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High-Entropy Alloys
High-Entropy Alloys
Second Edition
B.S. Murty
Department of Metallurgical and Materials Engineering,
Indian Institute of Technology Madras, Chennai, India
J.W. Yeh
Department of Materials Science and Engineering,
National Tsing Hua University, Hsinchu, Taiwan
S. Ranganathan
Department of Materials Engineering,
Indian Institute of Science, Bangalore, India
P.P. Bhattacharjee
Department of Materials Science and Metallurgical Engineering,
Indian Institute of Technology Hyderabad, India
Elsevier
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Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices, or
medical treatment may become necessary.
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instructions, or ideas contained in the material herein.
Metallurgy has been leading human civilization from time immemorial. Man knew
how to extract metals from ores, how to alloy metals to make them suitable for specific
needs, and how to prepare high-purity metals and compounds for electronic applica-
tions. Looking back into the last century, it may be said that developments in metal-
lurgy and materials science have played a significant role in several areas and
impacted the economy and well-being of people. Every other branch of science
and engineering has depended on advances in metallurgy to be applied in its domain.
Development of superalloys for jet engine applications, development of carbon-
carbon composites for wings of wide-bodied aircrafts, high-temperature superconduc-
tors, etc. are only a few examples to quote. It should also be mentioned here that the
availability of excellent high-resolution techniques has contributed immensely to the
understanding of the science and technology behind these developments, particularly
from the point of view of structure-property correlations coupled with phase
transformations.
Looking at the present century and the research areas covered in the last decade and
a half, it is not an understatement if I say that the topic of “High-Entropy Alloys”
(HEAs) aka “Multiprincipal Component Alloys” has been the main attraction of sev-
eral research groups all over the world. The number of publications on HEAs in recent
years in Acta Materialia has far exceeded that of any other topic. I am delighted to
write this Foreword for the Second Edition of the first book on High-Entropy Alloys.
The Foreword for the First Edition was written by Brian Cantor of the United
Kingdom.
The basic difference between conventional single base alloy systems and HEA is
that the latter deals with compositions at the center of a multicomponent phase dia-
gram. Several factors lead to the formation of single-phase HEA. Yeh, independent
inventor of HEA, attributed this to four core effects: high entropy, sluggish diffusion,
high lattice distortion, and cocktail effects. Several of the alloys chosen by him turned
out to be single phase, but some revealed additional phases on examination by high-
resolution techniques. Thus, there are challenges in understanding the evolution of
phases in HEAs. However, HEAs have given impetus for the evaluation of mul-
ticomponent phase diagrams, and new multicomponent thermodynamic databases
are being developed by agencies such as Thermo-Calc. These alloys have also opened
new avenues to probe into diffusion and mechanical behavior to understand the dis-
location dynamics and phase transformations in multicomponent systems.
Early work on HEAs by several groups was mainly focused on 3-d transition
metals partly due to our familiarity with these metals, stainless steels, and superalloys.
These crystallized in FCC or BCC structures. The mechanical properties of 3-d HEAs
x Foreword for the second edition
were only marginally better than the existing alloys, but their oxidation and corrosion
resistance in a few cases were better than conventional materials. Improvements in
strength in FCC alloys were obtained by particulate strengthening, while ductility
in BCC was brought in by eutectic microstructure. However, the so-called Cantor
alloy containing FeCrMnNiCo showed high strength and high ductility over a wide
range of temperatures. This leads one to concentrate on the deformation mechanisms
that operate in HEAs for a better design of the alloys.
With the interest to develop alternatives to superalloys, which have reached a sat-
uration, a few researchers focused their attention on refractory HEAs containing Hf,
Nb, W, Cr, Zr, etc. as they expected these to yield better high-temperature properties.
While the strength levels were high, ductility was found to be low. It was realized that
equiatomic compositions are not likely to yield the desired properties suitable for spe-
cific applications and compositions were tailored to obtain the requisite properties.
I feel one has to be innovative and intuitive in selecting the compositions of alloys.
Possibly, minor additions of some elements such as C, B, and RE in HEAs may yield
improved properties. I expect greater emphasis by researchers on this aspect in the
coming years.
The last chapter in this book is on application. There should be a concentrated effort
on the use of HEA coatings for environmental protection, as the underlying structure is
well established and HEAs may extend their useful life. At the same time, focused
emphasis is needed to develop refractory HEAs as their use is likely to increase
the efficiency of energy systems and at the same time reduce pollution levels. The
industries, R&D laboratories, and academic institutions should join hands in bringing
HEAs to the market as early as possible.
