TheAlloyedPleasure:

BulkMetallicGlasses(BMGs)&
HighEntropyAlloys(HEAs)

ShengGUO
MaterialsandManufacturingTechnologyDepartment
ChalmersUniversityofTechnology
November,2013

AlloyedPleasures:
ScienceofMulticomponentAlloys

TheEnglishlanguageinsistsonunalloyedpleasures,therebyimplying
thatthesensationofpleasuremustbepure andnotadmixedwithother
emotions.
Exactlytheoppositerulesinmetallurgy,wherepuremetalshavefew
uses andcanalwaysbeimproveduponbyalloying.
The20thcenturysawtheslowtransformationoftheart ofalloyinginto
thescience ofalloying.

BMGs;GumMetal; HEAs

Outline
TwoPleasures(mainpart)
BulkMetallicGlasses(BMGs)
HighEntropyAlloys(HEAs)

MyPleasures(orPains)(brief)
PhaseSelectionRules
Metastability ofSolid
Solutions
MechanicalBehavior
SolidificationBehavior

Challenges(brief)

Metallicglasses

MetallicGlasses(AmorphousAlloys)
Au75Si25

PDuwez

WKlement,RWillens,PDuwez,Noncrystalline StructureinSolidified
GoldSiliconAlloys, Nature,1960,187:869

meltspinning

volume

BulkMetallicGlasses(BMGs)

80*85mm

AInoue

(~1990)Inouesthreeempirical
rulestoprepareBMGs(>1mm):

Pd42.5Cu30Ni7.5P20 BMG

atleast3 alloying
elements;
largemismatchingatomicsizes of
constituentelements
3.4Kg!
largenegativeheatofmixing
amongmajoralloyingelements
(NishiyamA,Intermetallics,2012)

Attractivepropertiesofbulkmetallicglasses
(BMGs)
Highstrength :>2000MPa
Highhardness:6001300 DPH
Highfracturetoughness:>70
MPa .m1/2
Highelasticstrain:~2%elastic
strain
Goodformability:>1000%
elongation
Superioraqueouscorrosion
resistance
Goodwearresistance
Excellentsoftmagneticproperties:FebaseBMGs
Otherinterestingopticalandphysical properties

BulkStructural
Metallic Glasses

FromLiquidmetalTechnologies

Microdevices:microgearsmadeofBMGs
Onlyonecastingprocess

100m

Superprecisiongearmold

Superprecisiongearpartsmadeofglassyalloy

Newlydevelopedgear

Conventional
machinedgear

Diameter = 288 m
Teeth = 9 p
Module = 25 m

Diameter=647mm
Teeth=14p
Module=40mm

Humanhair
d=80m
(Nishiyamaetal,2005)

Microgearsformicrodeviceapplications

Advancedmedical
equipments
Endoscope

Precision optics
Lenzdrive
Smallcamera

forMicroindustries

Microrobots
Measurements&
Analyticequipments

Microfactory
Microlathe

Rotablator
Aneurysm
Rotablator

Capsuleendoscope

Micropump

Catheterforthrombusremoval

BlowmouldingofBMGs

BMGsandAppleproducts

SIMtraytool

Achillesheel:(Tension)Brittleness

Glasstransitionisstillamystery

Whatisthenatureofglassystate?wasselected
asoneofthemostimportant125scientific
questionstoberesolvedthiscentury Science,
2005
Glasstransitionisoneofthedeepestandmost
importantunsolvedproblemsincondensed
matterphysics NatureMaterials,2008

(Yeh,etal.,MaterChem Phys,2007)

Introduction:HighEntropyAlloys

N=7
N=6
N=5
N=4
N=3

(Adv.Eng.Mater, 2004)

