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F UYANG T IAN

Doctoral Thesis

School of Industrial Engineering and Management, Department of

Materials Science and Engineering, KTH, Sweden, 2013

ISBN 978-91-7501-899-7

Materialvetenskap

KTH

SE-100 44 Stockholm

Sweden

framlagges

avlaggande av tenknologie doktorsexamen in materialvetentill offentlig granskning for

skap fredagen den 29 Nov. 2013 kl 10:00 i B2, Kungliga Tekniska Hogskolan,

Brinellvagen

23, Stockholm.

c Fuyang Tian, 2013

Tryck: Universitetsservice US AB

Abstract

Ab initio theory provides a powerful tool to understand and predict the behavior of

materials. This thesis contains both of these aspects. First we use ab initio alloy theory

to investigate a new kind of complex alloy (high-entropy alloy). Second we introduce a

novel potential (interlayer potential), which can be extracted from ab inito total energy

inversion method.

High-entropy alloys (HEAs) are composed of four or more metallic elements with nearly

equimolar composition. In spite of the large number of components, most of the HEAs

have a simple solid-solution phase rather than forming complex intermetallic structures. Extensive experiments have reported the unique microstructures and special

properties of HEAs. Single-phase HEAs may be divided into three types, i.e. the 3dHEAs adopting the face centered cubic (fcc) phase, the refractory-HEAs with a body

centered cubic (bcc) phase, and the HEAs with the duplex fcc-bcc structure. We employ

the exact muffin-tin orbitals (EMTO) method in combination with the coherent potential approximation (CPA) to investigate the electronic structure, the equilibrium volume

and the elastic properties of these three-type HEAs.

First we compare the CPA with the super cell technique (SC) to assess the performance

of the EMTO-CPA method. As typical fcc 3d-HEAs, we consider the CuNiCoFeCrTix

systems in the paramagnetic state. Starting from the calculated electronic structure,

we give an explanation for the observed magnetic states. Furthermore, we provide

a theoretical prediction for the elastic parameters and polycrystalline elastic moduli for

CuNiCoFeCrTix (x = 0.00.5, 1.0) and NiCoTeCrTi. A detailed comparison between the

theoretical results and the available experimental data demonstrates that ab initio theory

can properly describe the fundamental properties of this important class of engineering

alloys.

Refractory-HEAs are composed of Ti, Zr, Hf, V, Nb, Ta, Mo, and W. These HEAs have a

simple bcc structure. Taking the TiZrNbMoVx and TiZrVNb HEAs as examples, we provide a detailed investigation of the effect of alloying elements on the elastic parameters

and the elastic isotropy. Our results indicate that vanadium enhances the anisotropy

and ductility of TiZrNbMoVx . As an application of the present theoretical database, we

verify the often quoted correlation between the valence charge concentration (VEC) and

the micro-mechanical properties in the case of multi-component alloys. Furthermore,

we predict that the present HEAs become elastically isotropic for VEC 4.72.

With increase of the aluminum content, phase transformations (fcc(fcc+bcc)bcc) occur in NiCoFeCrAlx HEAs. Our ab initio results predict that at room temperature the

paramagnetic NiCoFeCrAlx HEAs adopt the fcc structure for x 0.60 and the bcc structure for x 1.23, with an fcc-bcc duplex region in between the two pure phases. The

ii

calculated single- and polycrystal elastic parameters exhibit strong composition and

crystal structure dependence. Based on the present theoretical findings, it is concluded

that alloys around the equimolar NiCoFeCrAl composition have superior mechanical

performance as compared to the single-phase regions.

Many modern materials and material systems are layered. The properties related to

layers are connected to interactions between atomic layers. We introduce the interlayer

potential (ILP), a novel model potential which fully describes the interaction between

layers. The ILPs are different from the usual interatomic potentials which present inter

action between atoms. We use the Chen-Mobius

inversion method to extract the ILPs

from ab initio total energy calculations. The so obtained ILPs can be employed to investigate several physical parameters connected with the particular set of atomic layers,

e.g. surface energy, stacking fault energy, elastic parameters, etc.

As an application, we adopt the supercell method and the axial interaction model in

connection with the ILPs to calculate the stacking fault energy along the fcc 111 direction, including the intrinsic stacking fault energy, extrinsic stacking fault energy and

twin stacking fault energy as well as the interactions between the intrinsic stacking

faults. We find that the data derived from ILPs are consistent with those obtained in

direct ab initio calculations. Along the fcc 111 direction, we study the surface energy

and surface relaxation using the ILPs. The phonon dispersions are also described.

Our conclusions are as follows

the EMTO-CPA ab initio alloy theory can be used to understand and predict the

fundamental properties of multicomponent alloys.

inversion method may pro the interlayer potentials based on the Chen-Mobius

vide a new way to investigate the properties related to layers in layered materials,

inversion method

offers a powerful technique to study the properties of complex alloys.

Preface

List of included publications:

I Empirical design of high-entropy alloys with optimal properties

Fuyang Tian, Lajos Karoly Varga, Nanxian Chen, Jiang Shen, and Levente Vitos,

Journal of Alloys and Compounds (under review) (2013).

II Ab initio investigation of high entropy alloys of 3d elements

Fuyang Tian, Lajos Karoly Varga, Nanxian Chen, Lorand Delczeg, and Levente

Vitos,

Physical Review B 87, 075144 (2013).

III Ab initio design of elastically isotropic TiZrNbMoVx high-entropy alloys

Fuyang Tian, Lajos Karoly Varga, Nanxian Chen, Jiang Shen, and Levente Vitos,

Journal of Alloys and Compounds (under review) (2013).

IV Structural stability of NiCoFeCrAlx high-entropy alloy from ab initio theory

Fuyang Tian, Lorand Delczeg, Nanxian Chen, Lajos Varga, Jiang Shen, and Levente Vitos,

Physical Review B 88, 085128 (2013).

V A novel potential: the interlayer potential for the fcc (111) plane family

Fu-Yang Tian, Nan-Xian Chen, Jiang Shen, and Levente Vitos,

Journal of Physics: Condensed Matter 24, 045001 (2012).

VI Interlayer potentials for fcc (111) planes of Pd-Ag random alloys

Fu-Yang Tian, Nan-Xian Chen, Lorand Delczeg, and Levente Vitos,

Computational Materials Science 23, 045006 (2012).

Comment on my own contribution

I All experimental collections, 80% data analysis; the manuscript was written jointly

(70%).

II All calculations, data presentation, literature review; the manuscript was written

jointly (75%).

III All calculations, data presentation, literature survey; the manuscript was written

jointly (80%).

IV All calculations, data presentation, literature survey; the manuscript was written

jointly (90%).

vi

V All calculations, data presentation, literature survey; the manuscript was written

jointly (50%).

VI All calculations, data presentation, literature survey; the manuscript was written

jointly (75%).

I High-strength and ductile Ti20 Zr20 Hf20 Nb20 X20 (X=V or Cr) refractory high entropy alloys

Fazakas, V. Zadorozhnyy, L. K. Varga, A. Inoue, D.V. Louzguine-Luzgin, Fuyang

E.

Tian, and L. Vitos, in manuscript (2013).

II Density functional theory of light actinides with substitutional point defects in

face centered and body centered cubic descriptions

L. Delczeg, E. K. Delczeg-Czirjak, Fuyang Tian, B. Johansson, and L. Vitos, in

manuscript (2013).

III Interlayer interactions in graphites

Xiaobin Chen, Fuyang Tian, Clas Persson, Wenhui Duan, and Nan-xian Chen,

Scientific Report (accepted).

IV An ab initio investigation of boron nanotube in ringlike cluster form

Fu-Yang Tian, Yuan-Xu Wang, V. C. Lo, and Jiang Shen,

Applied Physics Letters 96 131901 (2010).

V The competition of double-, four-, and three-ring tubular B3n (n = 8 32) nanoclusters.

Fu-Yang Tian and Yuan-Xu Wang,

The Journal of Chemical Physics 129, 024903 (2008).

Contents

Preface

Contents

1

vi

Introduction

1.1

Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2

High-entropy alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.3

Interlayer potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2 Ab initio theory

2.1

Many-particle problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2

2.2.1

Exchange-correlation approximations . . . . . . . . . . . . . . . . .

2.2.2

2.3

3

14

3.1

General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.2

3.3

3.4

3.5

Elastic anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

4.1

19

vi

CONTENTS

vii

4.1.1

4.1.2

4.1.3

4.2

4.3

4.4

Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

5.1

5.2

5.3

5.4

28

Assessing CPA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

5.1.1

CPA versus SC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

5.1.2

Partial CPA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

CuNiCoFeCrTix HEAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

5.2.1

Equilibrium volumes . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

5.2.2

Magnetic structures . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

5.2.3

Elastic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

TiZrNbMoVx HEAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

5.3.1

Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

5.3.2

Ductile behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

5.3.3

Elastic isotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

NiCoFeCrAlx HEAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

5.4.1

Phase transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

5.4.2

Elastic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Interlayer potentials

50

6.1

6.2

Process of inversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

6.3

6.4

6.3.1

6.3.2

CONTENTS

viii

7

7.1

59

Equilibrium properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

7.1.1

7.1.2

7.2

7.3

7.4

Surface energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

7.5

Phonon dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

70

Acknowledgements

71

Bibliography

72

Chapter 1

Introduction

1.1 Overview

In this thesis, we discuss the structural and elastic properties of high-entropy alloys

inversion in layered materials. We give a brief description of the density functional theory (DFT) methods in Chapter 2, which are used to calculate the total energy and magnetic properties.

Chapter 3 is about the elastic properties of solids. Results for three types of HEAs are

given in Chapter 4 and 5. ILPs in metals and alloys are discussed in Chapter 6 and 7.

Chapter 8 is the summary of all results and further work.

1.2

High-entropy alloys

The design of conventional alloys is based on one or two principal elements, and some

minor elements are added to modify their microstructure and properties, for examples,

steel and aluminum alloys.

In the early 2000s, a simple solid-solution phase was discovered in the equimolar multicomponent alloys [1, 2]. Yeh et al. named the new type of metals high-entropy alloys (HEAs). These metastable solid solutions are composed of at least four equimolar

or near-equimolar metallic elements and are stabilized by the mixing entropy Smix

= kB lnn (kB is the Boltzmann constant and n is the molar fraction of equimolar alloy

components) [1]. Due to the unique microstructures and special properties, such as

high strength, good wear, corrosion resistance, oxidation, hydrogen storage, diffusion

barrier and even biomedical applications, HEAs have attracted a rapidly increasing attention in the scientific community. The amorphous phase and nanostructure have also

been reported [3]. Nevertheless, our discussions of HEAs are based on the single-phase

solid solutions, i.e. bcc or fcc crystallographic structure.

1

CHAPTER 1. INTRODUCTION

In the experimental area, researchers used different tools, including traditional casting, mechanical alloying, sputtering, splat-quenching, etc., to obtain the HEAs with

different alloying elements and then to investigate the corresponding microstructures

and mechanical, thermal, and electronic performances [325]. With the appearance of a

large number of different-type of HEAs, one could establish general rules of physics of

HEAs. Such empirical assessments were based on the regular solid solution theory, and

made use of the atomic mismatch, mixing entropy and enthalpy, electronegativity, and

valence electron concentration [2631].

On the other hand, atomistic simulation methods were applied to study the features

connected to the microstructure of the HEAs. For instance, del Grosso et al. employed

the Bozzolo-Ferrante-Smith (BFS) method for alloys to investigate the transition to the

high entropy regime for alloys with refractory elements [32]. Based on ab initio simulation combined with the supercell technique, it was reported that the bcc phase has

partial ionic bonding between Al and other transition metals for the series of HEAs

Alx Cry CoNiFe (x = 1, 1.5, 2, 2.5, and 3, y = 1 and 2) [33]. Zhang et al. used the sublattice

model, supported by first-principles total energy calculations, to explore the possibility

of forming fcc HEAs of CoFeMnNiM and CoFeMnNiSmM (M=Cr, Zn, Ru, Rh, Pd, Re,

Os, Ir and Pt) [34].

At present, single solid-solution HEAs are mainly divided into three types. Namely,

the HEAs with fcc structure are composed of 3d transitional elements, for example

NiCoFeCrx (x = 0.5 1.15) [35], Ni-Co-Fe-Cr-Mn [2], and Cu-Ni-Co-Fe-X (X=Cr, V,

Ti, Mn) [1, 26, 36, 37] etc.; the HEAs with bcc structure are mainly consist of refractory elements, for instance, Ti-Zr-Hf-Nb(V)-Ta(Nb), Ti-Zr-V-Nb-Mo or Ti-Zr-Nb-Mo-V

etc [10,1315,3843]; for the HEAs with the fcc+bcc phase, the main reason of the duplex

phase is the addition of the bcc (fcc) stabilizer Al (Ni) or the increase of the bcc stabilizer

Cr (Co) [1, 25], for instance CuNiCoFeCrAlx (x = 0 3.0) [1, 4, 44], Cu0.5 NiCoFeCrAlNix

[25], NiCoFeCrAlx (x = 0 3.0) [10, 1820, 4552], CuNi2 FeCrAlx [28, 53], etc.

Despite of the single solid-solution phase characteristic to HEAs, it is particularly difficult to use conventional ab initio atomistic simulation methods to investigate these

systems. That is because HEAs are chemically and often also magnetically disordered

multicomponent extended solid solutions. To assess the performance of standard alloy theory based on ab initio DFT [54, 55] for the case of HEAs first we employ the

EMTO method [5659] in combination with the CPA [6063] and investigate the basic bulk properties of the HEA based on 3d transition metals. Using NiCoFeCr as a

four-component model system and NiCoFeCrAl0.2667 alloys we establish the accuracy

of the single-site mean-field approximation by comparing the CPA results with those

generated by the supercell technique.

Then the three-types HEAs are investigated. We select CuNiCoFeCr, NiCoFeCrTi and

CuNiCoFeCrTix (x = 0 0.5, 1.0) HEAs to study the bulk properties of the 3d-HEAs

with the fcc structure. Taking TiZrVNb and TiZrNbMoVx (x = 0 1.5) as examples, we

study the equilibrium volumes and elastic properties of refractory HEAs adopting the

bcc phase. NiCoFeCrAlx (x = 0 2.0) HEAs are used to study the HEAs with the phase

transformation. We focus on the equation of state, electronic structure, magnetic state,

and elastically properties.

Ab initio density functional theory (DFT) [54, 55], as a powerful ground state theory,

has been widely applied to investigate the structural and electronic properties of solids.

However, the application of DFT to study thermodynamical behavior of realistic materials is usually accompanied by a heavy increase of the computational effort. On the

other hand, model potentials, derived from experimental or ab initio data, may be used

to simulate large systems and are usually implemented in classic molecular dynamics.

These potentials make relatively easy to investigate systems containing thousands of

atoms and enable one to determine the trends of essential physical properties. Often by

model potentials we mean interatomic interactions. In this work, we introduce a new

type of potential, namely the interlayer potential (ILP) that describes the interaction

between atomic layers.

Materials are composed of many atoms with ordered or disorder arrangements. In fact

many modern materials and material systems are layered. The properties related to

layers are derived from the interaction between layers. The interactions between the

atomic layers are usually different from those within the layers and describe the layered character of the material. As a typical example, graphite is composed of hexagonal

carbon sheets. The interlayer bonding properties have widely been studied [6469]. In

ordered crystals, there may be a multiple (up to infinite) of distinct lattice planes with

different directions. For example, common slip planes are {110} in bcc metals, {111}

in fcc metals, and {0001} in hcp metals, respectively. Many material properties have

some connections with the lattice planes, such as stacking fault energy (sf ), surface

energy (s ), and interfacial coherent energy on different lattice planes. Therefore, the

lattice planes are very crucial in the description of material properties. We consider

herein each lattice plane as a unity and investigate the interaction between layers. The

proposed interlayer pair potential transforms the three-dimensional structure into an

one-dimensional chain and thus decreases the complexity of the many-body interaction. The ILPs can easily be applied to discuss some material properties associated with

lattice planes.

The interatomic potential is of primary importance for the molecular dynamics simulations. Still, it is extremely difficult to get reliable interatomic potentials, which prevents

that the interatomic potentials are applied to complex alloys. Considering the advantage of the present model potentials, we make an attempt to derive the interaction potentials between close-packed lattice planes of disordered alloys.

In order to obtain the ILPs for metals and random alloys, here we employ the Chen-

CHAPTER 1. INTRODUCTION

Mobius

inversion method [70]. Previously, the Chen-Mobius

inversion has successfully been applied to extract the interatomic potentials from ab inito calculations for

rare earth-transition intermetallic compounds [71], ionic crystals [72], compound semiconductors [73], transition metal carbides or nitrides [74, 75] and metal/ceramic interfaces [76] as well as metal/SiC interface [77]. Recently, Yuan et al. proposed the lattice

inversion embedded-atom-method (LI-EAM) with Chen-Mobius

inversion method and

improved effectively the embedded-atom-method (EAM) potentials of metals [78].