The first edition of the book brought out in 2014 had 10 chapters and written by
three authors. It has been expanded now by adding three more chapters, with an addi-
tional author. All the appendixes have been updated. In addition, I should also point
out that Chapter 5 includes information on the use of “Artificial Intelligence in
HEAs,” which would be useful to researchers in the field.
R. Krishnan
Former Director, Gas Turbine Research Establishment, Bengaluru, India
Foreword for the first edition
In the 1970s, I became excited about the idea of multicomponent alloys. I realized that
the materials we use are almost all based on a single component with a primary prop-
erty and an admixture of small amounts of other components to provide secondary
properties. Effectively, all our known materials are at the corners and edges of a mul-
ticomponent phase diagram consisting of all possible components. This means that
there are a vast number of possible materials in the middle of this phase diagram that
have never been investigated. It turns out that this unknown field of materials is truly
enormous and the number of unexplored materials is many times greater than the num-
ber of atoms in the universe.
This explains why we keep discovering exciting new materials: high-temperature
superconductors, glassy alloys, quasicrystals, compound semiconductors, and so on.
And we will keep finding exciting new materials as long as we have the courage as
experimenters to try innovative, new mixtures of constituents. I now tell every PhD
student in materials science to be aggressive and ambitious in exploring this amazing
array of potential new materials.
In the 1970s, I found it hard to persuade other people to be similarly enthused by my
ideas on the topic of multicomponent alloys. I could not get funding, and I could not
get research colleagues to undertake preliminary experiments. Everyone wanted to
work in much better known fields. Everyone was very conservative. Finally,
I persuaded a young undergraduate student, Alan Vincent, to do preliminary work.
He immediately found exciting results including the first high-entropy alloys. Nearly
20 years later, I persuaded another young undergraduate student, Peter Knight, to
repeat the work. And finally, a couple of years later, my long-standing research col-
league, Isaac Chang, repeated the experiments for a third time but more carefully and
with more time to document the results fully and in a publishable way. We presented
the results, first found by Alan Vincent in 1979, at a conference in 2002, which was
published in 2004, more than 25 years since my first idea. In parallel, Professor
S. Ranganathan (my old friend, Rangu) and Professor J.W. Yeh (my new friend,
Jien-Wei) published independently papers on, respectively, material cocktails and
high-entropy alloys, closely related and essentially similar concepts to my idea of mul-
ticomponent alloys.
In the last few years, as a consequence of the outstanding continuing work by Jien-
Wei, the field of multicomponent and high-entropy alloys has taken off, with literally
hundreds of publications each year. Most notably, Vincent, Knight, Chang, and
I discovered in the late 1970s a single FCC solid solution consisting of six components
in equal proportions, namely, FeCrMnNiCo. This alloy has been shown to have out-
standing mechanical properties, with high strength and high ductility. I realized in the
xii Foreword for the first edition
late 1970s that the mechanical behavior of this material would be very unusual. Metal
and alloy mechanical properties depend primarily on the behavior of dislocations and
how they move in response to stress, but the concept of a dislocation as a line defect
with a consistent core structure becomes complex when there are many different com-
ponents distributed on a single lattice.
Professors Murty, Yeh, and Ranganathan have now written a book on this new
group of materials. The book covers the structure, processing, and properties of the
materials, insofar as we have been able to explore them. Some multicomponent alloys
are solid solutions with high entropy. Some are not. In either case, there are wonder-
fully exciting new structures and properties to be found. This book is the first about
this field. It contains many valuable and interesting insights. But ultimately, it can
only hint at the full range of new materials that remain to be discovered. The authors
should be congratulated on doing an important job that will help us on our exciting,
exploratory journey into the materials of the future.
Prof. Brian Cantor
Vice Chancellor, University of Bradford, United Kingdom
Preface for the second edition
The high-entropy alloy (HEA) field has been growing leaps and bounds. The first edi-
tion of HEA book has been published in 2014, mostly based on the publications until
2013. The number of publications in the last 5 years (2014–June 2018) is six times
(more than 2600) that of the publications that have come out in the first decade of
the field (about 400 from 2003 to 2013). This has necessitated the release of the second
edition of the book. The current edition adds on the new research that has been brought
out in the last 5 years to the first edition.
While the number of new equiatomic compositions that have been investigated in
the last 5 years has not been many, researchers realized the need to develop non-
equiatomic compositions (and with minor additions of certain elements) to bring
out significant improvements in various properties. New subclasses in HEAs such
as eutectic HEAs, HEA superalloys, TWIP- and TRIP-type HE steels, dual-phase
HEAs, light HEAs, and HEA oxides have been developed in recent years.
