application of amorphous alloys: potential and challenges to
TRANSCRIPT
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!
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Glassy alloys: historical development
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Glassy alloys: mechanical properties
A. Inoue et al.: Acta Mater. 52 (2004) G.Y. Wang et al.: Intermetallics 12 (2004)
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G. Herzer: Acta Mater. 61 (2013)
adapted from R. Boll: Weichmagnetische Werkstoffe, VAC GmbH, Ed. Siemens AG (1990)
Glassy alloys: magnetic properties
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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
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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
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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
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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
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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
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Preparation of BMGs: powder metallurgy
powder metallurgy
Ribbons by
melt spinning
Ball
milling
Hot
pressing
Elemental
powders
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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)
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Jewelry Sensing units Mechanical tools
Fine mechanic Medical tools Magnetic parts
Applications- possible fields
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Applications- examples / prototypes
A. Inoue & N. Nishiyama: MRS Bulletin 32 (2007)
www.liquidmetal.com
www.arcmg.imr.tohoku.ac.jp
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Applications- examples / prototypes
A. Inoue & N. Nishiyama: MRS Bulletin 32 (2007)
www.liquidmetal.com
www.arcmg.imr.tohoku.ac.jp
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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)
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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)
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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
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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
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Summary: pros & possible applications
M.F. Ashby & A.L. Greer: Scripta Mater. 54 (2006)
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- 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
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Improved casting method: current-assisted casting
M. Stoica et al.: Adv. Eng. Mater. 13 (2011)
DE, EP, WO registered (IFW Dresden)
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Non-wetting conditions:
a = 180° – q
!! as small as possible !!
The goal: avoid heterogeneous nucleation by non-wetting
M. Stoica et al.: Adv. Eng. Mater. 13 (2011)
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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
M. Stoica et al.: Adv. Eng. Mater. 13 (2011)
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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
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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
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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
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• O: no significant influence of atmosphere
• N: lowest values for casting in air Cast in air = less gas
trapped in cast products !
Influence of casting atmosphere
N. Van Steenberge, ISMANAM 2010
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But: No clear correlation with Hc
N. Van Steenberge, ISMANAM 2010
Influence of casting atmosphere
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 !)
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Expanding the application field: heterogeneities
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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
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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
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S. Scudino et al.: several works 2006-2010
PSS-RRL, Scripta Mater., etc.
Metal matrix composites
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Ni54Nb23Y23
N. Mattern et al.: Scripta Mater. (2007)
Zr64.13Cu15.75Ni10.12Al10
Science (2007), W.H. Wang’s group
BMG phase separation
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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
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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)
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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
Stress-induced heterogeneities
(hard and soft regions)
Hardness maps
Cold rolling: enhancing compressive deformability
Zr58.5Ti8.2Cu14.2Ni11.4Al7.7
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as-cast
CDC 10 %
Stress-induced heterogeneities
(hard and soft regions)
S. Scudino et al.: Adv. Eng. Mater. 12 (2010)
Channel-die compression: enhancing compressive deformability
Zr41.2Ti13.8Cu12.5Ni10Be22.5 Hardness maps
39 8.05.2013 Jürgen Eckert | Res Metallica 2013 |
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
Stress-induced heterogeneities
(hard and soft regions)
but
only limited tensile ductility
Cold rolling: enhancing tensile deformability
Zr52.5Ti5Cu18Ni14.5Al10
S. Scudino et al.: J. Alloys Compnd. 509S (2011)
Hardness maps
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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
Zr52.5Ti5Cu18Ni14.5Al10
S. Scudino, M. Stoica: ISMANAM 2012
41 8.05.2013 Jürgen Eckert | Res Metallica 2013 |
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
Zr52.5Ti5Cu18Ni14.5Al10
S. Scudino, M. Stoica: ISMANAM 2012
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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
43 8.05.2013 Jürgen Eckert | Res Metallica 2013 |
Thank you for your
kind attention !