Although one can in principle extract the model potentials from the experiments, such

data are usually obtained at different experimental conditions and thus includes some

degree of uncertainty. On the other hand, modern ab initio calculations can provide

total energies for complex alloys and thus can be used to derive reliable ILPs. In the

present thesis, we use the CASTEP [79] and EMTO [63] computational tools to obtain

the interlayer energy versus the interlayer distance for metals and alloys.

In fcc metals and alloys, there are several physical properties associated with the fcc

(111) planes, such as the elastic constant c44 , stacking fault energy, and surface energy

or the phonon dispersion, which are all basic and important quantities in materials science. Taking pure metals Al, Ni, Cu, Ag, Au and Pd as well as random alloy Pd-Ag as

examples, we discuss the properties related to layers, including the stacking fault energy (intrinsic fault, extrinsic stacking fault and twin fault), the interaction between two

intrinsic stacking faults, surface energy, surface relaxations, and the phonon dispersion.

Chapter 2

Ab initio theory

In the field of computational materials science, electronic structure calculation has become a very useful tool. It is often called ab initio (first principles) calculation. Many

physical or chemical properties of materials can be predicted directly from the solution

of the fundamental equations for the electrons.

The electronic and nuclei system in a material can be described the many-particle Schrodinger

equation

b = E,

H

(2.1)

where is the many-particle wave function, = (r1 , r2 , rN , R1 , R2 , , RM ) which

is a function of all the positions (rN for electrons, RM for ions) in the system. E is the

eigenvalue of the Hamiltonian

2

elec

nucl

elec

nucl

~2 2

1 e2

1 e2 Zi Zj

~2 Rj

b

H =

ri

+

+

2me i

2 j Mj

2 i=j |ri rj | 2 i=j |Ri Rj |

elec

nucl

e2 Zj

,

|ri Rj |

(2.2)

describing electrons with mass me and ions with mass Mj . Here ~ = h/2, h is Planck

constant, Zi and Zj are the nuclear charges. The first two terms represent the kinetic

energy of nuclei and electrons, respectively. The last term is the Coulomb interaction

between the electrons and the nuclei, while the other two terms account for the electronelectron and the nucleus-nucleus interactions, respectively.

5

For solid systems composed of thousands of nuclei and electrons we have to make

approximations for Eq. 2.2 in order to find the eigenvectors and eigenvalues for this

b Firstly the nuclei are far more massive than the electrons and their

Hamiltonian H.

velocities are therefore relatively low in comparison. Therefore, one may neglect the

second term in Eq. 2.2. This is called the Born-Oppenheimer (BO) approximation. We

can use BO approximation to separate the time scales of electron and atom motions and

thus to treat the terms in dealing with the electron states separately from the ones dealing with the atomic nuclei. Further, the BO approximation allows us to recast the last

term in Eq. 2.2 describing the Coulomb interaction between the atomic nuclei and the

electrons as an external potential acting on the electrons. Hence Eq. 2.2 can be simplified

as

elec

elec

elec

nucl

1 e2

~2 2

e2 Zj

b

ri +

H =

2me i

2 i=j |ri rj |

|ri Rj |

i

j

(2.3)

= Te + Vee + Vext ,

where Te is the kinetic energy of electron, Vee for electron-electron interactions, and the

last term Vext is the external potential. So within the framework of BO approximation,

the many-particle electron-nucleus problem has been reduce to n electron-electron problem. In the following sections, we will use atomic Rydberg units (~ = 2me = e2 /2 = 1).

Today, as one of the most popular ab initio methods to solve Eq. 2.3, density functional

theory [54, 55] is extensively applied to calculate the electronic properties of molecules

and solids. The two theorems behind of the density functional theory [54] are

the ground state of an interacting electron system is uniquely described by an

energy functional En of the electron density,

the true ground state electron density n(r) minimizes the energy functional En and

the minimum gives the total energy.

Within the Kohn-Sham method [55], the total energy of a system of electrons is given as

Etot = Ts +

1

vext (r)n(r)d r +

2

3

n(r)n(r ) 3 3

d rd r + Vnn + Exc ,

|r r |

(2.4)

where Ts is the kinetic energy of a system of noninteracting electrons, the three middle terms represent the electron-nucleus, electron-electron, nucleus-nucleus electrostatic

energies, and the last term Exc is the exchange-correlation energy which can be decomposed into its exchange and correlation parts (Exc =Ex +Ec ). The corresponding

xc Exc [n(r)]/n(r).

(2.5)

[2 + Vef f (r)]ik = ki ik ,

where

n(r )

dr + xc (r),

|r r |

(2.6)

(2.7)

ki are the one electron energies and ik the corresponding Kohn-Sham orbitals. For

solving Eq. 2.6 one can use fully-relativistic, scalar-relativistic or non-relativistic techniques. Because the exact form of xc is not known, we have to adopt different approximations. The local density approximation (LDA) [80] and the generalized gradient approximation (GGA) [81] are the two most widely applied approximations for the

exchange-correlation terms. There serval methods for solving the Kohn-Sham equations, of which full-potential, pseudopotential, and muffin-tin methods are extensively

applied in the calculations of materials .

In our work, we use the EMTO and the CASTEP computational tools. In following

sections, we introduce the two versions of GGA (Perdew-Burke-Ernzerhof (PBE) [81]

and PBEsol [82]) as well as the ultrasoft pseudopotentials (USP) and the EMTO method.

In the local density approximation (LDA), the exchange-correlation energy is written as

LDA

3

Exc (n) = n(r)LDA

(2.8)

xc (n(r))d r,

where LDA

= LDA

+ LDA

, in which, LDA

is the exchange-correlation energy of homogexc

x

c

xc

is the exchange energy per electron

neous electron system expressed per electron, LDA

x

LDA

and c is the correlation energy per electron.

In order to better describe an inhomogeneous system, the gradient of the electron density should also be taken into account. This results in the so-called GGA functional

family. Compared to the LDA, the exchange energy of GGA is

GGA

(2.9)

(n)FxGGA (s),

Ex (n) = d3 rnLDA

x

where the enhancement factor FxGGA has the asymptotic behavior

(2.10)

s=

|n|

,

2kF n

(2.11)

kF =(3 2 n)1/3 is the Fermi wave vector and is the parameter of gradient expansion.

The GGA correlation term is

EcGGA (n)

d3 rn(r){LDA

(n) + t2 (r) + },

c

(2.12)

t=

|n|

,

2kT F n

(2.13)

screening wave vector kT F = (4kF /)1/2 ).

For the spin polarized system, the PBE is written as

GGA

Exc

(n , n )

where

=

d3 rnLDA

xc (n)Fxc (rs , , s),

(2.14)

n n

.

n + n

(2.15)

The PBE functional is nowadays the most commonly used functional for solid-state calculations. There are no empirical parameters in PBE. The PBEsol has the same analytical

form as the PBE. The differences between PBE and PBEsol are the values of and .

The Blochs theorem shows that the electronic wavefunctions at each k-point can be

expanded in terms of a discrete plane-wave basis set. The number of plane waves in

this expansion should be infinite in principle. In practise the plane wave basis set can

be truncated to include only plane waves that have kinetic energies that are smaller than

some particular cutoff energy. The truncation of the basis set produces an error in the

calculations of total energy. Increasing the value of the cutoff energy may reduce the

magnitude of the error. According to the requirement of converge with respect to the

number of plane waves, we need to choose the proper cutoff energy.

In the USP plane-wave total energy method, the accuracy of the pseudopotential is of

particular importance. Vanderbilt introduced USPs in 1990 [83]. USPs are optimized to

the plane-wave solid-state calculations and needs the lowest possible cutoff energy for

the plane-wave basis set.

The general form of the pseudopotential is expressed as

VNL =

|lmVl lm|,

(2.16)

lm

where Vl is the pseudopotential for angular momentum l, |lm are the spherical harmonics.

In the USP plane-wave method, the nonlocal potential VNL is given as

(0)

I

VNL =

Dnm

|nI m

|,

(2.17)

n,m,I

where the projectors and coefficients D(0) characterize the pseudopotential and differ

for different atomic species. For the derivations of and D(0) , one can refer to Ref.

[83, 84]. The index I refers to an atomic site. The valence charge density is defined as

n(r) =

|i (r)|2 +

I

QInm (r)i |nI m

|i ,

(2.18)

nmI

where are the pseudo-wave functions and Q(r) are the augmentation functions that

are strictly localized in the core regions, viz.

Qnm (r) = n (r)m (r) n (r)m (r),

(2.19)

where (r) are all-electronic wave functions. The are constructed from (r) and satisfy

i |S|j = ij ,

(2.20)

S =1+

I

qnm |nI m

|,

(2.21)

nmI

Kohn-Sham equation can be rewritten for the USP method as

H|i = i S|i ,

where H can be presented as a sum of kinetic energy and local potential

(2.22)

10

H = Ts + Vef f (r) +

I

I

Dnm

|nI m

|,

(2.23)

nm

loc (r), Hartree potential and exchange-correlation

terms. All the terms arising from the augmented part of electron density are grouped

with the nonlocal part of the pseudopotential by defining new coefficients

(0)

I

(2.24)

Dnm = Dnm + drVef f QInm (r).

In the USP plane-wave method, the eigenvalues from the pseudo potentials are equal

to that from all-electron potentials. Their corresponding orbitals match exactly outside

the core radii. Because the scattering properties are correct at each reference energy, the

transferability can be systematically improved by increasing the number of such energies. The valence charge density is precisely equal to the all-electron valence density in

the reference configuration [79].

In the KKR or traditional methods, the space is divided into non-overlapping muffin-tin

(MT) spheres, centered at the nuclei positions. Within the muffin-tin approximation, the

effective potential is represented by non-overlapping spherically symmetric potentials

around the atomic nuclei and a constant potential in the interstitial region, i.e

{

v(|r R|) if |r R| < r0 ,

vmt (r) =

(2.25)

vmtz

if |r R| r0 ,

where R is the position of atom, r0 is the radius of the spherical, and Vmtz is the constant

potential outside the sphere.

The EMTO theory belongs to the 3rd generation muffin-tin approximation family. This

theory is an improved KKR method, which uses large overlapping muffin-tin potential

spheres which can describe the exact one-electron potential rather accurately, viz.

Vef f vmt (r) v0 +

|vR (r R) v0 |,

(2.26)

on lattice sites R. We can solve the Kohn-Sham equation (Eq. 2.6) by assuming a linear

a

combination of the exact muffin-tin orbitals RL

(j , rR ) as following

j (r) =

RL

a

a

.

(j , rR )vRL,j

RL

(2.27)

11

a

The expansion coefficients, vRL,j

are determined in a way that j (r) is a solution for Eq.

2.6 in the entire space.

The exact muffin-tin orbitals are constructed using different basis functions inside the

potential sphere (r R < sR ) and in the interstitial region (r R > sR ), herein sR is

the radius of the potential sphere centered at site R. The basis functions used are called

partial waves (aRL ) inside the sphere and screened spherical waves (aRL ( V0 , r-R)) in

the interstitial zone.

Inside the potential sphere, the basis functions aRL are constructed from solutions of

(Dirac) equations (RL ) and the real harmonics

\

(YL (r R))

a

aRL (, r R) = NRL

()RL (, r R)YL (r[

R).

(2.28)

a

The normalization factor NRL

() assures a proper matching at the potential sphere boundary to the basis function outside of the potential sphere.

In the interstitial region the screened spherical waves are solutions of the free electron

Schrodinger

equation. The boundary conditions for the free electron Schrodinger

equation are given in conjunction with non-overlapping spheres, called hard spheres, centered at lattice site R with radius aR . The screened spherical waves are just defined as

being free electron solutions which behave as real harmonics on their own a-spheres

centered at site R and vanish on all the other sites.

These basis functions, partial waves and screened spherical waves, must join continuously and differentiable at aR . This is implemented using additional free electron wave

a

functions (RL

(, aR )), by which the connection between the screened spherical waves

and the partial waves is obtained. It joins continuously and differentiable to the partial

wave at sR and continuously to the screened spherical wave at aR . Because of aR < sR ,

the additional free-electron wave function should be removed, which is realized by the

so-called kink-cancelation equation.

In the calculation of the total energy, the EMTO method employs the Full Charge Density (FCD) technique, which not only improves the calculation efficiency but also ensures total energies with an accuracy similar to that of the full-potential methods. The

total charge density is obtained by summations of the one-center densities, which may

be expanded in terms of real harmonics around each lattice site

n(r) =

nR (r R) =

R).

(2.29)

RL

The total energy of the system is obtained via the FCD technique using the total charge

density. The space integrals over the Wigner-Seitz cells in Eq. 2.4 is solved via the shape

function technique. The FCD total energy is expressed as

12

Etot = Ts [n] +

(2.30)

where Ts [n] is the kinetic energy, FintraR is the electrostatic energy due to the charges

inside the Winger-Seitz cell, ExcR is the the exchange-correlation energy, and Finter is the

electrostatic interaction between the cells (Madelung energy).

Coherent potential approximation

The Coherent Potential Approximation (CPA) was introduced by Soven for the electronic structure problem and by Taylor for phonons in random alloys [85, 86]. Later,

Gyorffy formulated the CPA in the framework of the multiple scattering theory using

the Green function technique [87]. In this theory, the real atomic potential is replaced

by an effective (coherent) potential constructed from real atomic potentials of the alloy

components. The impurity atoms/alloy components are then embedded into this effective potential. Two main approximations are applied. First, it is assumed that the local

potentials around a certain type of atom from the alloy are the same, i.e. the effect of

local environments is neglected. Second, the system is replaced by a monoatomic set-up

described by the site independent coherent potential P .

Disordered local magnetic moment model

Disordered local magnetic moment (DLM) model [88, 89] is a approach to simulate the

paramagnetic state of random alloys using CPA . The DLM model is expected to correctly account for the random distribution of the local magnetic moments of the PM

state well above the magnetic transition temperature, where the local magnetic moments show negligible short range order. According to that model, an alloy component

M of concentration m is presented by its spin-up () and spin-down () counterparts

assumed to be distributed randomly on the underlying sublattice, i.e. each magnetic

alloy components are treated as Mm Mm/2 Mm/2 . For example, NiCoFeCr is described

as a quasi-eight component random solid solutions, viz. Fe0.125 Fe0.125 Cr

Ni0.125 Ni0.125 Co0.125 Co0.125 .

0.125 Cr0.125

EMTO-CPA

Today, CPA represents the most efficient alloy theory for the electronic structure calculations in multicomponent random solid solutions. The CPA has been successfully

implemented in the EMTO method [57]. The single-site nature of the CPA limits its

applicability to systems with negligible short-range order and local lattice relaxation effects. Nevertheless, it turned out that the EMTO-CPA method can accurately capture

13

the structural energy differences and trace energy changes related to lattice distortions

in complex alloys.

The above details about the EMTO-CPA method are from Ref. [63].

Chapter 3

Elastic properties of solids

The shape of materials changes when the external stress is applied. This deformation

is often described in terms of stress or force per unit area and strain or displacement

per unit distance. In studying of elastic properties, the stress-strain relation follows the

Hookes law, i.e. the deformation of materials is reversible.

For a single crystal, the elastic constant c or elastic compliance s are used to describe the

elastic properties. For an isotropic and quasi-isotropic materials in a statistical sense, the

elastic properties can be completely described by any two of the polycrystalline elastic

moduli, the bulk modulus (B), the shear modulus (G), and the Youngs modulus (E) as

well as the Possion ratio (v). Using averaging methods, we may obtain the polycrystalline elastic moduli from the single crystal elastic constants.

According to Hookes law, the stress ij is proportional to the elastic strain kl

3

ij =

cijkl kl ,

(3.1)

k,l=1

where i, j, k, and l are indices running from 1 to 3. cijkl are called elastic constants.

Eq. 3.1 indicates that the number of coefficients cijkl is 81. Because cijkl = cklij = cjikl =

cijlk , there are at most 21 different elastic constants, which can be arranged in a 6 6

matrix. This matrix is symmetric, i.e. c =c . The relations between c and cijkl are

listed in Table 3.1.

Eq. 3.1 can be rewritten as

=

=1

14

c .

(3.2)

15

i, j or k, l

or

11 22

1 2

33

3

23 or 32

4

13 or 31

5

12 or 21

6

=

(3.3)

s ,

=1

The elastic compliance tensor s multiplied by the elastic stiffness tensor c satisfy a 6 6

identity matrix, i.e.

cs = I6 .

(3.4)

For different structural solids, crystal symmetry can reduce the number of independent

elastic constants. For instance, there are only 3 independent elastic constants (c11 , c12

and c44 ) for the cubic crystal, 5 independent elastic constants (c11 , c12 , c13 , c33 and c44 ) for

the hexagonal crystal [90].