The efforts on predicting the phase formation in HEAs through thermodynamic
calculations and attempts to calculate multicomponent phase diagrams through
CALPHAD approaches have significantly grown. Thermo-Calc has brought out a
new HEA thermodynamic database (TCHEA) to assist researchers in the calculations
in multicomponent space. In addition to first principle calculations, researchers also
started exploring artificial intelligence as a tool to understand the behavior of HEAs in
terms of phase formation and properties.
In addition to the existing routes for the synthesis of HEAs, new routes such as
carbothermal shock synthesis to prepare nanoparticles of HEAs and 3-D printing
through additive manufacturing routes developed recently have widened the scope
of the field. In addition to the traditional applications, HEAs are being explored for
a variety of functional applications such as magnetic, thermoelectric, and biomedical
applications.
It is also pertinent here to say that a number of large-scale initiatives are being taken
in various countries through public and private partnerships to bring out both scientific
and technological advances in this field. In recent years, almost every conference in
metallurgy has special sessions on HEAs. In addition, exclusive conferences/sympo-
sia/workshops are being conducted regularly in this field to share the knowledge being
gained by various researchers. Mention can be made of biennial International Confer-
ence on High-Entropy Materials (ICHEM), the first one held in Taipei, Taiwan, in
2016 and the second one being held in Jeju, Korea, in December 2018. In India also,
a similar biennial International Workshop on High-Entropy Materials (IWHEM)
started in 2015 at Chennai and subsequently at Hyderabad in 2017, and the next
one will be held in Kanpur. A website (https://mme.iitm.ac.in/hea/) is being main-
tained by the group of B.S. Murty in the research activities in this field, with particular
xiv Preface for the second edition
emphasis on Indian research activity. This webpage is updated monthly, and one can
get a list of up-to-date publications in this field from this source.
This second edition of the HEA book brings out all the recent advances in this
exciting new class of alloys. We are confident that it would excite the reader.
B.S. Murty,
J.W. Yeh,
S. Ranganathan,
P.P. Bhattacharjee
Preface for the first edition
Alloys traditionally have been based on a solvent element to which various solute
atoms are added for improving specific properties. Thus, alloys are usually named
after the major element in the alloy, for example, Fe-base, Al-base, Cu-base,
Mg-base, and Ni-base alloys. Two people, in recent times, have changed the way peo-
ple look at alloys, and they are Prof. Brian Cantor and Prof. Jien-Wei Yeh by coming
up with equiatomic and nonequiatomic multicomponent alloys. Incidentally, though
each of them started working on these alloys independently at different times (Cantor
starting in 1981 and Yeh starting 1996), their work came to open literature in the same
year, 2004. Interestingly, even before the papers of these two pioneers got published in
2004, Prof. S. Ranganathan felt the importance of this new class of alloys and wrote
about them in his classic paper “Alloyed pleasures: multimetallic cocktails” in 2003,
which has been cited more than 100 times now as the first publication on this class of
alloys.
Yeh christened these alloys as “high-entropy alloys (HEAs),” rightly so, as the con-
figurational entropy of these alloys is expected to be very high at their random solution
states. Such a high entropy is expected to let the alloys tend to form simple solid solu-
tions (crystalline or amorphous) rather than complex microstructures with many com-
pounds. The concept has caught the attention of many in the last one decade witnessed
about 400–500 papers being published on HEAs with various elemental combinations.
Two major observations can be made from all this work, namely, the alloys do form
simple solid solutions in most of the cases, and the number of phases observed in these
alloys is much less than the maximum predicted from the Gibbs phase rule.
There are also clear indications that the high entropy in these multicomponent
equiatomic and nonequiatomic alloys is not able to act like a glue holding all the atoms
together in a single solid solution, and there are reports on the formations of two or
more phases in which intermetallic phases and even segregation of certain elements
might form. This could be related with the various thermodynamic and kinetic factors.
There has been intense activity in the past few years to predict the phases that can form
in such multicomponent alloys through various modeling approaches including inte-
grated computational materials engineering (ICME) using various tools such as
CALPHAD, ab-initio, molecular dynamics, Monte Carlo, and phase-field approaches,
which have been supported by Materials Genome Initiative (MGI).
Besides the science curiosity, researchers also wish that HEAs can substitute con-
ventional materials in advanced applications so that the limitations in service life and
operation conditions could be overcome by providing superior performance.
