Application of amorphous alloys: potential and challenges to

Application of amorphous alloys:

potential and challenges to overcome

Jürgen Eckert

Institute for Complex Materials,

IFW Dresden, Germany

2

Glassy alloys: historical development

Silicate glass (window glass) Metallic glass

• the oldest from 7000 B.C.

• transparent

• hard and brittle

• massive first time in 1989

• metallic luster

• not transparent

• very hard

• good elasticity, partially deformable

but: different atomic structure!

8.05.2013 Jürgen Eckert | Res Metallica 2013 |

3 8.05.2013 Jürgen Eckert | Res Metallica 2013 |

Glassy alloys: historical development

4 Jürgen Eckert | Res Metallica 2013 | 8.05.2013

Glassy alloys: mechanical properties

A. Inoue et al.: Acta Mater. 52 (2004) G.Y. Wang et al.: Intermetallics 12 (2004)


G. Herzer: Acta Mater. 61 (2013)

adapted from R. Boll: Weichmagnetische Werkstoffe, VAC GmbH, Ed. Siemens AG (1990)

Glassy alloys: magnetic properties


P.F. Gostin et al.: Corr. Science 52 (2010)

H2SO4 0.5 M

100 days (2400 hours)

(Fe44.3Cr5Co5Mo12.8Mn11.2

C15.8B5.9)98.5Y1.5 BMG

H2SO4 0.5 M

20 hours

X210Cr12

NaCl 0.01M

X210Cr12

NaCl 0.6M

(Fe44.3Cr5Co5Mo12.8Mn11.2

C15.8B5.9)98.5Y1.5

Glassy alloys: electrochemical properties

Sharp margins of a

former Y2O3 inclusion


Nonferrous alloy systems Mg-Ln-M (lanthanide metal; M: Ni,Cu,Zn

Ln-Al-TM (TM: Fe,Co,Ni,Cu)

Ln-Ga-TM

Zr-Al-TM

Ti-Zr-TM

Zr-Ti-TM-Be

Zr-(Ti,Nb,Pd)-Al-TM

Pd-Cu-Ni-P

Pd-Ni-Fe-P

Pd-Cu-B-Si

Ti-Ni-Cu-Sn

Cu-(Zr,Hf)-Ti

Cu-(Zr,Hf)-Ti-(Y,Be)

Cu-(Zr,Hf)-Ti-(Fe,Co,Ni)

1988

1989

1989

1990

1993

1993

1995

1996

1996

1997

1998

2001

2001

2002

Ferrous alloy systems Fe-(Al,Ga)-(P,C,B,Si,Ge)

Fe-(Nb,Mo)-(Al,Ga)-(P,B,Si)

Co-(Al,Ga)-(P,B,Si)

Fe-(Zr,Hf,Nb)-B

Co-(Zr,Hf,Nb)-B

Ni-(Zr,Hf,Nb)-B

Fe-Co-Ln-B

Fe-Ga-(Cr,Mo)-(P,C,B)

Fe-(Nb,Cr,Mo)-(C,B)

Ni-(Nb,Cr,Mo)-(P,B)

Co-Ta-B

Fe-Ga-(P,B)

Ni-Zr-Ti-Sn-Si

Ni-(Nb,Ta)-Zr-Ti

Fe-Si-B-Nb

Co-Fe-Si-B-Nb

Ni-Si-B-Ta

1995

1995

1996

1996

1996

1996

1998

1998

1999

1999

1999

2000

2001

2002

2002

2002

2002

A. Inoue et al.: Acta Mater. 52 (2004)

Compositional classes


l = 50 mm, d = 3 mm

1 - 6 mm × 50 mm

injection centrifugal suction cold crucible

1 - 8 mm × 75 mm 1 - 6 mm × 75 mm 6 -12 mm × 180 mm

mold casting

Master alloy by

arc melting

Preparation of BMGs: inexpensive casting


Preparation of BMGs: thermoplastic deformation

• amorphous granules or

semifinal product

• plastic deformation above Tg

J. Schroers et al.: Appl. Phys. Letters 87 (2005)

Au49Ag5.5Pd2.3Cu26.9Si16.3


Processing steps may be reduced from 8 to 4 (50 %)

by using metallic glasses as starting materials !!

No shrinkage !!!

Preparation of BMGs: (powder) injection molding


Preparation of BMGs: powder metallurgy

powder metallurgy

Ribbons by

melt spinning

Ball

milling

Hot

pressing

Elemental

powders


Preparation of BMGs: selective laser melting

SLM operating mode

Gas-atomized Fe74Mo4P10C7.5B2.5Si2 powder / 3D scaffold structure (CAD +

finished structure) / final scaffolds on top of the base plate (316L steel)


Jewelry Sensing units Mechanical tools

Fine mechanic Medical tools Magnetic parts

Applications- possible fields


Applications- examples / prototypes

A. Inoue & N. Nishiyama: MRS Bulletin 32 (2007)

www.liquidmetal.com

www.arcmg.imr.tohoku.ac.jp


Gain: international regulations

IE1 = Standard Efficiency (no more allowed in the EU !!)