3.2

The adiabatic elastic constants are the second order derivatives of the internal energy

with respect to the strain tensor e, viz.

c =

1 2E

,

V e e

(3.5)

where and are listed in Table 3.1, E represents the internal energy.

At volume V , we may obtain the elastic constants by straining the lattice and evaluating the total energy changes due to the stain as a function of its magnitude. Since the

change of total energy is usually more larger with the volume than with a general strain,

we choose the applied volume conserving, except for the bulk modulus. By choosing

volume conserving strains we can separate two contributions to the total energy. Using isochoric strains we assure the identity of our calculated elastic constants with the

stress-strain coefficients. We denote by e1 , e2 , ..., e6 the elements of strain matrix, i.e.

e1

D(e) = 12 e6

1

e

2 5

1

e

2 6

e2

1

e

2 4

1

e

2 5

1

e

2 4

e3

(3.6)

16

1

E(e1 , e2 , ..., e6 ) = E(0) + V

cij ei ej + O(e3 ),

2 i,j=6

(3.7)

where E(0) is the energy of the undistorted lattice and O(e3 ) stands for the terms proportional to ek with k 3.

For the volume conserving deformation, the criterion is det(D(e) + I) = 1, where I is the

3 3 identity matrix. As a result, the distortion matrix can be rewritten as a function of

a single parameter, and result in a particular combination of the elastic constants [63].

The elastic properties of a cubic lattice may be described by the three independent elastic

stiffness coefficients c11 , c12 and c44 or by the elastic compliance coefficient s11 , s12 and

s44 . The cij and sij satisfy

c11 + c12

,

(c11 c12 )(c11 + c12 )

c12

,

=

(c11 c12 )(c11 + c12 )

1

=

.

c44

s11 =

s11

s44

(3.8)

The two cubic elastic constants (c11 and c12 ) are derived from the bulk modulus

B=

c11 + 2c12

3

(3.9)

c11 c12

.

2

(3.10)

c =

The bulk modulus was extracted from the equation of state described by a Morse function [91] fitted to the total energy calculated for seven different volumes around the

equilibrium, i.e.

P

2 E(V )

=V

,

(3.11)

V

V 2

where P is the applied hydrostatic pressure, V represents volume. In this thesis, the

equilibrium volume is often expressed in terms of average Wigner-Seitz radius w.

B = V

17

In the calculations of two cubic shear elastic moduli, c and c44 , we make use of the

following volume conserving orthorhombic and monoclinic deformations

1 + o

0

0

1 o

0

0

0

1 m

0 and m 1

1

0

0

1 2

o

0

0 ,

1

2

1m

(3.12)

2

+

which lead to the energy change E(o ) = 2V c o2 + O(o4 ) and E(m ) = 2V c44 m

4

O(m ). Both energies can be computed for six distortions, = 0.00, 0.01, , 0.05.

For the cubic crystal, the mechanical stability criteria on the elastic constants are

c > 0, c44 > 0, and B > 0.

(3.13)

The Cauchy pressure (c12 c44 ) is used as an indicator of the brittle-ductile behavior.

Negative (c12 c44 ) has been associated with the covalent nature of the metallic bond and

is characteristic to brittle alloys, whereas positive (c12 c44 ) indicates metallic character

and enhanced ductility [92].

3.4

An isotropic polycrystalline system is described by the bulk modulus B and the shear

modulus G. For a cubic lattice, the polycrystalline bulk modulus is identical with the

single-crystal bulk modulus. For the shear modulus, we used the arithmetic Hill average

(GR + GV )

G=

,

(3.14)

2

where the Voigt and Reuss bounds are given by [90]

GR =

4c44 + 3(c11 c12 )

and GV =

.

5

(3.15)

The Youngs modulus E and Poisson ration are connected to B and G by the relations

E=

9BG

3B + G

and =

3B 2G

.

2(3B + G)

(3.16)

The B/G ratio is used as an indicator of the brittle-ductile behavior. High values of

B/G (>1.75) indicate that a material is ductile, while low values are associated with

brittleness. The may also be used to predict the brittle-ductile behavior [93]. It has

been reported that bulk metallic glasses with > 0.31 are ductile [94].

18

In cubic lattices the elastic anisotropy is often expressed in terms of Zener ratio

AZ =

c44

.

c

(3.17)

AVR =

GV GR

,

GV + GR

(3.18)

which is used as another measure of the elastic anisotropy. Elastically isotropic materials

have AVR = 0 and AZ = 1. We note that large AVR indicates large uncertainty in the

predicted shear and Youngs moduli and Poisson ration.

In an arbitrary direction [hkl], the E can be given in thems of sij [90]

E[hlk]1 = s11 + (2s11 2s12 s44 )N 4 ,

(3.19)

and for the shear modulus G(hkl) referring to torsion around [hkl], shear occurs in all

directions in the plane (hkl), then the general expression of G can defined as

G(hlk)1 = s44 + 2(2s11 2s12 s44 )N 4 ,

(3.20)

(3.21)

where

and n1 , n2 , n3 are direction consines for the direction [hlk], i.e.

h

,

+ k 2 + l2

l

=

,

2

h + k 2 + l2

k

=

.

2

h + k 2 + l2

n1 =

n2

n3

h2

(3.22)

Chapter 4

Single phase high-entropy alloys

As single-phase solid solutions, most of HEAs has a single crystallographic structure

(bcc or fcc) or the mixture of bcc and fcc phases. In order to distinguish the crystal

structures (bcc and fcc) and understand the effect of different phases on the mechanical

properties, especially on hardness, in this chapter we show the structural properties

and hardness of single-phase HEAs via the standard solid-solution theory including

the average equilibrium volume (wmix ), atomic size difference (), the average valence

electron concentration (VEC), and hardness (Hv).

We may estimate the equilibrium volume of an alloy using Vegards rule. In order to

be able to compare different lattices and account for elements adopting different parent

lattices, here we use the Wigner-Seitz radius rather than the lattice parameter. Accordingly, the average Wigner-Seitz radius of the solid solutions is given by

wmix =

ci wi ,

(4.1)

where n stands for the number of alloy components, ci is the atomic percent of the

ith component, wi is the Wigner-Seitz radius of the ith component obtained from the

experimental data collected, e.g., in Ref. [63].

The average valence electron concentration (VEC) is calculated as

VEC =

ci (VEC)i ,

(4.2)

where (VEC)i is the valence electron concentration of the ith alloy element. The VEC

counts for the total electrons including the d-electrons in the case of transition metals.

The atomic size difference () is defined coventionally as

19

20

v

u n

u

ri

ci (1 )2 ,

= 100t

r

i=1

where r =

4.1

i=1 ci ri ,

(4.3)

According to the available experiments, we divide the one-phase HEAs into three types.

One type is about the 3d HEAs with fcc structure, the second is the refractory HEAs with

bcc structure, and the last is about the HEAs with the duplex fcc-bcc phase.

4.1.1

From Table 4.1, we can see that HEAs with the fcc phase are mainly composed of late

3d transition elements. The calculated wmix is consistent with the experimental w. The

largest VEC is 9.50 for CuNiCoFe HEA [95]. The atomic size difference is smaller than

5%, except for CuNiCoFeTi with 1 = 6.50% (2 = 6.13%) [51], Cu0.75 NiCoFeCrTi0.5 Al0.25

with 1 = 5.40% (2 = 5.03%) [96], and NiCoFeMnCrNb with 1 = 5.49% (2 = 6.03%) [2].

According to Senkovs data [97], 1 is the smallest for the ternary equimolar NiFeCr,

whereas the smallest 2 obtained from [98] is 0.92 for the equimolar CuNiCoFeMn and

NiCoFeMnCr HEAs. Note that Vickers hardness in dendrite are very different from that

in interdendritic for NiCoFeMnCrNb and NiCoFeMnCrV HEAs [2].

From Table 4.2, we can see that HEAs adopting bcc phase are mainly composed of refractory elements. The refractory elements adopt a bcc crystal structure below their

melting temperature, but Ti, Zr and Hf are stable in the equilibrium volume of hcp

phase at ambient conditions. We use the thermal expansion method to estimate wmix of

Ti, Zr, and Hf with bcc phases [125, 126]. The so obtained wmix of the ETM-type HEAs

are in good agreement with the experimental data. The relatively small atomic radius

of V results in the large atomic size difference 1 and 2 for MoNbZrTiV, NbVZrTi, and

NbVHfZrTa HEAs. Although 1 and 2 are obtained from different data [97, 98], the

smallest is obtained for WMoTaNb alloy, while the large for NbVZrTi and NbVHfZrTi refractory HEAs.

21

Table 4.1. Structural properties for HEAs with a fcc structure, w is the Wigner-Seitz radius

(Bohr) converted from experimental lattice parameters via 4 43 w3 = a3 for fcc structure

and 2 43 w3 = a3 for bcc structure, a is the cubic lattice parameter; wmix is the average

Wigner-Seitz radius (Bohr); VEC stands for the average valence electron concentration

(e/a); is the atomic size difference (%), 1 is calculated based on the data of Ref. [97], 2

is calculated from Ref. [98]; Vickers hardness Hv (HV). The corresponding sources are

listed in the last column.

HEAs

CuNiCoFeCr

CuNiCoFeCrTi0.5

CuNiCoFeCrAl0.5 V0.2

CuNiCoFe

CuNiCoFeMn

CuNiCoFeV

CuNiCoFeTi

CuNiFeCr

CuNiFeCrMo

CuNi2 FeMn2 Cr

Cu0.75 NiCoFeCrTi0.5 Al0.25

Cu0.75 NiCoFeCrAl0.25

Cu0.5 NiCoFeCrAl0.3

Cu0.5 NiCoCrAl0.5 Fe2

Cu0.5 NiCoCrAl0.5 Fe3

Cu0.5 NiCoCrAl0.5 Fe3.5

NiCoFe

NiCoFeCr0.5

NiCoFeCr0.6

NiCoFeCr0.7

NiCoFeCr0.8

NiCoFeCr0.9

NiCoFeCr0.95

NiCoFeCr1.05

NiCoFeCr1.10

NiCoFeCr1.15

NiCoFeCr

NiCoFeCrMo0.3

NiCoFeCrMo0.1 Al0.3

NiCoFeCrTi0.1 Al0.3

NiCoFeCrTi0.3

NiCoFeMnCr

NiCoFeMnCrNb

NiCoFeMnCrV

NiCoFeCrPd

NiCoFeCrPd2

Ni1.5 Co1.5 FeCrTi0.5

Ni1.5 Co1.5 FeCrTi0.5 Mo0.1

NiFeCr

w

2.643

2.667

2.648

2.651

2.667

2.676

2.653

2.650

2.638

2.639

2.639

2.640

2.641

2.641

2.642

2.642

2.642

3.577

2.659

2.659

2.658

2.651

2.673

2.644

2.693

2.738

2.651

wmix

2.647

2.670

2.683

2.638

2.673

2.721

2.656

2.710

2.699

2.663

2.666

2.677

2.676

2.675

2.627

2.709

2.637

2.638

2.639

2.640

2.641

2.642

2.643

2.643

2.642

2.661

2.672

2.675

2.670

2.681

2.708

2.673

2.677

2.651

VEC

8.80

8.36

8.16

9.50

9.00

8.60

8.40

8.75

8.20

8.43

8.00

8.40

8.21

8.00

8.00

8.00

9.00

8.57

8.50

8.43

8.37

8.31

8.28

8.22

8.20

8.17

8.25

8.09

7.84

7.80

7.88

8.00

9.17

9.17

8.60

8.83

8.09

8.05

8.00

1

1.07

4.82

4.15

1.14

3.18

2.20

6.50

1.15

3.58

3.57

5.40

3.43

3.58

4.08

3.84

3.74

0.33

0.31

0.31

0.31

0.30

0.30

0.30

0.30

0.30

0.30

0.30

2.38

3.90

4.40

3.76

3.27

5.49

3.29

4.04

4.69

4.89

4.92

0.26

2

hardness

Ref.

1.07

133

[1, 5]

4.46

[5, 96]

3.87

202

[99]

1.03

[95]

0.92

[36]

2.88

[26]

6.13

[51]

0.96

[100]

4.10

263

[6]

0.99

[101]

5.03

[96]

3.00

[27]

3.30

[102]

3.67

[25]

3.41

[25]

3.30

[25]

0.75

124

[37, 103]

0.95

[35]

0.97

[35]

0.99

[35]

1.00

[35]

1.02

[35]

1.02

[35]

1.03

[35]

1.04

[35]

1.04

[35]

1.03

116

[9, 45]

2.92

210

[104]

3.74

[48, 105]

4.06

[105]

3.49

350

[106]

0.92 300/290

[2]

6.03 1031/399

[2]

2.70 1007/287

[2]

3.76

[9]

4.33

[9]

4.60

[107]

4.72

[107]

0.98

[100]

22

Table 4.2. Structural properties for HEAs with the bcc structure. See caption for

Table 4.1.

HEAs

Cu0.5 NiCoCrAl

Cu0.25 NiCoFeCrAl

WMoTaNb

WMoTaNbV

TaNbHfZrTi

TaNbVTi

TaNbVTiAl0.25

TaNbVTiAl0.5

TaNbVTiAl1.0

MoNbZrTi

MoNbZrTiV0.25

MoNbZrTiV0.5

MoNbZrTiV0.75

MoNbZrTiV

MoNbCrTiAl0.5

MoNbCrVAl0.5

MoNbCrVTiAl0.5

NbVZrTi

NbVHfZrTi

NbHfZr

w

2.683

2.990

2.962

3.167

3.094

3.150

3.244

wmix

2.717

2.709

3.000

2.964

3.169

3.003

3.002

3.001

3.000

3.090

3.074

3.059

3.046

3.035

2.940

2.887

2.917

3.066

3.115

3.239

VEC

6.09

7.38

5.50

5.40

4.40

4.75

4.65

4.56

4.40

4.75

4.76

4.78

4.79

4.80

5.00

5.22

5.00

4.50

4.40

4.33

1

2.81

5.65

2.31

3.15

4.99

3.93

3.83

3.73

3.57

5.99

6.31

6.55

6.73

6.85

5.88

5.40

5.52

7.05

7.07

5.00

2

5.44

5.13

2.27

3.21

4.01

3.53

3.42

3.33

3.16

4.92

5.24

5.48

5.65

5.77

5.11

4.90

4.90

6.78

6.75

3.69

hardness

496

445.5

525

382.6

328.5

380

Ref.

[3]

[26]

[12]

[12]

[108]

[15]

[15]

[15]

[15]

[109]

[109]

[109]

[109]

[109]

[110]

[110]

[110]

[42]

[111]

[43]

23

2.80

2.80

2.78

2.76

2.74

2.78

w

w

w

w

(fcc)

mix

2.76

(fcc)

(bcc)

mix

2.74

(bcc)

2.72

2.72

2.70

2.70

2.68

2.68

2.66

2.66

2.64

2.64

2.62

2.62

fcc

bcc

Figure 4.1. The comparison between the experimental w and the calculated wmix

for HEAs with the fccbcc transformation.

The HEAs with the fccbcc phase transformation are mainly derived from the additions of Al or the increase of the bcc stabilizer Cr, whereas the additions of the fcc stabilizer Ni or Co induces the bccfcc transformation of HEAs. The calculated wmix of

the HEAs with the fcc structure is consistent with the experimental w. Whereas for the

HEAs with bcc structure the wmix is slightly larger than the experimental w, which indicate that some solid-solution ordering may be occurring for these HEAs, especially

for the Al containing HEAs [53]. The detailed comparisons between the experimental w

and the calculated wmix are shown in Figure 4.1.

4.2

The atomic size difference is basic and important quantity for solid solution state. For

this reason, in Eq. 4.3 we use two different sets of to study distortion of structure.

One is from Ref. [97], which is applied to study glass forming ability of amorphous

metallic alloys. Another is metallic radius from Ref. [98] which is derived from the

twelve coordinated metal. Note that the large difference of between Ref. [97] and

Ref. [98] mainly results from atomic radius of Mn. Interestingly, these of HEAs with

the fcc phase are small, compared to the HEAs with the bcc structure.

24

Table 4.3. Structural properties for HEAs with the fccbcc phase transformation.

See caption for Table 4.1.