A number of processing routes, including conventional melting and casting, mechan-
ical alloying, various coating techniques, and even combinatorial materials science
approaches, are being used to synthesize and process this new class of alloys. There
Acknowledgments for the second
edition
The authors are grateful to Dr. R. Krishnan for readily agreeing to write a foreword for
the second edition of the book. He has also made immense contributions by critically
examining each chapter and helping to improve its quality. We are also grateful to all
the authors of various publications that we refer to in this book.
Prof. Murty would like to specially thank his group members, Dr. Nagini, Dr.
Satish, Dr. Ram, Gopi, Lava Kumar and Adil, who have helped in collecting the arti-
cles and going through the write-up to bring it to good shape. Among all, Lava
Kumar’s help is immense, and Prof. Murty is indebted to him for it.
Dr. Pinaki Bhattacharjee would like to thank his group members, Seelam,
Narayanswamy, Veerasham, and Jaydeep, for their immense help in collecting the rel-
evant research papers.
Prof. Yeh would like to thank his research assistant, Hsuan-Chu Chen, for updating
the statistical analysis of published SCI and EI papers on high-entropy alloys and
related materials. He also thanks his PhD student, Ko-Kai Tseng, for preparing
new figures.
Prof. Ranganathan is thankful to Ms. S. Varalakshmi and Dhairyasheel Patil for
their help in compiling the chapters.
B.S. Murty,
J.W. Yeh,
S. Ranganathan,
P.P. Bhattacharjee
Acknowledgments for the first
edition
The authors are grateful to Prof. Brian Cantor for readily agreeing to write a foreword
for the book, in spite of his hectic schedule as Vice Chancellor of University of Bradford,
the United Kingdom. We are also highly indebted to all the authors and publishers of
various works that we refer to, who have significantly improved the quality of the book.
Prof. Murty would like to specially thank his group members, Mayur, Guruvidyathri,
Anirudh, Arul, Ameey, and Dr. Sanjay, who have untiringly helped at various stages.
Meeting the deadline of the publisher would not have been possible without their help.
He would also like to gratefully acknowledge the collaboration with his students,
Varalakshmi, Praveen, Pradeep, Sriharitha, Ashok, Durga, and Raghavan, and
collaborators Dr. Ravi Sankar Kottada, Prof. M. Kamaraj, and Prof. K.C. Hari Kumar
of IIT Madras; Dr. Sheela Singh, Dr. N. Wanderka, and Prof. J. Banhart of Helmholtz-
Zentrum Berlin; and Prof. D. Raabe of Max-Planck-Institut f€ur Eisenforschung,
D€usseldorf. He thanks all of them for joining him in this exciting journey so far.
He is also indebted to his family members for their patience and continuous support.
Prof. Yeh would like to thank two important group members, Prof. Su-Jien Lin and
Prof. Swe-Kai Chen, for their long-term contributions in the research on high-entropy
alloys since 1995. He also expresses sincere thanks to Profs. Tsung-Shune Chin, Jan-
Yiaw Gan, Tao-Tsung Shun, Chun-Huei Tsau, Shou-Yi Chang, Tung Hsu, and Wen-
Kuang Hsu and all graduated students for their significant efforts and contributions in
HEA-related research. In addition, he specially thanks Dr. Chun-Ming Lin and PhD
student Chien-Chang Juan for their help in searching related papers, plotting figures,
and providing suggestions for this book. Finally, he also gratefully thanks his beloved
wife and daughters for all their encouragement and supports during writing this book.
Prof. Ranganathan records his gratitude to numerous teachers, colleagues, and
students who instilled him an abiding interest in physical metallurgy. Special thanks
are due to T.R. Anantharaman, P. Rama Rao, Alan Cottrell, David Brandon, Robert
Cahn, A.L. Mackay, Gareth Thomas, J.W. Cahn, P. Ramachandra Rao,
K. Chattopadhyay, D. Shechtnan, K.H. Kuo, and A. Inoue. Grateful thanks are
expressed to members of his family Sucharita, Satyajit, Bratati, Viswajit, and Gopika
for the support in writing this book.
The authors are deeply indebted to Dr. R. Krishnan for his meticulous reading of
the entire book and thank him profusely for his useful suggestions.