IE2 = High Efficiency (EU since 16.06.2011)

IE3 = Premium Efficiency (EU from 1.1.2015, compulsory after 1.1.2017)

IE4 = Super-Premium Efficiency (EU expected ~ 2021/2022)

IE5 under consideration (the question is rather WHEN than IF...)

IEC 60034-30 norm, EU norm 640/2009 (22.07.2009)

http://www.copper.org/ environment/sustainable-energy/electric-motors/motor-rotor/pdf/vanson.pdf

The most used electrical industrial motor:

6 poles, 20 HP (~15 kW)


Gain: environmental impact

(a) grain-oriented steel trafo

(b) amorphous metal trafo

Infrared photograph during

functioning under identical

conditions.

N. DeCristofaro: MRS Bulletin 23

(1998) & Metglass® Solutions (2002)


Market potential

Pressure sensors in automotive industry: > 100 mil EUR / year

C. Suryanarayana & A. Inoue: “Bulk Metallic Glasses”, 2011 CRC Press

Watch export market for

Switzerland

(1 CHF = 0.81 EUR)

Main watch exporting countries,

market evolution in 2011 vs. 2010


2.0 2500 146 5 mm Cu54Zr27Ti9Be10

2.0 2100 110 4 mm Ti50Cu20Ni24Sn3B1Si2

2.0-2.7 1700-1800 70-90 5 mm

few cm

Zr52.5Ti5Cu17,5Ni14,6Al10

Zr41.2Ti13.8Cu12.5Ni10Be22.5

2.4 3010 140 3 mm Ni53Nb20Ti10Zr8Co6Cu3

< 2 5185 268 2 mm Co43Fe20Ta5,5B31,5

< 2 3000 257 12 mm (Fe44.3Cr5Co5Mo12.8Mn11.2C15.8B5.9)98.5Y1.5

1.7 490-650 39 9 mm Mg65Cu7.5Ni7.5Zn5Ag5Y10

ey

[%]

sf

[MPa]

E

[GPa]

amorphous

up to

Alloy

Examples of alloy compositions


Summary: pros & possible applications

M.F. Ashby & A.L. Greer: Scripta Mater. 54 (2006)


- reduced reproducibility (purity of the elements, preparation parameters)

- relatively high price (need for lab-grade elements, high-price consumables)

- very brittle in tension, reduced plastic deformation in compression

M. Telford: Mater. Today 7 (2004)

Summary: pros & cons


Improved casting method: current-assisted casting

M. Stoica et al.: Adv. Eng. Mater. 13 (2011)

DE, EP, WO registered (IFW Dresden)


Non-wetting conditions:

a = 180° – q

!! as small as possible !!

The goal: avoid heterogeneous nucleation by non-wetting



I 0 s decrease

worse wetting

better flowability

easier & faster filling of

complicated cavities

increase the energy barrier

suppress the

heterogeneous nucleation

increase the undercooling

The process in details



Current-assisted casting of “dirty” alloys

Fe70.7C6.7P10.4B5Si1.1Mn0.1Cr2Mo2Ga2 = Industrial Cast Iron + P + B + Cr + Mo + Ga

A. Bárdos et al.: Czech. J. Phys. 55 (2005)

200 EUR

per tone

enhance

the GFA

corrosion, mec

props, etc.

desired elements,

but not required


Influence of casting atmosphere- a case study

• ferromagnetic Fe-based alloy

• rule of thumb: Hc < 10 A/m ≡ fully amorphous N. Van Steenberge, ISMANAM 2010


Influence of casting atmosphere

• Best results: cast in air

• Worst results: vacuum casting

• Ar casting: large scatter; best results Ar with lowest initial vacuum

N. Van Steenberge, ISMANAM 2010


• O: no significant influence of atmosphere

• N: lowest values for casting in air Cast in air = less gas

trapped in cast products !




But: No clear correlation with Hc



Composites

Amorphous matrix plus metallic crystalline particles (ductile)

in-situ

ex-situ Metal matrix (ductile) + glass particle (hard, high strength)

ex-situ

Local fluctuations

Phase separation in BMGs

Designed heterogeneities: mechanical treatments

(simple & effective !)


Expanding the application field: heterogeneities


Fe77Mo5P9C7.5B1.5

S.F. Guo et al.: Scripta Mater. (2010)

(Cu50Zr50)100-x-yTixAly ; S. Pauly, PhD thesis (2010)

(Mg0.65Cu0.075Ni0.075Zn0.05Ag0.05Y0.1)100-xFex

H. Ma et al.: Appl. Phys. Letters (2003)

Amorphous matrix composites: in-situ


Mg63Cu16.8Ag11.2Er9 + Ti

Y. Sun et al.: Appl. Phys. Letters (2009) Zr41Ti14Cu12.5Ni10Be22.5 + C

W.H. Wang at al.: Mater. Letters (2000)

Amorphous matrix composites: ex-situ


S. Scudino et al.: several works 2006-2010

PSS-RRL, Scripta Mater., etc.