HEAs

CuNiCoFeCrAl0.3

CuNiCoFeCrAl0.5

CuNiCoFeCrAl0.8

CuNiCoFeCrAl1.0

CuNiCoFeCrAl2.3

CuNiCoFeCrAl2.5

CuNiCoFeCrAl2.8

CuNiCoFeCrAl3.0

CuNi2 FeCrAl0.2

CuNi2 FeCrAl0.4

CuNi2 FeCrAl0.5

CuNi2 FeCrAl0.7

CuNi2 FeCrAl0.8

CuNi2 FeCrAl1.0

CuNi2 FeCrAl1.2

CuNi2 FeCrAl1.5

CuNi2 FeCrAl1.6

CuNi2 FeCrAl1.8

CuNi2 FeCrAl2.0

CuNi2 FeCrAl2.2

CuNi2 FeCrAl2.5

Cu0.5 CoFeCrAl

Cu0.5 CoFeCrAlNi0.5

Cu0.5 CoFeCrAlNi1.0

Cu0.5 CoFeCrAlNi1.5

Cu0.5 CoFeCrAlNi2.0

Cu0.5 CoFeCrAlNi2.5

Cu0.5 CoFeCrAlNi3.0

Cu0.5 NiFeCrAl

Cu0.5 NiFeCrAlCo0.5

Cu0.5 NiFeCrAlCo1.5

Cu0.5 NiFeCrAlCo2.0

Cu0.5 NiFeCrAlCo3.0

Cu0.5 NiFeCrAlCo3.5

Cu0.5 NiCoFeAl0.5 Cr

Cu0.5 NiCoFeAl0.5 Cr2

Cu0.5 NiCoFeAl0.5 Cr3

Cu0.5 NiCoFeAl

Cu0.5 NiCoFeAlCr0.5

Cu0.5 NiCoFeAlCr1.0

Cu0.5 NiCoFeAlCr1.5

Cu0.5 NiCoFeAlCr2.0

phase

fcc

fcc

fcc+bcc

fcc+bcc

fcc+bcc

fcc+bcc

bcc

bcc

fcc

fcc

fcc

fcc

fcc+bcc

fcc+bcc

fcc+bcc

fcc+bcc

bcc

bcc

bcc

bcc

bcc

bcc

bcc

bcc

bcc+fcc

bcc+fcc

bcc+fcc

fcc

bcc

bcc

bcc+fcc

bcc+fcc

fcc

fcc

fcc

bcc+fcc

bcc

fcc

fcc+bcc

bcc

bcc

bcc

w

2.646

2.644

2.700

2.696

2.661

2.648

wmix

2.666

2.667

2.755

2.762

2.770

2.776

2.658

2.670

2.676

2.687

2.729

2.736

2.744

2.751

2.760

2.731

2.718

2.708

2.679

2.729

2.717

2.682

2.678

2.679

2.681

2.645

2.706

2.704

VEC

8.47

8.27

6.97

6.87

6.72

6.63

8.77

8.56

8.45

8.26

7.55

7.41

7.29

7.17

7.00

7.00

7.30

7.55

8.20

7.22

7.40

7.93

8.00

8.00

7.43

8.56

7.55

7.42

7.31

1

3.42

4.17

6.40

6.48

6.57

6.61

2.94

3.84

4.20

4.74

6.02

6.17

6.30

6.40

6.52

5.86

5.68

5.51

4.93

5.92

5.71

4.88

4.75

4.37

3.77

0.84

5.34

5.18

2

3.15

3.82

5.84

5.91

5.99

6.09

2.69

3.48

3.82

4.30

5.46

5.60

5.71

5.80

5.91

5.21

5.12

5.02

4.60

5.21

5.12

4.60

4.51

4.00

3.38

1.06

4.82

4.64

hardenss

Ref.

18020

[1, 112]

20820

[1, 112114]

27120

[1, 112]

40620

[1, 112]

600

[1]

620

[1]

655

[1]

635

[1]

160

[53]

172

[53]

270

[53]

290

[53]

320

[53]

390

[53]

520

[53]

550

[53]

557

[53]

550

[53]

570

[53]

580

[53]

600

[53]

[25]

[25]

458

[25, 114]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

[25]

174

[25, 115, 116]

[25]

[25]

[25]

[25]

HEAs

Cu0.5 NiCoFeCr

Cu0.5 NiCoFeCrAl0.5

Cu0.5 NiCoFeCrAl1.0

Cu0.5 NiCoFeCrAl1.5

Cu0.5 NiCoFeCrAl2.0

NiCoFeCrAl0.25

NiCoFeCrAl0.3

NiCoFeCrAl0.375

NiCoFeCrAl0.5

NiCoFeCrAl0.75

NiCoFeCrAl0.875

NiCoFeCrAl

NiCoFeCrAl1.25

NiCoFeCrAl1.5

NiCoFeCrAl2.0

NiCoFeCrAl2.5

NiCoFeCrAl3.0

phase

fcc

fcc

bcc

bcc

bcc

fcc

fcc

fcc

fcc+bcc

fcc+bcc

fcc+bcc

fcc+bcc

bcc

bcc

bcc

bcc

bcc

w

wmix VEC

2.648 2.645 8.56

2.661 2.679 8.00

2.708 7.55

2.731 7.17

2.751 6.92

2.653 2.662 7.94

2.659 2.666 7.88

2.656 2.671 7.80

2.684 2.737 6.82

2.686 2.758 6.50

2.681 2.776 6.23

2.686 2.791 6.00

25

1

0.84

4.37

5.51

6.11

6.46

3.47

3.76

4.08

5.95

6.16

6.41

6.53

6.56

2

hardenss

Ref.

1.06

174

[25, 115, 116]

4.00

[25, 27]

5.02

458

[25, 114]

5.56

[25]

5.87

[25]

3.25

1102

[45]

3.49

[48]

3.80 130.80.5

[45]

159.02

[45]

388.05

[45]

538.012

[45]

484.026

[45]

5.55

487

[45]

5.77 403/580

[45, 49]

6.04 432/615

[45, 49]

6.19 487/690

[49]

6.26 506/740

[49]

From Table 4.1-4.3, we can see that for small values of VEC the structure is bcc and

for large values fcc. Figure 4.2 depicts this correlation. Obviously, the VEC of the

HEAs with fcc is larger than that of HEAs with bcc. The largest VEC for bcc phase

is 7.55 for Cu0.5 NiCoFeCrAl [25], and the smallest VEC is 4.33 for the ternary equimolar

NbHfTi alloy [43]. In the case of HEAs with fcc structure, the smallest VEC is 7.80 for

NiCoFeCrAl0.375 [45], while the largest is about 9.5 for CuNiCoFe [95] HEA among the

availably experimental results. Note that the exact delimitation of VEC is difficult to assess due to the lack of more data of alloys and especially the fccbcc transformation of

phase in some HEAs. For instance NiCoFeCrAl0.5 is a single fcc structure in Ref. [51], but

fcc+bcc in Ref. [45, 47]. NiCoFeCrAl has only one bcc phase in Ref [10, 19] whereas the

mixed phase of fcc+bcc in Ref [45, 47]. Here we should mention that recently the crystal

structure versus VEC correlation was confirmed by us in the case of NiCoFeCrAlx HEA

by using ab initio calculations based on modern alloy theory [117].

4.4 Hardness

The hardness Hv shows a maximum value as a function of the VEC. For the singlephase HEAs a similar behavior is expected. In Table 4.1-4.3, we list the data of Vickers

26

7.80

BCC

FCC

4.33

4.5

5.0

9.50

7.55

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

VEC

Figure 4.2. The crystal structure versus the average valence electronic concentration (VEC) for the single solid solution HEAs.

hardness of the available single-phase HEAs, but some are from macro measures, while

others are micro values. Here we employ the values of macro hardness. As shown in

Figure 4.3, the hardness as a function of VEC follows Gauss type distributions. The

maximum value is obtained at VEC 6.8. Note that the data of hardness are particularly limited under VEC = 6.20 and some hardness values were not included in this

correlation as they show large deviations for the same HEAs.

The solid solution hardening mechanism originates from the distortion of the crystalline

cell preventing the easy motion of the dislocations necessary for the plastic deformation.

This is why one can expect a monotone increase of the hardness (and of the ultimate

tensile stress , Hv 3) with the lattice deformation expressed through . Figure 4.4

shows that hardness as a function of . The scatter around an average linear relationship

is smaller for Pearsons 2 [98], compared to Senkovs 1 [97]. The increase of hardness

as a function of atomic size difference is about 107 HV/% and 90 HV/% for Pearsons

[98] and Senkovs data [97], respectively. Despite of the scattering of the hardness data,

one can approximate 100 HV/ % for the effect of atomic size difference. For the high

atomic mismatch, 6%, which is similar with the maximum (about 650 HV) shown

in Figure 4.4. Applying Hv 3, the maximal strength for one phase bcc HEA can be

estimated as 200 HV, which is a value comparable to the best known steels value.

In order to make a more fundamental assessment between the atomic size and hardness

one may make use of classical hardening theories based on the size and elastic misfit

parameters. Such approach was successfully combined with ab initio calculations in the

case of steel and aluminum alloys [118, 119].

4.4. HARDNESS

27

700

600

Hardness (HV)

500

6.80

400

300

200

100

6.0

6.4

6.8

7.2

7.6

8.0

8.4

8.8

VEC

700

600

Hardness (Hv)

500

400

300

200

100

1

Chapter 5

Structural and elastic property of HEAs

5.1 Assessing CPA

5.1.1 CPA versus SC

In order to assess the performance of CPA in the case of HEAs, we select NiCoFeCr and

set up a simple supercell (SC) with fcc underlying lattice. To mimic a homogeneous

solid solution, we distribute the four alloying elements so that they are neighbors to

each other within a conventional fcc unit cell, as shown in Figure 5.1. Similar structure for different HEAs are suggested in Refs. [120, 121]. We notice that NiCoFeCr is

found to show no tendency for long-range ordering [121]. Taking into account that the

long-range order has a rather small effect on the elastic properties of alloys [122], a direct comparison between the CPA and the SC results calculated for the present ordered

structure seems to be well founded.

The results obtained for the supercell from Figure 5.1 and those calculated for the corresponding Ni0.25 Co0.25 Fe0.25 Cr0.25 random solid solution are listed in Table 5.1. The

average SC equilibrium Wigner-Seitz radius is 2.601 Bohr, which is rather close to 2.607

Bohr obtained for solid solution using CPA. The agreement between the SC (207 GPa)

and CPA (208 GPa) bulk moduli is also excellent. For all theoretical parameters, we

find a good consistency between the CPA and SC results. In particular, the three cubic

elastic constants, c11 , c12 and c44 , obtained with the two methods differ on the average by 4%. The somewhat larger relative errors in the Zener anisotropy (c44 /c ) and

the Cauchy pressure (c12 c44 ) are still acceptable, especially if we consider that the

present supercell is the simplest periodic approximant of the four-component random

alloy considered in the CPA calculations. The good agreement seen for the shear and

Youngs modulus, Poisson ratio and polycrystalline anisotropy ratio AVR indicate that

the CPA is an efficient and accurate method to investigate the bulk properties of these

multicomponent alloys.

28

29

Figure 5.1. The supercell used to model the NiCoFeCr alloy [121].

Table 5.1. Theoretical bulk parameters for fcc NiCoFeCr alloy calculated using the CPA and

SC approximations. Listed are the equilibrium Wigner-Seitz radius w (Bohr), cubic elastic constants c11 , c12 , and c44 , and c (GPa), the Zener anisotropy AZ , the

Cauchy pressure (c12 c44 ) (GPa), the bulk modulus B (GPa), the shear modulus

G (GPa), the Young modulus E (GPa), the Poisson ratio , and the polycrystalline

elastic anisotropy ratio AVR .

Method

c11

c12

c44

c

AZ

CPA

271.0 175.0 189.3 48.0

3.9

SC

257.1 183.5 193.9 36.8

5.2

w

B

G

E

CPA

2.607 207

110

280 0.275

SC

2.601 208

101 262 0.290

(c12 -c44 )

-14.3

-10.4

AVR

0.21

0.29

In order to further assess the performance of our calculations derived from the meanfield CPA, we construct two 2 2 2 cubic supercells. The supercell formed by the

bcc (fcc) unit cells is treated as simple cubic (body centered cubic), where we introduce

one (two) Al atom per 16 (32) atomic sites. All other sites are occupied by an equimolar

four component NiCoFeCr alloy. We note that similar partially ordered solid solution

has been reported in FeCrNiCoAl0.3 alloys. The present supercells have the molar radio

Ni15/4 Co15/4 Fe15/4 Cr15/4 Al1 , corresponding to NiCoFeCrAl0.2667 HEA. The Wigner-Seitz

radii obtained for these supercells are 2.620 Bohr for fcc, and 2.634 Bohr for bcc, which

are practically the same as those obtained in the CPA calculations (2.620 Bohr for fcc

and 2.635 for bcc). The corresponding bulk moduli are 197 and 193 GPa for the fcc and

bcc supercells, respectively, which are also close to the CPA results (198 GPa for fcc and

193 GPa for 135 bcc).

30

For 3d- HEAs adopting the fcc phase, we take CuNiCoFeCrTix as examples to study

the equilibrium volume, electronic structures, magnetic state and elastic properties for

NiCoFeCr, CuNiCoFeCrTix (x = 0 0.5, 1.0) and NiCoFeCrTi HEAs.

Table 5.2. Theoretical (EMTO) and experimental (Expt.) Wigner-Seitz radii (Bohr) for

NiCoFeCr, CuNiCoFeCr and NiCoFeCrTi HEAs. For reference, former theoretical

(PBE-level, wc ) and experimental (we ) radii for the elementary solids in their ground

state crystallographic structures (indicated in parentheses) are also listed [63]. is

the relative difference between w(EMTO) and w(Expt.). wc and we represent the

alloys Wigner-Seitz radii as estimated from the quoted wc and we values, respectively, according to Vegards rule.

HEAs

NiCoFeCr

CuNiCoFeCr

NiCoFeCrTi

CuNiCoFeCrTi0.1

CuNiCoFeCrTi0.2

CuNiCoFeCrTi0.3

CuNiCoFeCrTi0.4

CuNiCoFeCrTi0.5

CuNiCoFeCrTi1.0

Element

wc

we

str.

fcc

fcc

fcc

fcc

fcc

fcc

fcc

fcc

fcc

Ti (hcp)

3.04

3.053

w(EMTO) w(Expt.)

2.607

2.632 [9]

0.95%

2.628

2.643 [5]

0.57%

2.682

2.650 [7]

1.21%

2.635

2.643

2.651

2.655

2.663

2.694

Cr (B2)

Fe (bcc) Co (hcp)

2.65

2.64

2.60

2.684

2.667

2.613

wc

2.623

2.636

2.706

2.644

2.652

2.659

2.666

2.673

2.703

Ni (fcc)

2.60

2.602

we

2.642

2.647

2.724

2.655

2.663

2.670

2.677

2.684

2.715

Cu (fcc)

2.69

2.669

In Table 5.2, we list the PBE-level results from Ref. [63] as well as some experimental

data for the elementary solids in their low-temperature crystallographic phases. It has

been found that density functional theory (PBE) underestimates the hcp Ti, antiferromagnetic B2 Cr, ferromagnetic body centered cubic (bcc) Fe, ferromagnetic hcp Co and

fcc Ni, whereas for fcc Cu a weak underbinding is observed [63]. Using the Wigner-Seitz

radii for the alloy constituents, we may estimate the equilibrium volume of the HEAs

via Vegards rule. In Table 5.2, wc stands for the estimated volume based on the previous PBE-level theoretical data, and we the one obtained from the experimental data.

Rather interestingly, we gives an excellent estimate for the equilibrium radius of the

equimolar NiCoFeCr, CuNiCoFeCr, and CuNiCoFeCrTix (x = 0.1 0.5, 1.0) alloys. As

31

2.70

2.68

2.66

2.64

2.62

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

The content of Ti

content of Ti x for CuNiCoFeCrTix (x = 0.0 0.5, 1.0).

shown in Figure 5.2, we can see that with increasing Ti content the equilibrium volume

of CuNiCoFeCrTix linearly increases.

According to the present calculations, the local magnetic moments vanish on the Ni, Cu

and Ti sites in for all volumes. We should note that thermal effects would eventually

induce local magnetic moments on the Ni sites as well at finite temperature. Such longitudinal spin fluctuations have been neglected in the present study. For all alloys, Fe

possesses a significant ( 1.8 2.0B ) local magnetic moment around the equilibrium

volume. Cobalt remains non-magnetic in NiCoFeCr and NiCoFeCrTi but shows a small

( 0.6B ) magnetic moments for CuNiCoFeCr.

In order to understand the magnetic state of the present 3d-HEAs, we investigate the

electronic structure of the hypothetical non-magnetic and paramagnetic fcc solid solutions. The non-magnetic total density of states (DOS) and partial density of states

(pDOS) for CuNiCoFeCr, NiCoFeCr and NiCoFeCrTi are plotted in Figure 5.3. The corresponding paramagnetic DOS are shown in Figure 5.4. All DOS calculations were done

at the proper theoretical equilibrium volume.