N=2
N=1

Highlyconcentrated
solidsolutions

Newapproachforalloydesign
Traditionalalloyshaveonly1 (steels,Alalloys,Cu
alloys,etc.)or2 principle elements(NiAl,FeAl,etc.)
Highentropyalloyshaveatleast5(4?)principal
metallicelements,andhaveequalorclosetoequal
compositions
Example,AlCoCrCuFeNisystem
Equimole: AlCoCrCuFeNi
Nonequimole: AlCo0.5CrCuFe1.5Ni1.2
Minor elementaddition: AlCo0.5CrCuFe1.5Ni1.2B0.1C0.15

Whyaretheycalledhighentropy alloys?
Highconfigurationentropy
N

R ci ln ci
i 1

(Yeh,8th IWIAMtalk)

Merits of highentropyalloys (HEAs)

Hardness rangesfrom100to1100HV
Excellentcorrosion resistance,wear resistance
andoxidation resistance
Highelectricalresistivity withalowornegative
temperaturecoefficient
Thermallystable microstructure
Excellentresistancetotempersoftening
Hightemperature precipitationhardening

CoreEffectsofHighEntropyAlloys
(suggestedbyProf.JWYeh)

1.Thermodynamics highentropy
2.Kinetics sluggishdiffusion
3.Structure severelatticedistortion
4.Properties cocktaileffect

 Thermodynamics
HighEntropyEffect

Highentropyeffectenhancesthe
formationofsolutionphases
Possiblecompetingstates
(elementalphases,compounds,solidsolutions)
Gmix =Hmix TSmix

Solidsolutionphaseshavingthehighestmixing
entropy
thusbecomehighlycompetitiveand
morestableespeciallyathighT

ExtendedCrystalStructuresof
SolidSolutions
Conventionalcrystalstructurecanbeextended
formultiprincipalelementsolidsolutions.

 Kinetics
SluggishDiffusionEffect
1.Lowerdiffusionrate
2.Lowerphasetransformationrate

SluggishDiffusionKinetics:
Diffusioncoupleexperiments

Lowerdiffusioncoefficients
Higheractivationenergies
(TsaiKY,etal.,Acta Mater,2013)

Fineprecipitationincastalloys
Manyhighentropycastalloyshave
nanoorsubmicronprecipitatesinthematrix.
TEMmicrostructuresofascastequimolarAlCoCrCuFeNialloy

AdvantagesofSluggishDiffusion
Slowdownphasetransformation
Easytogetsupersaturatedstateandfine
precipitates
Raiserecrystallizationtemperature
Slowdowngraingrowth
Slowdownparticlecoarsening
improvecreepresistance

Theseadvantagesmightbenefit
microstructureandpropertycontrol

 Structure

SevereLatticeDistortionEffect

SevereLatticeDistortionEffect
Latticedistortionaffectspropertiesandreducesthe
thermalvibrationeffect:

HardnessandstrengthTemp.coefficient
ElectricalconductivityTemp.coefficient
ThermalconductivityTemp.coefficient
XRDpeakintensityTemp.coefficient

ephonon

X-ray

Thermal conductivity W/mK)

Thermalconductivityandresistivity
Ni-RT
90
80

CoNi

70
60
50

CoNiFe

40
30
20

CoNiFeCrMn

CoNiFeCr

10
1

Number of elements

CoNiFeCrAl0.25
5

 Properties

CocktailEffect
Ruleofmixture
Excesspropertiesduetomutualinteractions

CocktailEffect
Arisefromthebasicfeaturesandmutualinteractions
amongallconstituentelementsinasolutionphase.
Example: AlXCoCrCuFeNialloys
700

600

Hardness (Hv)

500

400

FCC phase

FCC + BCC phases

BCC phase

300

200

100
-5

10

15

20

25

Al content (at.%)

30

35

40

AlCoCrFeNiTi0.5

MechanicalProperties
ofHEAs

y=2.26GPa
f=3.14GPa
p=23.3%

(Yeh,etal.,Adv Eng Mater,2004)

(after 1000 oc/12h)