Metal matrix composites


Ni54Nb23Y23

N. Mattern et al.: Scripta Mater. (2007)

Zr64.13Cu15.75Ni10.12Al10

Science (2007), W.H. Wang’s group

BMG phase separation


Zhang et al.: Nature Mater. 5 (2006)

Zr41.2Ti13.8Cu12.5Ni10Be22.5

Plastic deformation constrained by

compressive residual stresses at surfaces

Shot peening: enhancing compressive deformability


Zr52.5Cu17.9Ni14.6Al10Ti5

Stress-induced heterogeneities

(hard and soft regions)

Heterogeneous stress field

Lateral pre-compression: enhancing compressive deformability

H.B. Yu et al.: Scripta Mater. 61 (2009)


K.G. Prashanth et al.: Materials 5 (2012)

0.0 0.2 0.4 0.6 0.8 1.00.0

0.2

0.4

0.6

0.8

1.0

Z-d

ire

ctio

n (

mm

)

X-direction (mm)

450.0470.0480.0490.0500.0510.0520.0530.0540.0550.0560.0570.0590.0590.0

0.0 0.2 0.4 0.6 0.8 1.00.0

0.2

0.4

0.6

0.8

1.0

Z-d

irection (

mm

)

X-direction (mm)

530.0540.0550.0560.0570.0580.0

cold-rolled

as-cast



Hardness maps

Cold rolling: enhancing compressive deformability

Zr58.5Ti8.2Cu14.2Ni11.4Al7.7


as-cast

CDC 10 %



S. Scudino et al.: Adv. Eng. Mater. 12 (2010)

Channel-die compression: enhancing compressive deformability

Zr41.2Ti13.8Cu12.5Ni10Be22.5 Hardness maps


0.0 0.3 0.6 0.9 1.2 1.5 1.8

0.2

0.4

0.6

0.8

1.0

1.2

Z-d

ire

ctio

n (

mm

)

Y-direction (mm)

360380400420440460480500520540560570

HV01as-cast

cold-rolled

0.0 0.3 0.6 0.9 1.2 1.5 1.80.0

-0.2

-0.4

-0.6

-0.8

-1.0

HV01

Z-d

ire

ctio

n (

mm

)Y-direction (mm)

360380400420440460480500520540560570

0 1 2 3 4 5 6

500

1000

1500

2000

hf

hi

rollingdirection

y

z

x y

z

x

wi

wf

rolled 5 %

Tru

e s

tre

ss (

MP

a)

True strain (%)

as-cast



but

only limited tensile ductility

Cold rolling: enhancing tensile deformability

Zr52.5Ti5Cu18Ni14.5Al10

S. Scudino et al.: J. Alloys Compnd. 509S (2011)

Hardness maps


imprinted

0.0 0.3 0.6 0.9 1.2 1.5 1.8

0.1

0.2

0.3

0.4

Z-d

irection (

mm

)

Y-direction (mm)

420440460480500520540560580

HV01

Hardness 2D and 3D maps:

Alternating hard and soft regions

Imprinting: simple and effective


S. Scudino, M. Stoica: ISMANAM 2012


0

500

1000

1500

2000

imprinted

& annealed

0.5 %

imprinted imprinted & polished

as-cast

Str

ess (

MP

a)

Strain

RT tensile tests (strain rate ~ 10-4 s-1) sf = 1740 MPa

ep = 0 %

sf = 1750 MPa

sy = 1440 MPa

ep ~ 1 %

sf = 1700 MPa

ep = 0 % Effect is reversible by heat treatment

Imprinting: simple, effective, reversible effect


S. Scudino, M. Stoica: ISMANAM 2012


U. Kühn, A. Gebert, N. Mattern, T. Gemming, M. Stoica, S. Pauly, S. Scudino,

J. Das, S. Venkataraman, H. Wendrock, M. Calin, I. Kaban, S.M. Gorantla, F.

Gostin, S. Roth, L. Schultz, J. Bednarcik, G. Vaughan .....

M. Frey, S. Donath, B. Bartusch, H. Merker, …..

A.L. Greer, A.R. Yavari, G. He, U. Köster, D.J. Sordelet, L.Q. Xing, Z.F. Zhang,

W.L. Johnson, A. Inoue, M.D. Baro, Y. Li, K. Lu, E. Ma, T.G. Nieh, S.K. Roy,

W.H. Wang, .....

Acknowledgements


Thank you for your

kind attention !

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