We observe that in spite of the compositional disorder, all alloys have a rather structured DOS with a substantial peak just below the Fermi level (EF ). This peak is mainly

due to the peaks in the pDOS of Co and Ni. The size of the total DOS at EF (D(EF )) decreases when adding Cu or Ti to the host composition. This DOS decrease is primarily

due to the 5% drop in the atomic fractions for Fe, Co, Cr and Ni, which cannot be compensated by the relatively low pDOS of Cu and Ti near EF . In nonmagnetic alloys, the

major peaks in the pDOS are located above the Fermi level for Ti and Cr and below the

Fermi level for Co, Ni and Cu. This can be explained by simple band filling arguments

considering that all alloy components experience the same fcc environment.

32

4.0

3.5

-0.6

-0.4

-0.2

0.0

0.2

-0.6

CuNiCoFeCr

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

0.0

0.2

NiCoFeCrTi

NiCoFeCr

3.0

2.5

2.0

1.5

1.0

Total

0.5

Fe

Fe

Fe

5.0

Cr

Cr

Cr

4.5

Ni

Ni

Ni

4.0

Co

Co

Co

3.5

Cu

0.0

Ti

3.0

2.5

2.0

1.5

1.0

0.5

0.0

-0.6

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

0.0

0.2

Energy (Ry)

Figure 5.3. Total (upper panels) and partial (lower panels) density of states (DOS)

for the nonmagnetic fcc CuNiCoFeCr, NiCoFeCr and NiCoFeCrTi alloys.

The position of the Fermi level is marked by vertical dashed lines.

-0.6

-0.4

-0.2

0.0

33

0.2

-0.6

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

0.0

0.2

0.0

0.2

2.0

CuNiCoFeCr

NiCoFeCrTi

NiCoFeCr

1.5

1.0

0.5

Total

0.0

2.0

1.5

Fe

Cr

Spin up

Co

1.0

0.5

0.0

-0.5

-1.0

-1.5

Spin down

-2.0

-0.6

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

0.0

0.2

-0.6

-0.4

-0.2

Energy (Ry)

Figure 5.4. Total (upper panels) and Fe, Co and Cr partial (lower panels) density of states (DOS) for the paramagnetic fcc CuNiCoFeCr, NiCoFeCr and

NiCoFeCrTi alloys. In the lower panels, only the Fe , Co and Cr partial

DOS are shown. Apart from a sign difference, the partial DOS for Fe , Co

and Cr are identical to those shown in the figure.

34

For all alloys, Fe has a moderate pDOS peak located very close to the Fermi level. It

is found that DFe (EF ) is the largest among all pDOS at EF , followed by DCo (EF ) and

DCr (EF ). This distinct Fe peak at EF leads to magnetic instability in Fe sublattice. Indeed, as shown in Figure 5.4, the spin-polarized pDOS of Fe has two separate peaks:

one above the Fermi level and one below the Fermi level. These two Fe peaks hybridize

with the Cr and Co peaks, respectively. As a result of the magnetic splitting, the total

D(EF ) drops significantly in all three alloys. In nonmagnetic CuNiCoFeCr, we have

DFe (EF ) DCo (EF ) and the Co peak is close to EF . This may explain the appearance of

the local magnetic moments on the Co sites in the paramagnetic state.

Additional total energy calculations performed for the hypothetical nonmagnetic fcc 3dHEAs give 2.592 Bohr, 2.610 Bohr, and 2.675 Bohr for the equilibrium Wigner-Seitz radii

of NiCoFeCr, CuNiCoFeCr, and NiCoFeCrTi, respectively. These values are smaller

than those listed in Table 5.2, which were obtained for the paramagnetic state. Taking

into account the uncertainty associated with the experimental equilibrium volume of

NiCoFeCrTi [7, 52], we may conclude that neglecting the paramagnetism in the present

3d-HEAs worsens the agreement between theory and experiment.

The three cubic elastic constants c11 , c12 , and c44 as well as the c , c44 /c , and (c12 c44 )

are shown in Figure 5.5 and Table 5.3 for NiCoFeCr, CuNiCoFeCrTix (x = 0 0.5, 1.0)

and NiCoFeCrTi HEAs.

Our calculations predict a moderate elastic anisotropy and negative Cauchy pressure for

NiCoFeCr. In lack of any experimental data, we compare the present results calculated

for paramagnetic NiCoFeCr with those obtained for paramagnetic austenitic stainless

steel alloys composed of 18% Cr, 8% Ni and balance Fe [123]. The three cubic elastic constants reported for this stainless steel are c11 = 208.6 GPa, c12 = 143.5 GPa and

c44 = 132.8 GPa, which yield 4.07 for the Zener anisotropy ratio and 10.7 GPa for the

Cauchy pressure. Therefore, compared to the austenitic stainless steels, the paramagnetic NiCoFeCr is predicted to be rather brittle. Equimolar Cu addition to NiCoFeCr is

found to increase slightly the Cauchy pressure from 14.3 GPa obtained for NiCoFeCr

to 10.7 GPa calculated for CuNiCoFeCr. For reference, fcc Ir has Cauchy pressure of

13 GPa, and undergoes both transgranular and intergranular fracture [92].

Next we compare the theoretical results with the available experimental data. It is particularly surprising that for CuNiCoFeCr, our Youngs modulus of 234 GPa is about

four times larger than 55.6 GPa found in experiment [5]. This alloy shows relatively low

anisotropy and thus the uncertainty associated with the Voigt-Reuss-Hill averaging are

expected to be small. Furthermore, as shown in Figure 5.6, the Youngs modulus of a

single-crystal CuNiCoFeCr changes between 102.79 GPa obtained for the <001> direction and 379.18 GPa calculated for the <111> direction. Therefore, even for a highly tex-

227.8

219.7

207.6

198.4

174.3

2.628

2.635

2.655

2.663

2.694

2.682

0

0.1

0.4

0.5

1.0

184.5 170.9

154.6

152.6

151.7

151.0

148.6

271.0 175.0

2.607

c12

c11

127.0

165.3

160.2

150.8

142.7

125.0

189.3

c44

6.8

36.6

33.5

27.9

23.7

12.8

48.0

c

(c12 -c44 ) B

G B/G

NiCoFeCr

3.9

-14.3

207 110 1.88

CuNiCoFeCrTix

4.6

-10.7

179 91 1.97

4.8

-7.5

175 87 2.01

5.4

2.0

171 78 2.19

6.0

8.3

169 71 2.38

9.8

23.6

157 54 2.91

NiCoFeCrTi

18.7

43.9

175 47 3.72

AZ

0.67

0.25

0.26

0.31

0.34

0.48

0.21

AVR

234.0

223.1

200.4

187.1

145.4

0.376 130.3

0.282

0.288

0.303

0.313

0.346

0.275 280.0

134 [7]

55.6 [5]

98.6 [5]

76.5 [5]

E(Expt.)

Table 5.3. Theoretical Wigner-Seitz radius w (Bohr), elastic constants c11 , c12 and c44 as well as c , c44 /c and

(c12 -c44 ); the elastic moduli B, G and E as well the Poisson ratio v for NiCoFeCr, CuNiCoFeCrTix

(x = 0.0 0.5, 1.0) and NiCoFeCrTi. For reference, the available experimental Youngs moduli are

also listed.

35

0.0

0.2

0.0

0.2

0.4

0.6

0.8

1.0

0.4

0.6

0.8

1.0

221

11

204

187

170

156

154

12

152

150

148

168

44

154

140

126

c'

37.5

30.0

22.5

15.0

9.8

12

44

44

/c'

8.4

7.0

5.6

4.2

24

16

8

0

-8

The content of Ti

Figure 5.5. Elastic constants (unit of GPa) as a function of the content of Ti x for

CuNiCoFeCr and CuNiCoFeCrTix (x = 0.1 0.5, 1.0).

450

400

NiCoFeCr

CuNiCoFeCr

CuNiCoFeCrTi

NiCoFeCrTi

350

300

E (GPa)

36

250

200

150

100

50

001

111

110

Figure 5.6. Theoretical Youngs modulus for NiCoFeCr, CuNiCoFeCr, CuNiCoFeCrTi and NiCoFeCrTi alloys as a function of direction including the three

main cubic directions.

37

Table 5.4. Wigner-Seitz radius w (Bohr) and bulk modulus B (GPa) for the refractory elements (M) and HEAs with bcc structure. wt represent the theoretical

(EMTO) Wigner-Seitz radius of pure elements, we stands for the experimental or extrapolated radius (those for Ti and Zr were extrapolated to 0 K,

Ref. [125, 126]), wt and we are the average Wigner-Seitz radii of the HEAs

estimated from the wt and we values of pure elements, respectively, according to Vegards rule.

M

Ti

we

Be

HEAs

wt

wt

we

a

3.038

TiZrVNb

3.054 3.057 3.062

3.043 96.7b TiZrNbMo

3.075 3.100 3.090

a

Zr 3.327 75.4 3.324

b

3.339 66.0

TiZrNbMoV0.50 3.046 3.068 3.059

V 2.789 176.3 2.813

155c TiZrNbMoV0.75 3.033 3.054 3.046

2.795 182.8b TiZrNbMoV1.00 3.023 3.042 3.035

Nb 3.081 150.5 3.071

169c TiZrNbMoV1.25 3.011 3.031 3.024

3.094 171.7b TiZrNbMoV1.50 3.002 3.022 3.015

Mo 2.944 249.6 2.928

261c

2.949 194.0b

a

estimated, Refs. [125, 126], b calculated, Ref [128], c experiment, Ref. [63].

wt

3.030

Bt

105.8

tured material theory would predict the lowest E to be around 100 GPa, which is still

almost double of the experimental value. For the two Ti-containing CuNiCoFeCrTi0.5

and CuNiCoFeCrTi alloys the calculated Youngs moduli differ from the reported experimental values by 90%. On the other hand, the agreement between theory and

experiment is almost perfect for NiCoFeCrTi. Such good agreement is rather unexpected since for this alloy we obtained very large anisotropy ratio. The single-crystal

Youngs modulus of NiCoFeCrTi changes significantly with direction (Figure 5.6), the

lowest value being close to 20 GPa (for <001>) and the largest around 307 GPa (for

<111>). Moreover, recent experiments show that NiCoFeCrTi is not a single fcc phase

alloy [124].

5.3.1 Structural properties

According to experiments, the HEAs composed of refractory elements have a singlephase bcc structure. It should be noted that the present refractory elements Ti, Zr, V, Nb

and Mo all adopt the a bcc crystal structure below their melting temperature, but Ti and

Zr (in contrast to V, Nb and Mo) are stable in the hcp phase at ambient conditions. Our ab

initio alloy theory predicts the bcc structure for TiZrVNb and TiZrNbMoVx (x = 0 1.5)

38

3.08

3.06

3.04

3.02

3.00

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

The content of V

x for TiZrNbMoVx (x = 0 1.5).

to be the most stable one among the three close-packed lattices (fcc, bcc and hcp).

First we study the atomic radius of the refractory elements and then turn to the corresponding HEAs. In Table 5.4, we list our theoretical results and the experimental

data, along with a few former theoretical values for the refractory elements in the bcc

phase. In order to estimate the Wigner-Seitz (WS) radius (w) of bcc Ti and Zr at 0 K,

we extrapolate the high temperature data assuming a linear thermal expansion, i.e.

w(T ) = w(0 K)(1 + T), where w(0 K) is the WS radius at 0 K, w(T ) at temperature

T, and is the linear thermal expansion coefficient. Using the experimental values

wTi (1155 K) = 3.077 Bohr and wZr (1140 K) = 3.358 Bohr [125] together with the reported

thermal expansion coefficients for bcc Ti (10.9 106 K1 ) and Zr (9 106 K1 ) [126],

we get 3.038 Bohr and 3.324 Bohr for w(0 K) of hypothetical bcc Ti and Zr, respectively.

Considering these estimated and the quoted experimental values for V, Nb and Mo

(Table 5.4), we conclude that the present theory correctly describes all five refractory elements. We also notice the reasonable agreement between the present theoretical values

and those from Ref. [128].

We show the calculated equilibrium WS radii for bcc TiZrVNb and TiZrNbMoVx (x =

0 1.50) HEAs in Table 5.4 and in Figure 5.7. The only experimental equilibrium radius we could find in the literature is 3.094 Bohr [42] reported for TiZrVNb. To further

assess the theoretical volumes predicted for the present HEAs, we make use of Vegards rule and estimate the mean equilibrium WS radii for alloys using those of the

alloy components. In Table 5.4, wt stands for the estimated radius based on the present

theoretical values, and we for the one obtained from the experimental data. The rather

good agreement between wt and we confirms the high performance of the present density functional approach for the alloy constituents. It is interesting to note that for all

HEAs considered here, the calculated equilibrium WS radius wt is slightly smaller than

wt . Hence all alloys show a small but systematic negative deviation relative to Vegards

rule. Similar to CuNiCoFeCrTix , the WS radius of TiZrNbMoVx has a linear change

shown in Figure 5.7 as a function of the content of Vanadium x (x = 0 1.50).

Alloy

TiZrVNb

TiZrNbMo

TiZrNbMoV0.25

TiZrNbMoV0.50

TiZrNbMoV0.75

TiZrNbMoV1.00

TiZrNbMoV1.25

TiZrNbMoV1.50

TiZrNbMo0.8

TiZrNbMo0.8 V0.2

TiZrNbMo0.9

TiZrNbMo0.8 V0.5

c11

166.4

209.9

211.0

212.2

213.2

213.7

218.0

219.3

199.0

200.8

204.3

203.7

c12

94.7

101.0

100.6

100.3

100.3

100.7

101.9

102.2

98.7

99.0

99.5

100.0

c44

53.8

52.6

52.1

51.6

51.2

50.9

50.0

49.8

52.8

52.5

52.6

51.9

c

35.9

54.4

55.7

55.9

56.4

56.5

58.0

58.5

50.1

50.9

52.5

51.9

AZ

1.500

0.966

0.944

0.923

0.908

0.900

0.861

0.850

1.054

1.031

1.004

1.000

(c12 c44 )

41.0

48.4

48.6

48.7

49.1

49.8

51.9

52.1

45.9

46.5

46.8

48.1

VEC

4.50

4.75

4.76

4.78

4.79

4.80

4.81

4.82

4.68

4.70

4.72

4.72

B

118.6

137.3

137.4

137.6

138.0

138.5

140.6

141.2

132.2

132.9

134.4

134.6

G

45.70

53.33

53.31

53.30

53.25

53.17

53.09

53.10

51.71

51.82

52.56

51.88

E

121.1

141.7

141.6

141.7

141.5

141.1

141.4

141.6

137.2

137.6

139.5

137.9

0.330

0.328

0.328

0.328

0.329

0.330

0.332

0.334

0.327

0.327

0.327

0.329

B/G

2.604

2.575

2.579

2.581

2.591

2.608

2.648

2.658

2.556

2.565

2.557

2.594

AVR

0.01958

0.00014

0.00041

0.00076

0.00111

0.00140

0.00268

0.00317

0.00033

0.00011

0

0

Table 5.5. Theoretical elastic constants c11 , c12 , c44 and c (GPa), the Zener anisotropy AZ (c44 /c ) and Cauchy pressure (c12 c44 )

(GPa); valence electronic concentration (VEC) (e/a); polycrystalline elastic moduli B, G, E (GPa), and Poissons ratio v, the

B/G ratio and the elastic anisotropy ratio AVR of the presently considered HEAs.

39

40

0.3344

0.3325

0.3306

0.3287

2.673

B/G

2.646

2.619

2.592

51.6

50.4

49.2

12

-c

44

(GPa)

52.8

48.0

0.00

0.25

0.50

0.75

1.00

1.25

1.50

V content ( )

Figure 5.8. Theoretical Poissons ratio (v), Pugh ration (B/G), Cauchy pressure

(c12 c44 ) as a function of V content x for TiZrNbMoVx (x = 0 1.5)

alloys.

In Table 5.5 we list the theoretical elastic constants c11 , c12 , c44 and c (GPa), the Zener

anisotropy AZ (c44 /c ) and Cauchy pressure (c12 c44 ) (GPa), valence electronic concentration (VEC) (e/a) as well as polycrystalline elastic moduli B, G, E (GPa), Poissons

ratio v, the B/G ratio and the elastic anisotropy ratio AVR of the presently considered

HEAs. The elastic ductility is often assessed via Poissons ratio (v), Pugh ration (B/G)

and Cauchy pressure (c12 c44 ). From Figure 5.8, we can see that the ductility is slightly

enhanced with increasing V content.

The valence electron concentration (VEC) has often been used to classify the single solidsolution phases (bcc, fcc or mixture of bcc and fcc). According to the experimental

findings, HEAs prefer to form bcc solid solution when VEC< 7.55 [127]. This correlation

is fully supported by the present theory and former experiments [10, 42]. In addition to

the phase stability, the VEC should also reflect the changes of the metallic bonds and

thus the changes of the polycrystalline elastic moduli. Indeed, as shown in Figure 5.9,

we find an correlation between the bulk and shear moduli of TiZrNbMoVx and the VEC.

The increase in the VEC with V content (we should remember that HEAs are equimolar

systems) is followed by an increase (slightly decrease) of the bulk (shear) modulus. The

opposite trends in B and G explains the enhanced ductility of TiZrNbMoVx for large x

values.

41

V content x

0.00

0.25

0.50

0.75

1.00

1.25

1.50

53.35

142

2.66

53.30

141

B

G

2.64

B/G

53.25

53.15

2.62

B/G

53.20

139

G (GPa)

B (GPa)

140

2.60

138

53.10

2.58

53.05

2.56

137

4.75

4.76

4.78

4.79

4.80

4.81

4.82

VEC (e/a)

Figure 5.9. Correlation between the bulk (B), shear (G) moduli and Pugh ratio B/G

of TiZrNbMoVx (x = 01.5) and the valence electron concentration (VEC).

In order to illustrate the effect of alloying on the elastic anisotropy of refractory HEAs, in

Figure 5.10, we plot the three dimensional E for TiZrVNb, TiZrNbMo and TiZrVNbMo.

Here E is the Youngs modulus along [hlk]. For TiZrVNb alloy, the E exhibits a rather

strong orientation dependence, so this system may be regarded as being anisotropic.

The largest value of E is 140.2 GPa realized along the [111] direction, whereas the smallest value of 97.7 GPa belongs to the [100] direction.

In contrast to the Mo-free alloy, the Mo-containing alloys seem to be almost isotropic.

Namely, their three dimensional E shown in Figure 5.10 have almost spherical shape.

The Youngs modulus changes between 136.0 and 149.2 GPa for TiZrVNbMo, and between 139.9 and 144.3 GPa for TiZrNbMo. The fact that Mo makes the alloy more

isotropic is in line with former studies. Theoretical calculations predicted nearly isotropic

surface energies for bcc Mo and, as a consequence, spherically shaped nano-particles for

this metal [129].

For a fully isotropic material, the tetragonal shear modulus c = (c11 c12 ) equals the

cubic shear modulus c44 , so we have AZ = 1 and AVR = 0. The latter condition reflects the fact that all statistical averaging methods (in the present case, the Voigt and

Reuss methods) lead to the same polycrystalline shear modulus. According to our calculations, V sightly enhances the anisotropy of TiZrNbMoVx , whereas equimolar Mo

addition to TiZrNbV turns the alloy almost isotropic. Based on this information, we

propose that one can optimize the content of Mo and V in TiZrNbMoy Vx so that the

resulting alloy is fully isotropic. We demonstrate this by performing calculations for

42

TiZrNbMo, TiZrVNbMo and TiZrNbMo0.8 V0.5 . The values on the color

scale and on the axes are in GPa, note that the same colorbar is for

TiZrVNb and TiZrNbMo0.8 V0.5 , another same colorbar is for TiZrNbMo

and TiZrVNbMo.

TiZrNbMoy Vx as a function of x and y (keeping the Ti, Zr, and Nb atomic fractions to

1). Some of the results of this additional study are shown in the lower part of Table

5.5. We find that TiZrNbMoy Vx becomes almost perfectly isotropic for (x, y) = (0, 0.9)

or (x, y) = (0.5, 0.8). Taking and TiZrNbMo0.8 V0.5 as example, we show the perfect

isotropy in Figure 5.10.

Very interestingly, for both isotropic TiZrNbMo0.9 and TiZrNbMo0.8 V0.5 HEAs, the VEC

is about 4.72. On this ground, we suggest that VEC=4.72 is an important criterion for

the isotropic HEAs. For comparison, Li et al. reported that the Ti-V alloys (Gum Metals)

become elastically isotropic for VEC 4.7 [130]. Since the present results correspond

to static conditions, the above conclusion is valid only at low temperatures. Due to the

particular electronic structure of the refractory HEAs alloys, the elastic anisotropy is

expected to depend strongly on temperature.

43

5.4.1 Phase transformation

82

80

Exp. a

Exp. b

Exp. c

Exp. d

Cal.

78

76

74

0.0

0.1

0.2

0.3

0.4

0.5

1.0

1.2

1.4

Exp. a

Exp. b

Exp. c

Exp. d

Exp. e

Cal.

1.6

1.8

3.6

bcc

82

2.0

80

2.4

78

1.2

x=1.11

76

-1.2

74

0.0

Energy (mRy)

fcc

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

Al content ( )

Figure 5.11. Upper panels: comparison between the theoretic and experimental

equilibrium volumes for fcc (x = 0.0 0.5, upper left panel) and bcc

(x = 1.0 2.0, upper right panel) FeCrNiCoAlx alloys. The quoted experimental data are a Ref. [47], b,c Ref. [45], d Ref. [51], and e Ref. [49]. Lower

panel: theoretical fcc and bcc equilibrium volumes and structural energy

difference for 0 x 2.5.

In the lower panel of Figure 5.11, we show the theoretical equilibrium volume (V ), bulk

modulus (B), and structural energy difference Et Etbcc Etfcc for the NiCoFeCrAlx

alloys as a function of Al content. The theoretical equilibrium volumes of the fcc and

bcc alloys are compared to the experimental data in the upper panels of Figure 5.11. Experimental volumes are available for the single fcc phase for x 0.5, and for single bcc

phase for x 0.9 [45,47,49,51]. Taking into account the large scatter in the experimental

data, we conclude that the present theory reproduces well the experimental trends of

V (x) for both fcc and bcc structures. Aluminum addition is found to increase the equilibrium volume of the solid solution, which is consistent with the fact that w of Al is

larger than those of the other alloy components. The slopes of w(x) and B(x) versus x

are larger in the fcc phase than in the bcc phase. This is likely to be due to the enhanced

flexibility of the bcc structure to incorporate a large substitutional element as compare

to the close-packed fcc lattice.

x=0.851

2

x=0.545

x=1.181

-2

-4

600 K

G (mRy)

0.0

44

0.1

0.2

0.3

0.4

0.5

0.4

0.5

x=0.982

2

x=0.597

x=1.229

-2

-4

300 K

0.0

0.1

0.2

0.3

x=1.11

bcc

x=0.651

fcc

x=1.277

-2

-4

0 K

0.0

0.1

0.2

0.3

0.4

0.5

Al content ( )

Figure 5.12. Comparison of the Gibbs free energies for bcc and fcc

(NiCoFeCr)1y Aly (y = 0.0 0.5) for T = 0, 300 and 600 K. Note

that y = x/(4 + x), where x is the atomic fraction of Al in NiCoFeCrAlx .

x

w(fcc) B(fcc) w(bcc)

0

2.607

207

2.626

0.10

2.611

200

2.629

0.25

2.619

197

2.634

0.30

2.622

196

2.636

0.375 2.626

194

2.639

0.50

2.632

190

2.644

B(bcc)

199

197

193

192

189

187

Et

3.937

3.408

2.523

2.380

2.021

1.566

x

1.00

1.25

1.30

1.50

2.00

2.50

2.654

183

2.659

2.664

173

2.667

2.666

172

2.670

2.673

170

2.675

2.691

159

2.690

2.705

151

2.701

B(bcc)

178

171

170

167

159

153

Et

0.228

-0.236

-0.239

-0.449

-0.773

-0.831

Table 5.6. Theoretical Wigner-Seitz radius w (Bohr), bulk modulus B (GPa), and energy difference between the bcc and fcc phases Et (mRy/atom) for NiCoFeCrAlx high entropy alloys calculated

for the fcc and bcc phases as a function of Al fraction x.

45

46

According to Table 5.6, the fcc structure is predicted to be more stable than the bcc one

for x = 0.0 1.0, and the bcc structure becomes stable from x = 1.25. Using a cubic

spline fit for the calculated energy points, we find that the structural energy difference

between ideal bcc and fcc lattices vanishes at 1.11 Al fraction (Figure 5.11, lower panel).

Due to the large atomic volume of Al, one may anticipate that the interatomic distance

between Al and the other elements is larger than the average bulk value. We estimated

the size of the local lattice relaxation (LLR) around the Al atoms in NiCoFeCrAlx alloys

by making use of the above 2 2 2 supercells, each of them containing one single

Al atom. We relaxed the first 12 nearest neighbor NiCoFeCr sites in the fcc supercell

and the first 8 nearest neighbor NiCoFeCr sites in the bcc supercell. For the energy

gain upon the LLR, we obtained Ebcc = 0.17 mRy and Efcc = 0.32 mRy. The larger

relaxation effect in the fcc lattice is in line with our previous observation that the bcc

lattice can accommodate the large substitutional Al easier than the fcc lattice. Then

we consider Etr x(Ebcc Efcc ) as the measure of the LLR effect on the structural

energy difference per Al fraction. Adding Etr to Et from Table 5.6, we obtain that

the total structural energy difference vanishes around x = 1.2, i.e. at only slightly larger

Al content than the one predicted from the total energies obtained for rigid underlaying

lattices.

Two phases arrive at equilibrium when their chemical potentials become equal. Here

we consider the NiCoFeCrAlx system as a pseudo-binary (NiCoFeCr)1y Aly alloy (with

y = x/(4 + x)) and compute the relative formation energy according to G (y) =

G (y) (1 2y)Gfcc (0) 2yGfcc (0.5), where stands for fcc or bcc, and G (y) is the

Gibbs free energy per atom for (NiCoFeCr)1y Aly in the phase. This is approxi

mated as G (y) E (y) T Smix (y) T Smag

(y), where E (y) is the total energy per

atom for (NiCoFeCr)1y Aly in the phase, and T is the temperature. The two entropy terms are estimated within the mean-field

5 approximation. Namely, the mixture entropy

5of ideal solutions is Smix = kB i=1 ci lnci , and the magnetic entropy

Smag = kB i=1 ci ln(1 + i ), where ci is the concentration and i the magnetic moment

of the ith alloying element. Accordingly, all chemical and magnetic short range order

effects and the longitudinal spin fluctuations are neglected (i.e. for each alloy composition we assume constant local magnetic moments with temperature). The above

phenomenological approximation for the magnetic entropy was previously used to estimate the free energy of paramagnetic Fe [131] and Fe-based alloys [132, 133] having

non-integer magnetic moments. The present Gibbs free energies at different temperature are plotted in Figure 5.12. According to the rule of common tangent line, we find

that at room temperature NiCoFeCrAlx has single fcc phase for x . 0.597 (y . 0.130),

single bcc phase for x & 1.229 (y & 0.235), and two phases (duplex) between the above

limits. In terms of valence electron concentration, the present theory predicts that at 300

K the fcc phase is stable for VEC & 7.57 and the bcc one for VEC . 7.04. These theoretical solubility limits should be compared to 8.0 and 6.87 estimated by Guo et al. [28] and

7.67 7.88 and 7.06 7.29 observed in experiments [45, 51].

47

1.229

0.597

0.32

0.31

0.30

0.29

fcc

bcc

B/G

12

-c

44

(GPa)

0.28

8

4

0

-4

-8

-12

2.4

2.3

2.2

2.1

2.0

1.9

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Al content ( )

Figure 5.13. Theoretical Poissons ratio (upper panel), Cauchy pressure (middle

panel) and Pugh ratio (lower panel) for NiCoFeCrAlx as a function of

Al fraction. Results are shown for the fcc phase for x 1 and for the bcc

phase for x 1. The two single phase regions (fcc or bcc) as well as the

two-phase (duplex) region (fcc and bcc) corresponding to Figure 5.12 (300

K) are marked by different (colored) areas.

The calculated elastic parameters of NiCoFeCrAlx HEAs are listed in Table 5.7. We

notice that the elastic parameters obtained for the fcc and bcc phases around x = 1 are

surprisingly close to each other. When considering the fcc or bcc structure separately, it

is found that the three cubic elastic constants (cij ) and the polycrystal elastic moduli (B,

G, and E) decrease with increasing Al content. However, the Cauchy pressure (c12 c44 ),

the two anisotropy ratios (AZ and AVR ), the Poissons ratio () and the B/G ratio increase

with x in the fcc phase.

The somewhat different impact of Al on the elastic parameters of fcc and bcc NiCoFeCrAl leads to local maxima in (c12 c44 ), and B/G versus x when plotted for fcc for

x 1 and for bcc for x 1 (Figure 5.13). In order to understand these trends, we should

see how alloying influences the single-crystal elastic parameters when going from Alfree fcc to bcc NiCoFeCrAl2 . As B(x) follows a nearly linear trend, the nonlinearity of

c11 and c12 is due to the particular trend obeyed by the tetragonal shear elastic constant

c = (c11 c12 )/2. This parameter is connected to the curvature of the total energy as

a function of the tetragonal lattice parameter c/a at fixed volume [63]. According to

the calculated trend of c (x) (Table 5.7), Al strongly reduces the dynamical stability of

48

Table 5.7. Theoretical single-crystal elastic constants (cij , c = (c11 c12 )/2, AZ = c44 /c ), Cauchy

pressure (c12 c44 ), and polycrystal elastic moduli (B, G, E, , AVR and B/G) for fcc

and bcc NiCoFeCrAlx alloys as a function of Al content. The unit is GPa except for the

dimensionless AZ , AVR , and B/G.

x

0

0.3

0.5

1.0

1.0

1.3

1.5

2.0

fcc

fcc

fcc

fcc

bcc

bcc

bcc

bcc

c11

271

246

233

214

214

208

205

197

c12

175

171

169

167

160

151

148

140

c44

189

177

171

158

152

150

149

147

c

48.0

37.3

32.2

23.5

27.2

28.1

28.5

28.3

AZ

3.94

4.75

5.29

6.85

6.72

5.59

5.34

5.26

(c12 -c44 )

-14.3

-6.12

-2.13

9.00

7.84

0.80

-1.66

-6.56

B

207

196

190

183

178

170

167

159

G

110

96

89

76

78

78

78

77

AVR

280 0.275 0.209

248 0.289 0.262

231 0.297 0.295

201 0.317 0.369

204 0.309 0.311

203 0.301 0.298

202 0.297 0.293

199 0.291 0.289

B/G

1.88

2.04

2.13

2.40

2.29

2.17

2.13

2.06

the fcc lattice and slightly increases that of the bcc lattice. At the same time, Al stabilizes thermodynamically the bcc structure relative to the fcc one (Figure 5.11 and 5.12).

Combining these two effects, we obtain that around the duplex region (Figure 5.13),

the NiCoFeCrAlx system has two very similar distinct local minima within the Bain

configurational space (described by c/a and volume) with a clear barrier between them

(Figure 5.14). One local

minimum corresponds to the bcc phase (c/a = 1) and another to

the fcc phase (c/a = 2). This situation is rather unusual for elemental cubic transition

metals and their alloys [134], for which the thermodynamically unstable cubic structure

is usually also dynamically unstable (or barely stable).

Negative Cauchy pressure has been associated with the covalent nature of the metallic

bond and is characteristic to brittle alloys [135]. According to Pugh [93] materials with

B/G ratio above 1.75 are ductile. For isotropic materials, the Pugh criteria for ductility implies > 0.26, which has been confirmed for bulk metallic glasses [94]. In the

case of NiCoFeCrAlx , alloys outside of the two phase region possess small or negative

Cauchy pressure, and their Pugh and Poissons ratios are also the lowest (Figure 5.13).

On the other hand, close to x = 1 both phases have large positive Cauchy pressure, and

large B/G and , indicating strong metallic character and enhanced ductility for these

systems. Our calculated Youngs moduli are very close for the fcc (201 GPa) and bcc

(204GPa) NiCoFeCrAl. In Figure 5.15, we show the change of Youngs modulus is from

70 to 370 GPa (77 to 355 GPa) for the fcc (bcc) NiCoFeCrAl along the different directions.

The experimental value of E (127 GPa) [20] is within this scope of our calculations.

49

4.00

2.72

3.42

2.83

2.70

2.25

1.67

1.08

2.66

0.50

2.64

-0.08

(Bohr)

2.68

-0.67

2.62

-1.25

-1.83

2.60

-2.42

2.58

-3.00

0.96

1.04

1.12

1.20

1.28

1.36

1.44

1.52

c/a

Figure 5.14. Energy contour (in mRy) for paramagnetic NiCoFeCrAl as a function

of the tetragonal ratio (c/a) and the Wigner-Seitz radius w.

350

bcc

300

fcc

250

200

150

E_exp.=127.0 GPa

100

50

001

111

110

Figure 5.15. Youngs modulus of NiCoFeCrAl (bcc and fcc structure) as a function

of direction including the three main cubic directions.

Chapter 6

Interlayer potentials

Within the theory of effective interaction potentials, the energy of different structural

models is usually expressed in terms of the model potentials. If the energy of a structural model is obtained by ab initio calculations or experiments, one can use different

inversion [70] is an efficient

inversion (d) is defined

in number theory. For the sum function

F (n) =

f (d),

(6.1)

d|n

f (n) =

(d)F (n/d),

(6.2)

d|n

d = 1,

1

r

(1) d has r distinct prime divisors,

(d) =

0

others.

(6.3)

Before defining the interlayer potentials (ILPs), we introduce the structural models

which are often used to derive the interactions between close-packed atomic layers.

These models are usually based on common close-packed layered arrangements such

as the fcc (111), hcp (0001) and dhcp (0001) structures shown in Figure 6.1. The stacking

sequence for the fcc (111) layers is ABCABC , for the hcp (0001) layers ABAB ,

50

51

Figure 6.1. The stacking arrangement for ABC, AB and ABAC structural models.

and for the dhcp (0001) layers ABACABAC . By the ABC structural model we mean

a stacking sequence as in the case of the fcc (111) lattice and with the interlayer distance

as the only free lattice parameter. Similarly, the structural models AB and ABAC correspond to the hcp (0001) and dhcp (0001) lattices with variable interlayer distances. For

the ABC model, the ILPs are denoted by AB , BC , CA , AC , BA , CB , AA , BB , and

CC . Similarly, the potentials are AB , BA , AA , BB in the AB structural model, and

AB , BA , AC , CA , BC , CB , AA , BB , and CC in the ABAC structural model. Due to

the symmetry, we have AB =BC =CA , AC =BA =CB , and AA =BB =CC .

By definition, the ILP ab (d) is between neighboring layers, i.e. between the A-B, A-C

and B-C layers, and aa (d) between aligned layers, i.e. between the A-A, B-B and C-C

layers. Here d represents the coordinate perpendicular to the layers.

In terms of the ILPs ab and aa , the total energy of the ABC structural model is given

by

E ABC (d) =

(6.4)

n=1

where d is the interlayer distance (separation between adjacent atomic layers) and the

energy is per 3 atoms. For the AB and ABAC models, the corresponding total energy

(per 2 and 4 atoms, respectively) may be written in the following forms

52

AB

(d) =

(6.5)

n=1

and

ABAC

(d) =

(4ab ((2n 1)d) + 2ab ((4n 2)d) + 2aa ((4n 2)d) + 4aa (4nd)). (6.6)

n=1

In the present thesis, we only use the ABC and AB structures as the calculation models

for the ILPs inversion.

We can solve ab and aa if E ABC and E AB are known. The energy difference ab (d) is

defined as

3

ab (d) = E ABC (d) E AB ( d),

2

then we obtain two following formulas

ab (d) =

ab ((3n 2)d)

n=1

or

ab (d) =

(6.7)

3

ab ((3n )d) +

ab ((3n 1)d),

2

n=1

n=1

(6.8)

(6.9)

r(n)ab (b(n)d).

n=1

Table 6.1. The data list for the coefficients b(n) and r(n) Eq. 6.9.

b(n)

r(n)

1 2 3 4 5

1 23 2 4 92

1 -1 1 1 -1

6 7

5 7

1 1

8

15

2

-1

9 10

8 10

1

1

Then it follows that

ab (d) =

n=1

R(n)ab (B(n)d).

(6.10)

{

R(n) =

53

0

if B(n)

/ {b(n)}.

(6.11)

According to Chen-Mobius

inversion method [70], we can get

ab (d) =

(6.12)

J(n)ab (B(n)d),

n=1

J(n)R(B 1 (

B(n)|B(k)

B(k)

)) = k,1 .

B(n)

(6.13)

The coefficients B(n), R(n) and J(n) are listed in Table 6.2.

Table 6.2. The data list for the coefficients B(n), R(n) and J(n) in Eq. 6.13.

1

B(n) 1

R(n) 1

J(n) 1

3

2

-1 1

1 -1

3

2

9

4

5

3

0 0

1 -2

27

8

7 8

4 92

0 1 -1

1 0 -2

9 10

5 81

16

1

0

-1

1

aa (d) = E

AB

d

1

( )

ab ((n )d),

2

2

n=1

(6.14)

aa (d) =

(n)aa (nd),

(6.15)

n=1

n = 1,

1

s

(1) n = p1 p2 . . . ps (p1 = p2 = . . . = ps ),

(n) =

0

others.

where the coefficient (n) are listed in Table 6.3.

(6.16)

54

(n)

1

1

2

-1

3 4

-1 0

5 6

-1 1

7 8 9 10

-1 0 0

1

inversion method. According to

Eqs. 6.5 and 6.15, the premise conditions of getting ab and aa are to obtain the energy

E ABC and E AB as a function of d.

6.3

inversion to get the ILPs.

In order to be able to provide the ILPs for an arbitrary distance, we need to assume

an analytical expression and fit the ab initio data using that form. According to the

distributions of the data, we employ different fitting functions.

For fitting the converted interlayer potentials inverted from the CASTEP calculations,

we used the Rahaman-Stillinger-Lemberg (RSL2) function

(

)

r

y 1 Rij

a1

b

e 1 (rij c1 )

a2

b

e 2 (rij c2 )

a3

.

b

e 3 (rij c3 )

(6.17)

1+

1+

1+

Here rij represents the interlayer distance. Note that there are totally 12 adjustable parameters in this function (D0 , y, R0 , a1 , a2 , a3 , b1 , b2 , b3 , c1 , c2 , and c3 ) and thus it offers a

rather flexible form to describe the pair interactions between layers. In Table 6.4, we list

the parameters. R0 is often set to 1.0.

ij = D0 e

The ILP ab is similar to the interatomic pair potential. At the equilibrium interlayer

distance, the ILP ab takes its minimum value. Note that ILP aa is plotted only for large

interlayer distances, since Eqs. 6.4 and 6.5 involve aa (d) only for d 2d1 , where d1

stands for the shortest interlayer distance defined.

55

0.2

0

0.2

0.4

Inversion

Fitting for

0.6

ab

0.8

1

0.1

0.2

Inversion

0.3

Fitting for aa

0.4

0.5

0.6

3.5

4.5

5.5

Figure 6.2. The CASTEP ILPs ab (a) and aa (b) of fcc (111) planes for Al, the dis

crete points are the ab initio data obtained by Chen-Mobius

inversion and

the lines represent the fitting potentials.

Table 6.4. The RSL2 parameters of the ILPs ab and aa from Eq. 6.17. The units

are indicated.

Parameter

ab

D0 (eV)

-7.372035

R0 (A)

1.000000

y

1.412776

a1 (eV)

8381.2168

1 )

b1 (A

3.150760

c1 (A)

1.567630

aa

-302.853273

1.000000

2.588845

-0.243731

365.406083

3.698911

Parameter

ab

a2 (eV)

-602.0528

1 )

b2 (A

2.819443

c2 (A)

1.766391

a3 (eV)

-7620.8720

1 )

b3 (A

3.23390

c3 (A)

1.565706

aa

-69.426275

7.853272

0.000432

0.651101

9.464628

1.409775

56

0

ab potential

0.02

0.04

0.06

0.08

0.1

3

2

x 10

0

10

aa potential

5

10

15

20

4

10

12

14

Figure 6.3. The EMTO ILPs (ab upper panel and aa lower panel) for Pd fcc (111)

planes plotted as a function of the interlayer distance.

In the calculations of Pd, Ag and Pd-Ag alloy with the EMTO-CPA method, we used

the Morse function [91] to fit the discrete data. We found that the Morse function could

represent well the data of the inversion of ILPs. The Morse function is an exponential

function

E(w) = a + bed + ce2d

(6.18)

written in terms of the average interlayer distance d. Here , a, b and c are the four

independent Morse parameter. In order to clearly express the ILP ab , we can write the

Morse function in another form

( Rd 1)

ab (d) = D0 e

2 ( Rd 1)

2D0 e

+ E0 .

(6.19)

Td

aa (d) = Y0 + A1 e

Td

+ A2 e

(6.20)

Figure 6.3 shows the interlayer potential ab and aa for the fcc (111) planes of Pd.

57

0

0.2

0.4

Interlayer

potential

Ab initio

0.6

0.8

2

0

0.2

2.5

3.5

4.5

b

Interlayer

potential

Ab initio

0.4

0.6

0.8

2

2.5

3.5

4.5

Figure 6.4. Comparison between the ab initio total energies of the structure model

ABC (panel a) and AB (panel b) (symbols) and the corresponding total energies obtained from the ILPs (lines). The energies are plotted as a function

of interlayer separation.

6.4

By contrasting the energies of the ABC and AB models as derived from the ILPs and the

original ab initio total energies, we learn about the accuracy of the inversion and fitting

procedures. Figure 6.4 shows this comparison taken Al as example. We find that the

ILPs reproduce well the results of the ab initio calculations from CASTEP method.

For the IILPs derived from the EMTO-CPA method, we compared the energies of the

ABC and AB model derived from the interlayer potentials (i.e. Eqs. 6.4 and 6.5) with the

ab initio total energies, At the same time, we also employed the ABAC model to check

the ILPs (in Eq. 6.6). A comparison is shown for Ag in Figure 6.5 for the ABC model

(upper panel), AB model (middle panel) and ABAC model (lower panel). We find that

the present interlayer potentials reproduce well the results of the ab initio calculations

including the ABAC model system which was not used to derive the potential.

The good agreement between the ILPs and ab initio calculations demonstrates the robustness of our approach.

58

ABC

0.02

0.04

E (Ry/layer)

0.06

2

0

AB

Ab initio data

Interlayer potentials

0.02

0.04

0.06

2

0

ABAC

0.02

0.04

0.06

2

d ()

Figure 6.5. Comparison between the ab initio total energy and the one calculated

with the ILPs for the Ag. Results are shown for the ABC model (upper

panel), AB model (middle panel) and ABAC model (lower panel).

Chapter 7

Properties related to atomic layers

7.1 Equilibrium properties

In order to get ILPs, we need to calculate equilibrium lattice parameter and cohesive

energy. Choosing the proper exchange-correlation approximation functional is particulary important. Different exchange-correction functionals have been compared in

Refs. [142146]. It was reported that PBE often overestimates the lattice constants and

underestimates the cohesive energy. On the other hand, PBEsol may accurately describe

the equilibrium properties of dense solids and their surfaces [147]. In the present thesis,

we employed the PBE generalized gradient approximation for Al, Ni, Cu, Ag and Au

in CASTEP and the modified PBE (PBEsol) for Pd-Ag random alloy in EMTO.

Table 7.1. Theoretical lattice constants (a, in units of A),

the interlayer distances (d0 , in

within the fcc (111) layers (a0 , in units of A),

units of A) for five fcc metals. For comparison, some experimental lattice constants and the deviations between theory and experiment (a/a, in %) are also

shown.

Metal

Al

a (PBE)

4.0492

a (Exp.) 4.0495 [149]

a/a

0.01

a0

2.8634

d0

2.3381

Ni

3.5294

3.5240 [150]

0.15

2.4918

2.0346

Cu

3.6261

3.6147 [151]

0.32

2.5560

2.0871

59

Ag

4.1384

4.0857 [152]

1.29

2.8890

2.3589

Au

4.1811

4.0789 [153]

2.51

2.8838

2.3548

60

For the elemental Al, Ni, Cu, Ag and Au metals, Table 7.1 shows the calculated lattice

parameters (a), the distance between two nearest neighboring atoms inside the close

packed atomic layers (a0 ), and the equilibrium interlayer distance (d0 ) for the ABC structure model. In general, the theoretical and experimental data are consistent with each

other, the average relative deviation between theory and experiment being below 1%.

The lattice parameters of Al, Ni and Cu are in good agreement with the experimental

data, whereas the PBE lattice parameters are somewhat larger than the corresponding

experimental values for Ag and Au.

Considering the large difference between the calculation from the PBE results and the

experimental data, we decided to use the PBEsol approximation to calculate the Ag, Pd

and Pd-Ag alloys in the EMTO-CPA method. Our calculations shown in Table 7.2 are in

good agreement with the experimental data.

Since EMTO is a muffin-tin method, special care must be taken on how the energies

are computed with this method for large interlayer distances. To this end, first we construct two hexagonal structures with six layers as the ABCABC and ABABAB models.

By that we can minimize the errors coming from different Brillouin zone samplings.

Next, when changing d we ensure that the linear overlap between the individual atomic

spheres (muffin-tin potential wells) remains below 15% in order to keep the overlap error small [63, 148]. Within this constrain, the range of allowed d/a0 values (a0 is the

equilibrium interatomic distance in the fcc lattice) in EMTO calculations is set to 0.7170.919. To illustrate the degree of lattice distortion upon changing d/a0 , in Figure 7.1

we show the Madelung constants of the ABC and AB structures as a function of d/a0 .

It is seen that within the above d/a0 interval, the ideal fcc or hcp Madelung constants

(both of them being close to 1.7917) drop below 1.7870, indicating a substantial reduction of the packing ratio as the interlayer distance starts to deviate from its equilibrium

value by more than 0.1a0 . For such open structures, the accuracy of the muffin-tin

approximation is not sufficient to produce highly accurate energies and thus interlayer

potentials. In order to overcome this problem, in EMTO calculations we consider additional systems with interlayer separation equal with the double of the equilibrium

separation dABC or dAB . Namely, for the ABC (AB) model we set up a supercell with

unit cell containing six (four) layers ordered according to AcBaCb (AcBc), where the

capital letter stand for atoms and small letters for empty sites, containing empty potential wells. With so the dressed-up structure we are able to compute EABC (2dABC ) and

in

EAB (2dAB ) with sufficiently high accuracy (see the separate symbols around 4.7 A,

Figure 6.5).

61

1,792

1,790

Madelung constant

0.8165

1,788

1,786

1,784

1,782

ABC

1,780

AB

1,778

1,776

1,774

1,772

0,60

0,65

0,70

0,75

0,80

0,85

0,90

0,95

1,00

1,05

d/a

Figure 7.1. The Madelung constant versus d/a0 value for the ABC and AB structural models.

Table 7.2. Equilibrium lattice constants (a) for fcc Pd, Ag and Pd0.5 Ag0.5 . The experimental

results corrected for the zero-point phonon term are shown in parentheses [154,155].

The quoted experimental values for Pd0.5 Ag0.5 were obtained for Pd0.5087 Ag0.4913

and Pd0.462 Ag0.538 (3.9850 A)

[137]. Previous theoretical values were ob(3.9766 A)

tained using full-potential methods [143, 144] as well as the EMTO-CPA method

[138]. In the lower panel of the table, a0 and d0 stand for the equilibrium nearestneighbor distance in the fcc (111) plane and the equilibrium interlayer distance perpendicular to the (111) plane as determined from the corresponding calculated a

values. dABC and dAB are the calculated equilibrium interlayer distance for fcc (111)

and hcp (0001) models, respectively. All parameters are expressed in units of A.

a (DFT)

a (Expt.)

a (Error)

a (Theo.)

a0

d0

dABC

dAB

Pd(EMTO) Pd(CASTEP)

3.8908

3.8795

3.881 (3.877) [154]

3.879 (3.875) [155]

+0.4%

-0.06%

3.876 [143], 3.882 [144]

2.7512

2.7432

2.2464

2.2389

2.2460

2.2419

2.2666

2.2659

3.9721

4.0681

4.0605

3.9766 [137]

4.069 (4.064) [154]

3.9850 [137]

4.061 (4.056) [155]

-(0.110.32)%

+0.1%

-0.08%

3.9711 [143]

4.053 [143], 4.059 [144]

2.8087

2.8766

2.8712

2.2933

2.3487

2.3443

2.2933

2.3489

2.3343

2.3080

2.3603

2.3389

62

For cubic crystals, there are three independent single-crystal elastic constants c11 , c12

and c44 . The elastic constant c44 is often referred to as the shear elastic constant and is

based on the deformation of the crystal along the fcc 111 direction. It is defined as the

second order derivative of the total energy with respect to the lattice strain. Using the

present ILPs, c44 may be expressed in terms of the second order derivatives of the ab (d)

and aa (d) potentials as a function of the interlayer separation d.

We notice that changing the interlayer distance while keeping the in-plane lattice constants fixed leads to volume change. This gives a term proportional to the bulk modulus, which should be taken into account when extracting c44 from the above total energy

curvature.

Taking Pd, Ag and Pd-Ag alloys as examples, we compared the c44 from the ILPs with

experimental data and ab initio calculations. The data from the ILPs are in good agreement with the ab initio calculations. The results of the EMTO method are consistent

with those from the CASTEP calculations. All theoretical results are slightly larger than

the experimental data.

Table 7.3. Elastic constant c44 (in GPa) for fcc Ag, Pd and PdAg. The EMTO and CASTEP

results were obtained using the ILP and DFT approaches, and are compared to the

available experimental data from Refs.

c44 (ILP)

105

107

83

55

61

c44 (DFT)

112 [138]

92a

94 [138]

61 [138]

69a

c44 (Expt.) 71.2 [156]

51.1 [156]

a

results obtained for the ideal interlayer distance.

In close-packed lattices, the partial dislocations are connected by stacking faults. The

size of the stacking fault energy (sf ) determines the width of the faulted ribbon and

by that influences the dislocation propagation mechanism and ultimately the plastic

deformation. In fcc metals, one can distinguish intrinsic stacking fault (ISF), extrinsic

stacking fault (ESF) and twin stacking fault (TSF).

The ideal fcc (111) arrangement is shown in Figure 7.2a. In this system the stacking

is ABC ABC ABC ABC (Figure 7.2b), i.e. a periodically repeated ABC sequence.

Introducing a stacking mistake leads to the so called stacking fault. The intrinsic fault is

displayed in Figure 7.2c. This is obtained be removing one atomic layer from the ideal

63

Figure 7.2. The stacking arrangement for fcc (111) planes, the perfect stacking arrangement (a), one dimension arrangement of viewing each layer as a

unity (b) and (d), the stacking arrangement with an intrinsic fault (c).

.

fcc (111) arrangement and can be expressed as ABC ABC ABC .. BC ABC ABC

.

(Figure 7.2d), where .. marks the missing layer.

The formation energy per area of a stacking fault in an otherwise perfect crystal is determined by the energy difference between structures with (Esf ) and without (Et ) the

stacking fault, viz.

sf =

Esf Et

,

A

(7.1)

where Et refers to the same number of layers (N ) as the faulted structure and A is the

area of the stacking fault plane.

In ab initio calculations of the stacking fault energy, the supercell approach and the axial

interaction model (AIM) have been applied [136, 139]. A comparison of these two approaches has been reported [140]. In the supercell model, Esf represents the total energy

of a supercell containing N layers and one stacking fault and Et = N Efcc , where Efcc

is the energy per atom of the ideal fcc stacking. Within the AIM approach including

interactions up to the third order, the ISF energy may be expressed as

sf =

.

A

(7.2)

64

In this expression all total energies are per atom. The total energies from Eqs. 7.1 and

7.2 can be determined either by direct DFT calculations or via Eqs. 6.4, 6.5 and 6.6 using

the ILPs.

For intrinsic stacking faults, the stacking fault energy is expressed directly with ILPs as

following

sf =

n=1 (3n

A

aa (3nd)]

.

(7.3)

The extrinsic stacking fault (ESF) is obtained by inserting an extra layer in the ideal

. .

fcc (111) arrangement. Its stacking is ABC ABC.. B .. ABC ABC , which is also

viewed as two next-nearest intrinsic stacking faults. While the twin stacking fault is

a plane boundary between two fcc stacking sequences with opposite orientation, i.e.

ABCABACBA .

The values of stacking fault energy are usually very small (order of 10-200 mJ/m2 ). Thus

obtaining accurate stacking fault energy is a rather difficult task in the experiments. Due

to the experimental uncertainties involved (e.g., temperature and alloying effects), the

reported values show large scatter listed in Table 7.4. In our calculations of the stacking

fault energy for Al, Ni, Cu, Ag and Au, we constructed the supercell with 12 layers

vacuum layers for the perfect stacking and the stacking with intrinsic stacking

and 14 A

fault. In the supercell method, the intrinsic stacking fault is the middle of 12 layers, the

same surface layers are constructed for the two stackings. So the total energy difference

between two stackings is the intrinsic fault energy. We found a good agreement between

the stacking fault energies from the ILPs and ab initio calculations (Table 7.4).

For Pd-Ag alloys and Pd and Ag, in addition to the comparisons between the supercell

and AIM results, we also contrast the values from EMTO and CASTEP.

The ILPs may be used to establish the interaction between two intrinsic stacking faults

located within the same plane family. To this end, we considered an ideal fcc supercell ABCABCABCABC from which we removed two layers separated by a specific

.

.

.

number of atomic layers (Ns ). For instance, in ABC..BCA..CABC (where .. stands

for the missing layer) the two ISFs are separated by three atomic layers (Ns = 3). The

EMTO-ILP formation energies for the above double-ISF in Pd, Ag and Pd0.5 Ag0.5 are

plotted in Figure 7.3 as a function of the number of layers separating the two faults. It

is expected that with increasing Ns , the energy of double-ISF should converge to twice

of that of the ISF from Table 7.3 (ILP supercell results). Indeed, for all three systems the

double-ISF energy reaches with good accuracy the converged value already for Ns 3.

For smaller separations, there is a clear attractive interaction between the ISFs. To understand this, we should realize that when the two ISFs become next-nearest neighbors

(Ns = 1), then the double-ISF reduces to an extrinsic stacking fault, viz. configuration

. .

ABC..B..ABCABC . The calculated (EMTO-ILP) ESF energies are 192.4, 20.6 and 89.6

65

mJ/m2 for Pd, Ag and Pd0.5 Ag0.5 , respectively. These values are marginally larger than

the corresponding ISF energies, meaning that energetically it is slightly more favorable

to have one ESF than two ISFs. It is noticeable that the double-ISFESF reconstruction

happens without a sizable energy barrier (except the one associated with the shift of the

atomic layers parallel to the stacking fault).

Using the ILPs derived from EMTO calculations, we also determined the formation

energy of a twin stacking fault described by the configuration ABCABCBACBA

for Pd, Ag and Pd0.5 Ag0.5 . The theoretical TSF energies are 155.7, 9.9 and 52.0 mJ/m2 ,

respectively. The small values of TSF indicate that these faults are created much easier

than the intrinsic and the extrinsic stacking faults.

Table 7.4. Stacking fault energies (sf , in units of mJ/m2 ) for Al, Ni, Cu, Al, and Au. The displayed data are as follows: ILP present results obtained using the interlayer potentials;

DFT present results obtained from direct DFT calculations; TBP, TB: calculations based

on tight-binding method; FLMTO: results of full potential linear-muffin-tin orbitals

calculations; EAM: calculations from the embedded-atom-method potentials.

Metal

ILP

DFT

TBP [157]

TB [158]

FLMTO [159, 160]

Potential [161]

EAM [162]

EAM [163]

Exp. [164]

Exp. [165]

Exp. [166]

Al

Ni

Cu

Ag

Au

180

213

33

16

26

180

183

34

22

41

305/265

21/15

1/0

96

18

29

50

164

46

146.0/95.4

304.4/120.3 20.6/33.5

352/361

104/109

119/121

67/73

41/44

146.47

90.99

74.59

44.19

61.58

170/200/240 64-140/410

40/169

21/26-58

24-47

166

64-140/410 40/45/169

24-47

16/43/58

166

128/250

48/55/78

16/22

Pd(E)

Pd(C)

PdAg(E)

Ag(E)

Ag(C)

a

sf (ILP)

185.6

199.3

81.1

15.0

24.7

sf (ILP)b

186.9

227.0

87.9

16.8

26.9

a

c

sf (DFT)

185.0

178.5

76.8

26.6

26.0/28.4c

b

c

sf (DFT)

192 [167]

164.3

83 [167]

23 [167] 19.5/20.3c

sf (Expt.)

180 [168]

a

b

c

AIM results; supercell results; results obtained for the ideal interlayer distance;

E(C) stands for the EMTO (CASTEP) method.

66

35

30

25

Ag

20

200

150

2Eist

Ag0.5Pd0.5

100

400

300

Pd

200

1

Figure 7.3. (Color online) The formation energy for two parallel intrinsic stacking

faults for fcc Pd, Ag and Pd0.5 Ag0.5 plotted as a function of the number of

atomic layers between the two faults. The dashed lines show the energy

corresponding to two non-interacting intrinsic stacking faults.

The surface energy is defined as the surface excess free energy per unit area of a particular crystal facet. The surface energy is often calculated using the supercell model in

Figure 7.4. We construct a supercell consisting of N atomic layers perpendicular to the

surface and separated by a wide vacuum layer that prevents the interaction between

neighboring surfaces. Then the surface energy is given by the formula

Es N Efcc

,

(7.4)

2A

where Es is the total energy of the supercell, Efcc is the bulk energy per layer and the

factor 2 arises from the two surfaces of the slab. The above energies can be computed

either by direct ab initio calculations or using the ILPs.

s =

Alternatively, in the case of the ILP-based description of the fcc (111) surface, we may

consider a semi-infinite surface geometry CBACBAVacuum , so that there is only

one surface layer. Then the surface energy is the sum of the ILPs between the atomic

layers and the removed layers, viz.

s =

k=1 [(3k

,

2A

(7.5)

where k represents a layer in the surface model and also indicates the number of inter-

67

Figure 7.4. Schematic plot of the structures used to calculate the surface energy.

Panel (a): perfect fcc (111) stacking arrangement; panel (b): 12-atomic layers slab geometry separated by vacuum.

The surface energies calculated with the ILPs and DFT are listed in Table 7.5. In general,

the ILPs and DFT formation energies are consistent with each other. For Ag (Pd) both

EMTO and CASTEP results based on the ILP calculations are slightly smaller (larger)

than the those calculated directly (DFT). On the other hand, for Pd0.5 Ag0.5 alloy, the

DFT and ILP values turn out to be very close to each other. Beyond the obvious numerical errors associated with surface energy calculations, one possible explanation for the

above discrepancies is that the surface physics is not completely captured by the ILPs.

The surface energies of close-packed metal surfaces show a weak layer relaxation dependence. The ILPs may be used to establish the size of the surface relaxation and

its impact on the formation energy. Changing the interlayer distance between surface

layer and its nearest neighboring layer in the semi-infinite surface geometry, we calculated a series of surface energies and used the interpolation method to obtain the

smallest surface energy sr , whose corresponding surface interlayer distance is ds12 after surface relaxation (shown in Table 7.5). The present theoretical equilibrium surface

(top-layer) and bulk interlayer distances are shown in Table 7.5. For all three metals,

the fcc (111) surfaces show small outward relaxations characteristic to the close-packed

surfaces of late transition metals [171174]. However, the impact of surface relaxation

on the surface formation energy in all cases remains below 0.5%, which is consistent

with the negligible effect reported for 4d metals [175].

7.5

Phonon dispersion

The vibration of atoms in the crystal is correlated and the collective vibration forms a

wave of allowed wavelength and amplitude. The quantum of such lattice vibration is

68

and

Table 7.5. Surface energy s (in mJ/m2 ), bulk equilibrium interlayer distance db12 (in A),

For ILP, the numbers in parenthesis

surface equilibrium interlayer distance ds12 (in A).

are the surface energies obtained for the semi-infinite surface model. sr (in mJ/m2 )

represent the surface energy after surface relaxation.

s (ILP)

s (DFT)

db12

ds12

sr (ILP)

2377.4

2189.0

1584.4

891.1

959.9

(2378.4)

(2192.9)

(1584.7)

(891.1)

(959.9)

2076

1877

1591

1201

1047/1235a

2.2460

2.2419

2.2933

2.3489

2.3343

2.2880

2.2764

2.3219

2.3674

2.3513

2365.2

2185.7

1579.7

889.7

958.5

a

2

called phonon. The phonon dispersion describes the wave vector dependence of the

phonon frequencies.

To establish the phonon spectra for a system, we first get the force constant matrix,

given by the second order derivative of the internal energy with respect to the Cartesian

coordinates. The force constant matrix, F , between two atoms i and j is given by

Fij (k) =

2U

(

)eik(rij +R) ,

(7.6)

where and are position vectors in the Cartesian coordinates. The dynamical matrix

D is

Dij =

1

(mi mj )1/2

Fij (k),

(7.7)

where mi and mj are the masses of atom i and j. Further details about the phonon

dispersion from the force constant matrix are discussed as in Ref. [141].

Possessing the phonon spectrum, one can predict a series of thermo-physical properties.

The phonon dispersions are represented by the interatomic forces derived from the interatomic potentials. Here we calculated the phonon dispersion for the fcc (111) planes

using the ILPs.

the whole fcc (111) layer as a unit, we consider the mass of the

Viewing

2

atoms in the 3a /4 area as the mass of the layer (a is the fcc lattice constant from Table 7.3). For each layer, we use the equivalent-atom model to represent the total layer

and the masses of these equivalent-atoms are identical.

Although the three layers in the fcc (111) planes are only different because of the relative

position of atoms, the one-dimension primitive cell contains three different atoms in

our phonon calculations, so there are six branches in the phonon dispersion. Note that

69

Frequency (THz)

Pd

Pd-Ag

Ag

Figure 7.5. The phonon dispersion for Pd and Ag metals and Pd0.5 Ag0.5 alloy.

the optical branches from Figure 7.5 are in fact the folded-in acoustic branches (there

is no gap at the zone boundary between the branches). In the fcc with one atom per

primitive cell, the real phonon dispersion only has two acoustical branches along the

fcc 111 direction, with degenerated transversal branches. Since we investigate the

interactions along one direction, the distinct number of phonon branches is reduced

along the principal symmetry direction G-Z as shown in Figure 7.5. Here we would like

to make an Erratum to the Supplements: in the figure of the dispersion phonon from the

published papers there is a small mistake in the transversal phonon branch as a result

of the employed phonon-calculation software.

Furthermore, the phonon density of states from the Supplements represent the density

of states of a hypothetical one-dimensional lattice and thus should not be compared to

the real three-dimensional results.

The interlayer interaction for Pd is stronger than that for Ag, and thus the vibrational

frequencies versus k for Ag are weaker than those for Pd. The vibrational frequency of

the Pd0.5 Ag0.5 alloy is in between those obtained for Pd and Ag metals. To our knowledge, this is the first phonon spectra presented for completely random alloy and calculated using the mean-field coherent potential approximation.

Chapter 8

Concluding remarks and Future work

Based on the available experiments, the structural properties and hardness of singlephase high entropy alloys were discussed. Using the exact muffin-tin orbitals method

in combination with the coherent potential approximations (EMTO-CPA), we investigated the structural, electronic and elastic properties of single-phase high-entropy alloys. Our ab initio predicted structural properties are consistent with the experimental

results, especially for the equilibrium volume and phase transformation. According to

the calculated elastic properties from ab initio alloy theory, we find that: 1) NiCoFeCr

and CuNiCoFeCr are more isotropic and less ductile than the Ti-containing single phase

alloys (CuNiCoFeCrTix with x & 0.4 and NiCoFeCrTi) in CuNiCoFeCrTix HEAs, 2) for

refractory- HEAs, we may design the elastically isotropic alloys according to the average

valence electron concentration VEC 4.72, 3) for the NiCoFeCrAlx HEAs with fccbcc

phase transformation, the HEAs abound the equimolar NiCoFeCrAl composition have

superior mechanical performance as compared to the single-phase regions.

Interlayer Potentials suit to describe the properties related to layers in layered materials. We should mention that due to the complex magnetic interactions along the closepacked layers, there are some limitations for using the ILPs to investigate the related

properties of magnetic materials. For the present systems, the high accuracy of the ILPs

originates from the fact that the total layer is considered as a unit and in a layered materials the interlayer interactions are usually much weaker than the interaction within

the layer. For some layered materials, for example graphite and BN, ab initio tools do

not accurately describe the interlayer cohesive energy. In such cases, one may use the

Chen-Mobius

inversion to get accurately ILPs starting from the experimental data.

The present results obtained for the random solid solutions show that the EMTO-CPA

method is a powerful tool to investigate complicated alloys and is able to provide accurate ILPs. For future works, I will continue to use the EMTO-CPA method to study

the high entropy alloys (HEAs). After performing an intensive theoretical investigation of the HEAs, we will use the above ILPs technique to describe the layer dependent

properties of this complex and promising family of engineering alloys.

70

Acknowledgements

First, I am grateful to my supervisors Prof. Levente Vitos and Prof. Nanxian Chen for

giving me the opportunity to learn the EMTO-CPA method and the Mobius

inversion,

for always showing a great interest to my work and for professional guidance.

Prof. Lajos Karoly Varga, at the Institute for Solid State Physics and Optics, Wigner

Research Center for Physics, Hungarian Academy of Sciences, Budapest, thank you for

providing the chance to know the experimental process of high-entropy alloys. I also

appreciate Prof. Jiang Shens help, at the Institute for Applied Physics, University of

Science and Technology, Beijing.

Lorand, Erna, B. Narisu, Hualei, Song, Wei, Guisheng, Xiaoqing, Stephan, Andreas,

Dongyoo: many thanks for helpful discussions. I would like to thank all the members

of the AMP group for creating an inspiring environment for my learning and for help.

I am grateful to Qingmiao Hu, Xiaojian Yuan, Ping Qian, Yudong Wang, Gang Liu, and

Hubin Luo for their great support.

The Swedish Research Council, the European Research Council, the China Scholarship

Council, National 973 Project of China, Swedish Foundation for International Cooperation in Research and Higher Education (STINT), and the Hungarian Scientific Research

Fund are acknowledged for financial support.

Last but not least, I would like to express my deepest thanks to my wife and daughter,

for their support and love. I also acknowledge my parents and my brother for great

support and encouragement.

71

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