B.S. Murty,
J.W. Yeh,
S. Ranganathan
List of abbreviations
AI artificial intelligence
AM additive manufacturing
ANN artificial neural networks
APS atmospheric plasma spraying
ATT accelerated technology transition
APT atom probe tomography
BCC body-centered cubic
BMGs bulk metallic glasses
CALPHAD CALculation of PHAse Diagrams
CNFs carbon nanofibers
COF coefficient of friction
CPA coherent potential approximation
CR cold rolling
CTCR cryogenic temperature multipass caliber rolling
CTS carbothermal shock
CVD chemical vapor deposition
DC direct current
DFT density functional theory
D-G Darken-Gurry
DLF direct laser fabrication
DR dendritic
DSC differential scanning calorimetry
DTA differential thermal analysis
DSS disordered solid solution
EBSD electron backscatter diffraction
EBW electron beam welding
ECCI electron channeling contrast imaging
EDS energy dispersive spectroscopy
EHEAs eutectic high entropy alloys
EMI electromagnetic interface
EMPA electron probe microanalysis
FCC face-centered cubic
FSP flame spray pyrolysis
GB grain boundary
GCP geometrically close-packed
GFA glass forming ability
GTAW gas tungsten arc welding
xxii List of abbreviations
Fig. 1.1 Historical evolution of engineering materials marked with the birth of HEAs published
in Advanced Engineering Materials (Yeh et al., 2004b).
Adapted from Ashby M.F., 2011. Materials Selection in Mechanical Design, fourth ed.,
Butterworth-Heinemann, Elsevier, Oxford, UK.
105 105
Strength–density Strength–density Ceramics
4 Metals
10 Ceramics 104
and glasses Metals Composites
Polymers and
103 103
Strength sf (MPa)
Strength sf (MPa)
elastomers
Natural
102 Natural 10
2
materials
materials
10 10
Foams
1 1
0.1 0.1
0.01 0.01
10 100 1000 10,000 100,000 10 100 1000 10,000 100,000
(A) Density r (kg/m3) (B) Density r (kg/m3)
Fig. 1.2 The explosion in the diversity of materials in the modern era (Ashby, 2011):
(A) prehistoric era (50,000 BCE) and (B) current status.
Alloying was an accidental discovery. In the primitive fires in the caves, ores of
copper got mixed with ores of arsenic, zinc, and tin. The first alloy of copper and arse-
nic (arsenical bronze, 3000 BCE) was entirely accidental. A more intentional alloying
of tin with copper (tin bronzes in 2500 BCE) gave birth to the Bronze Age, as bronze
was superior in its mechanical properties.
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Language: Finnish
Kirj.
Suomentanut
Toini Kalima
MUNKIN HÄÄT.
Avarassa liedessä roihuavan takkavalkean ääreen oli asettunut
nuorta hoviväkeä mitä mukavimpiin asentoihin nuoren hallitsijan ja
kahden kukoistavan naisen ympärille. Lieden vasemmalla puolella
istui ruhtinaallinen ryhmä, johon muut liittyivät neljännesympyrässä,
jättäen hovitapaa noudattaen tyhjäksi lieden koko toisen puolen.
Hovin valtias oli Scala-sukuinen ruhtinas, jota kutsuttiin
Cangrandeksi. Naisista, joiden välissä hän istui, lienee
puolihämärään, lähimmäksi liettä vetäytynyt ollut hänen puolisonsa,
tulen selvästi valaisema taas hänen sukulaisensa tai ystävättärensä.
Merkitsevin katsein ja puoliääneen nauraen kerrottiin kertomuksia.
*****
Taivaallisen ihanana kesäpäivänä huilujen vienosti soidessa liukui
seppelöity alus täynnä juhlapukuista väkeä Brentan nopeilla mutta
rauhallisilla aalloilla, missä joki hennossa kaaressa lähenee Paduan
kaupunkia, siihen vielä koskematta. Umberto Vicedomini ja Diana
Pizzaguerra olivat häämatkallaan. Padualainen toi morsiantaan
virran yläjuoksun varrella olevasta luostarista, jonne kaupungin
vanhan tavan mukaan ylhäistä sukua olevat tytöt vetäytyivät ennen
häitään hartautta harjoittamaan. Morsian istui keskellä alusta
purppuranpunaisilla patjoilla sulhasen ja tämän edellisestä
avioliitosta olevain kolmen kukoistavan pojan välissä. Umberto
Vicedomini oli kätkenyt maan poveen nuoruutensa rakastetun, ruton
raivotessa Paduassa viisi vuotta sitten, ja oli vanhan ja kivulloisen
isänsä alituisista kehoituksista hyvin vastahakoisesti päättänyt
mennä toisiin naimisiin, vaikka olikin vasta parhaassa miehuuden
iässä.
»Ja sitä sinä, julmuri, kerrot niin tyynesti, kuin puhuisit hevosen tai
viljan häviöstä», raivosi vanhus epätoivossaan. »Sinä olet vienyt