460 MPa@1600 oC
better than superalloys
(Zhou et al., APL, 2007)

(Senkov,etal.,Intermetallics,2011)

Veryhighhardnesscanbeachieved

Disorderedbccsolidsolutionwasreserved
evenafterannealingat1400ocfor19h

CoCrFeNiTi partsinhightemperatureweartest

Highstrength,toughnessandoxidation
resistanceathightemperatures
Lowthermalconductivity
weartestingmachine
performedupto1000
connection rotationdisk
holder
rods

Hardmetals basedonHEAs
WC grainsinAlCoCrCuFeNimatrixaremuchsmallerthan
thatinComatrix
80%WC+20%AlCoCrCuFeNi (1400)

80%WC+20%Co (1400)

ThermalspraycoatingsofHEAs
Forprotectivecoatingsonheatexchangersand
hightemperaturecomponents
AlCoCrFeNiSiTi HV800

304substrateHV150

OxidationResistance
Thermalannealingat1100 for10hoursonlycausesadarkgray
coloronthesurfaceofHEAcoatings.
HEAcoatingsprovidesanexcellentprotectionforalloysubstrate.
Dense oxide layer
Oxidedebrisdetached
fromunprotectedsubstrate

HardfacingHEAs

HENitrideCoatings
AllHEnitrideshavesimpleFCCstructure.
TheFCCstructureisstableevenafter1100/5hannealing.
AlN+CrN+TaN+TiN+ZrN(AlCrTaTiZr)N
Hardness
(GPa)

Modulus
(GPa)

(AlCrMoTaTiZr)N

40

379

Strengthening

(AlCrTaTiZr)N

36

360

mechanisms:

(AlCrMoSiTi)N

35

325

1. Strongbonding

(AlCrSiTiV)N

31

300

HENitrides

2. Nanograinstructure

(AlBCrSiTi)N

25

260

3. Solidsolution
hardening

(AlCrNbSiTiV)N

42

350

4. Residualstress

(AlCrSiTaTiZr)N

34

343

(AlMoNbSiTaTiVZr)N

37

350

(AlCrTaTiZr)SiNcoatings
oncarbideinserts
Filmthicknessis1m.
(AlCrTaTiZr)SiNhasbetterflank
wearresistancethanthatofTiNand
TiAlNcommercialcoatings.

Potentialapplicationsinhardcoatings
TiN

TiAlN
CrN

(Chuang et al., Acta Mater, 2011 )

ExcellentWearResistance &
FatigueProperties ofHEAs
HEAs

(Hemphill, et al., Acta Mater, 2012)

40

Otherapplicationexamples
FlexibleSubstrate
Cuinterconnects

AlCrFeMnNi,
rolling extension
up to 4900%
(304 SS: 1543%)
(HV: 160)

DiffusionBarrier
(AlCrTaTiZr)N

(Chang et al., APL, 2009)

MyResearchArea
Overall:AlloyDesign andMechanicalBehavior ofHEAs
Morespecifically,
PhaseSelectionRules

Solidsolutions/Amorphous phase/Intermetalliccompounds

Single solidsolutions

fcc orbcc solidsolutions

Metastability ofSolidSolutionPhases

Thermolmechanical tests+ThermoCalc
calculations()

Solidsolutionlimit
MechanicalBehavior
Hardness/Tensileproperty/Toughness
SolidificationBehavior

Eutectic solidificationmicrostructure

Directionalsolidification/Singlecrystal()
()collaboration

Al0.5,fcc

Challengesinthefield
Somereal andscalable applications
Conflictbetweenstrengthand
ductility/toughness

Al0.8,fcc+bcc

Al1.0,fcc+bcc

(Tongetal.,Metall MaterTransA,2005)

Thanksforyourattention!
Dr.ShengGuo
AssistantProfessor
MaterialsandManufacturingTechnologyDepartment
ChalmersUniversityofTechnology
Gothenburg,Sweden
sheng.guo@chalmers.se

shengguo.weebly.com