optimization, and cost-effectiveness. To overcome these obstacles and realize the full potential
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of RHEAs made using additive manufacturing, researchers and industry players are

collaborating.
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7. Future Scope
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Additively manufactured RHEA’s have a promising future ahead of them and present a wide

range of opportunities in the industrial and materials research domains. These salient features
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emphasize the potential applications of this technology in the future:

1) Aviation and Aerospace Industry: RHEAs have the power to completely

revolutionize the aviation and aerospace domain. Turbine blades and other high-

temperature, high-strength components can be made with additively built RHEAs. This

may result in aeroplanes with higher performance and reduced fuel consumption.

2) Space Industry: The design and manufacture of modern spacecraft and space systems,

such as heat shields, and rocket nozzles, may heavily rely on additively manufactured

63
 RHEAs due to the increased interest in exploring space and the necessity of materials

that can withstand harsh environments.

3) Regulatory Frameworks: In order to ensure safety and quality, regulatory agencies

and standardization organizations may establish rules and standards for the

manufacturing and utilization of RHEAs as their use in important applications

increases.

4) Development of Novel RHEA’s: Novel RHEA compositions with greater optimized

features are probably going to be produced via ongoing study. The range of possible

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uses for these novel materials will increase, and they will also improve component

performance in harsh situations.

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In conclusion, a number of sectors stand to benefit from the future expansion of
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RHEAs developed through additive manufacturing. These materials have unique
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characteristics that can meet the need for high-performing areas under challenging

circumstances. We may anticipate more applications and greater industry-academia

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collaboration as research and AM techniques develop, which will spur innovations in materials
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science and manufacturing.

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8. Conclusions
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This review gives a comprehensive overview RHEAs fabricated through AM in terms of

microstructural characterization and mechanical properties. RHEAs have promising utility in

applications such as the aircraft industry, defence industry, nuclear industry, and other fields.

However, they are currently limited to laboratory research. RHEAs are not feasible because of

their high cost and immature fabrication process. The mechanical properties of AM prepared

RHEAs are comparable to the conventionally manufactured counterparts.

This study demonstrates that the potential of additively manufactured RHEAs is enormous, and

the properties obtained by the deposited RHEAs collected from existing literature can compete

64
effectively with wrought RHEAs. However, there is no generic way to define the design theory

for RHEAs. Simulation could be a practical approach for determining the phase compositions

and mechanical properties, significantly reducing production time and cost. RHEAs fabricated

through AM exhibit finer microstructure with outstanding mechanical properties because of

the higher cooling rates. Compared to its counterparts for fabricating RHEAs, additive

manufacturing could be a promising technique, despite drawbacks such as high susceptibility

to cracking. Extreme High-Speed Laser Cladding on rotating components could be a promising

technique for depositing thick coatings with high strengths at elevated temperatures and high

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wear and corrosion resistance. This paper is intended to stimulate the researcher’s attention and

provide useful information for the fabrication of this unique class of RHEAs.

Credit author Statement

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Akshay Yarlapati: Writing-original draft, investigation, writing- review & editing; Y.N.
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Aditya: Writing-original draft, Supervision, investigation; Deepak Kumar: Investigation,

editing, validation and guidance; R. J. Vikram: Investigation, editing, validation, and

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guidance; Mayank Yadav: Writing-original draft, investigation, Kallem Shekar Reddy:

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Investigation, validation, and guidance; K. G. Prashanth: Conceptualization, Formal

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analysis, review and editing of manuscript.

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Declaration of interests
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☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
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☐ The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests: