HIGH ENTROPY

ALLOYS

DEVANG GANDHI
M.TECH 1ST YR
IIT ROORKEE
16544016
INDEX
L i t e r a t u re Re v i e w

Introduction

P h a s e Fo rm a t i o n Ru l e s

F o u r C o r e E ff e c t

Pro c e s s i n g Ro u t e

Mechanical Properties

Examples

Applications

Re f e re n c e s
LITERATURE REVIEW

200 High Entropy Alloys were discovered by Yeh

4 and Cantor.

200 Four Core Effects were Observed in High

6 Entropy Alloys

200 Phase Formation Rules were framed by Zhang

8 et al.

201 Applications of CoCrFeMnNi in Sub-Zero

4 Region.

201 Future Prospects of HEA being considered.

6
 INTRODUCTION

5-13 principal elements

% of Elements between 5% and 35%
Density 6.7-7.3 gm/cm3
Hmix between -10kJ/mol and 5kJ/mol
Sconfig >1.5R
Difference in Atomic Radii < 6.6%

Fig 1. CoCrFeMnNi FCC High Entropy Alloy

Table 1 : Sconfig vs N
N 1 2 3 4 5 6 7 8 9 10

Sconfig 0 0.69 R 1.1 R 1.39 R 1.61 R 1.79 R 1.95 R 2.08 R 2.2 R 2.3 R
(-R)

Fig 1 Ref : Wang S. (2012) Atomic Structure Modeling of Multi-Principal Element Alloys by the Principal of Maximum
Entropy, Entropy 15, 5536-5548
PHASE FORMATION RULES

Hmix =

Sconfig = -R

Gmix = Hmix - TSmix

Fig. 2 : Variation of Hmix with for a number of alloys

Fig 2. Ref : Tsai MH, Yeh J (2014) High Entropy Alloys: A Critical Review Mater. Res. Lett. 2, 107-123
PHASE FORMATION RULES

Possible Elemental Compounds Random Partially

States Phase Solid Ordered Hmix =
Solutions Solid
Solutions
Hmix ~0 Large Medium Medium
Negative Negative Negative
Sconfig = -R
-TSmix ~0 ~0 -RTln(n) <-RTln(n)

Gmix ~0 Large
Negative
Large
Negative
Large
Negative Gmix = Hmix - TSmix
Solution Parameter Crystal Structure

Single Solid > 1.1 BCC
Solution
< 6.6 VEC < 6.87
=
FCC
-15 kJ/mol < Hmix < 5 VEC > 8

kJ/mol

=
Ordered and
Disordered < 6.6 BCC+FCC
Solid
Solution
-22 kJ/mol < Hmix < 7 6.87 < VEC < 8
kJ/mol
Table 2 : Determination
of Crystal Structure

FOUR CORE EFFECT

Thermod
ynamics
High
Entropy

High
Structure Entro Propertie
Lattice py s Cocktail
Distortion Effect
Alloy
s

Kinetics
Sluggish
Diffusion
 FOUR CORE EFFECT HIGH ENTROPY EFFECT

Formation of Solution Phase to

render Simple Microstructure.

High Configuration Entropy

suppresses Ordered phase formation,
especially at Higher Temperatures.

Enhances formation of solution

phase, increase strength and
ductility of solution phase due to
solution hardening.

Stronger Bond Energies Enhance

Solid Solution & Inhibits formation of
Intermetallics.
Fig 3. : Variation of Potential Energy with distance between Lattice Sites

Fig 3. Ref : Yeh J. (2015) "Physical metallurgy of high-entropy alloys" JOM, 67, 2254-2261.
FOUR CORE EFFECT LATTICE DISTORTION EFFECT

Every atom in multi-principal

element matrix is surrounded by
different kinds of atom and suffer
lattice strain.

Severe Lattice Distortion can

increase Hardness and Strength by
Solid Solution Hardening.

Factors contributing to the Lattice

Strain include :
Atomic Size Difference
Difference in Bonding Energies
Crystal Structure

Fig 4. : Distorted or Strained Lattice of High Entropy Alloy

Fig 4. Ref : Yeh J. (2015) "Physical metallurgy of high-entropy alloys" JOM, 67, 2254-2261.
 FOUR CORE EFFECT SLUGGISH DIFFUSION EFFECT

Vacancy Concentration for

Substitutional Diffusion is limited in
HEA.

Positive Enthalpy of Formation and

Excess of Mixing Entropy needed.

Higher Activation Energy needed,

Slower Diffusion. Only one HEA
tested till date, CoCrFeMnNi.

Slower Diffusion indicates Slower

Kinetics or Slower Phase
Transformation. Hence, better
Microstructure and Property control.
Fig 5. : Normalized Activation Energy of Diffusion
for Cr, Mn, Fe, Co and Ni in different matrix

Fig 5 Ref : Tsai KY, Tsai MH, Yeh JW (2013) Sluggish diffusion in Co-Cr-Fe-Mn-Ni high-entropy alloys. Acta Mater
61:48874898
FOUR CORE EFFECT COCKTAIL EFFECT

Alloyed Pleasures : Multi-Metallic Cocktails

S. Ranganathan: Alloyed pleasures: multimetallic cocktails, Curr. Sci., 2003, 85, 14041406.

overall effect resulted from mutual interactions among composing elements,

which would bring excess quantities to the average values simply predicted by the
mixture rule
E. J. Pickering, N. G. Jones: High-entropy alloys: a critical assessment of their founding principles and future prospects, Int. Mat. Reviews,
2016, 61, 183-202

the overall effect from composition, structure, and microstructure

J.W. Yeh: Physical metallurgy of high-entropy alloys, JOM, 2015, 67, 22542261.
PROCESSING ROUTES

Schematic of Fabrication Process of High Entropy Alloys

 PROCESSING ROUTES

(a) Arc Melting (b) Bridgman Solidification

Fig 6. : Processing from the Liquid State

Fig 6. Ref : Ioannis S.Aristeidakis Maria-Ioanna T.Tzini (2016) High Entropy Alloys, Univ. of Thessaly, Jan. 2016
 PROCESSING ROUTES

Mechanical Alloying Sputter Deposition Process

Fig 7. Processing from the Solid State Fig 8. Processing from Gaseous State

Fig 7. & Fig 8. Ref : Ioannis S.Aristeidakis Maria-Ioanna T.Tzini (2016) High Entropy Alloys, Univ. of Thessaly, Jan.
2016
 MECHANICAL PROPERTIES

High Strength

High Hardness

Good Fracture Toughness

Good Creep Strength

Excellent Wear Resistance

Excellent Corrosion Resistance

High Thermal Stability

Fig 9. Fracture Toughness and Yield Strength Comparison in Materials

Fig 9. Ref : Gludovatz B. et al. (2016) Exceptional damage-tolerance of a medium entropy alloy CrCoNi at cryogenic
temperatures, Nature Comm, 7, 10602
CoCrFeMnNi

As the Number of Elements Increase As the Number of Elements Increase

Peak Intensity Decreases & Number of Peaks Increase Stacking Fault Energy decreases continuously

Fig 10. XRD Pattern of CoCrFeMnNi Fig 11. SFE vs Number of Elements in CoCrFeMnNi

Fig 10. & Fig 11. Ref : Yeh J. (2015) "Physical metallurgy of high-entropy alloys" JOM, 67, 2254-2261.
 CoCrFeMnNi

Presence of Twins in Microstructure As the Temperature Decreases

XRD Pattern shows FCC Crystal Structure Ductility and Strength Increases

Fig 12. Micrograph of CoCrFeMnNi Fig 13. Stress Strain Curve of CoCrFeMnNi

Fig 12 & Fig 13. Ref : Gludovatz B. et al. (2015) "Processing, microstructure and mechanical properties of the
CrMnFeCoNi high entropy alloy" JOM, 67, 2262-2270.
EXAMPLES

Alloy Structure Property Application

FeCoCrAlNi Single BCC Solid Solution Less Corrosive Enhance Corrosion and Coating on 304 Stainless
Cavitation Erosion Resistance Steel

TiNbTaZrMo Two BCC Solid Solution Considerable Strength with Superior Metallic BioMaterial
Biocompatibility

AlxCoCrCuFeNi FCC+BCC Change of Crystal Structure, Binder in WC and

High Strength to Weight Ratio Inhibit WC Coarsening

MoNbTaVW BCC Retain Strength at Elevated Temperature Refractory HEA

HfNbTaTiZr BCC Excellent Compression Ductility Refractory HEA

Table 3 : Examples of High Entropy Alloys

 APPLICATIONS
High Entropy Refractory Carbides and
High Entropy
Bulk Metallic High Entropy Cermets
Alloy Coatings
Glass Alloys with HEA Binders

HEA deposited on substrates for protection against wear, corrosion and heat.
Thin Film Coating processes include Electroless Plating, Physical Vapor Deposition, Chemical
Vapor Deposition.
Example : AlCrSiTiV HEA Coating on Ti-6Al-4V substrate

Fig 14. Surface Morphology and SEM Micrograph of

AlCrSiTiV HEA Coating on Ti-6Al-4V substratettim

Fig 14. Ref : Huang C et al. (2012) Dry sliding wear behavior of laser clad TiVCrAlSi high entropy alloy coatings on
Ti-6Al-4V substrate. Mater Des 41:338343
APPLICATIONS
High Entropy Refractory Carbides and
High Entropy
Bulk Metallic High Entropy Cermets
Alloy Coatings
Glass Alloys with HEA Binders

High Entropy feature along with Amorphous nature of Bulk Metallic Glass.
Small Hmix , Large (greater than 6.6%)
Example : Ti40Zr20Cu5Al5Be30

Fig 15. High Entropy Bulk Metallic Glass Ti40Zr20Cu5Al5Be30

Fig 15. Ref : http://www.techbriefs.com/component/content/article/ntb/tech-briefs/materials/23866

 APPLICATIONS
High Entropy Refractory Carbides and
High Entropy
Bulk Metallic High Entropy Cermets
Alloy Coatings
Glass Alloys with HEA Binders

Improved Elevated Temperature Strength, Reduced Density and High Melting Point.
Lower Yield Strength, High Ductility and High Strain Hardening.
Example : MoNbTaW and MoNbTaVW

Fig 16. Refractory HEA MoNbTaW

Fig 16. Ref : Zou Y. et al. (2015) Ultrastrong ductile and stable high-entropy alloys at small scales. Nature Comm
6, 8748
 APPLICATIONS
High Entropy Refractory Carbides and
High Entropy
Bulk Metallic High Entropy Cermets
Alloy Coatings
Glass Alloys with HEA Binders

High Hardness, Softening Resistance at High Temperature, Wear Resistance, Corrosion

Resistance.
Provides higher hot hardness due to finer WC grain size of WC/HEA carbide than WC/Co.
Example : Al0.5CoCrCuFeNi HEA as Binder.

Fig 17. HEA As Binder

Fig 17. Ref : Chen CS et al. (2014) Novel cermet material of WC/multielement alloy. Int J Refract Hard Met 43:200
204
REFERENCES

S. Ranganathan, "Alloyed pleasures: Multimetallic cocktails," Curr. Sci. , vol. 85, pp. 1404-
1406, 2003.

J. Yeh, S. Chen, S. Lin, G. J.Y., T. Chin, T. Shun, T. C.H. and S. Chang, "Nanostructured high-
entropy alloys with multiple principal elements: Novel alloy design concepts and
outcomes.," Adv. Eng. Mater, vol. 6, no. 5, p. 299303, 2004.

B. Cantor, I. T. H. Chang, P. Knight and A. J. B. Vincent, "Microstructural development in

equiatomic multicomponent alloys," Mater. Sci. Eng. A, pp. 375-377,213-218, 2004.

J. Yeh, "Physical metallurgy of high-entropy alloys," JOM, vol. 67, pp. 2254-2261, 2015.

B. Gludovatz, A. Hohenwarter, C. D., E. H. Chang and R. O. Ritchie, "A fracture-resistant

high-entropy alloy for cryogenic applications.," Science, vol. 345, pp. 1153-1158, 2014.
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