Introduction to metallic glasses

GFA of metallic glasses

Mechanical properties
Open questions

Metallic Glasses and Bulk Metallic Glasses

D. Crespo1
1 Departament

de Fsica i Enginyeria Nuclear

Universitat Politcnica de Catalunya

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Why metallic glasses?

(Loading ball_bounce_DSL.wmv)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Why not?

Metallic glasses show

oustanding mechanical
properties.

(W.H. Wang, Mat. Sci. Eng. R 2004)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

The first amorphous metals.

Metallic glasses are "newcomers" in the
glass family.
1960 (Duwez et al.). First amorphous
alloy: Au75 Si25 .
Development of Rapid Quenching
Techniques (105 106 K/s).
1969 (Turnbull et al.). Well-defined glass
transition observed in some alloys.

Rapid solidification by melt spinning.

Geometry limited by the high cooling

rates.
Production of ribbons, lines and sheets.
Applications as functional materials.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

The first amorphous metals.

Metallic glasses are "newcomers" in the
glass family.
1960 (Duwez et al.). First amorphous
alloy: Au75 Si25 .
Development of Rapid Quenching
Techniques (105 106 K/s).
1969 (Turnbull et al.). Well-defined glass
transition observed in some alloys.

Rapid solidification by melt spinning.

Geometry limited by the high cooling

rates.
Production of ribbons, lines and sheets.
Applications as functional materials.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Metallic glasses at sight.

HRTEM of a crystalline metal.

ETSEIB - 08/05/2008

HRTEM of a metallic glass

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Metallic glasses at sight.

XRD of several rare earth Bulk Metallic Glasses.

Wang, J. App. Phys. 99 (2006) 093506

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Conventional metallic glasses.

Table: Values of Tg , and Tl for some typical marginal glass-forming

compositions.
Composition
Fe80 B20
Fe40 Ni40 B20
Pd80 Si20
Zr65 Be35
Zr50 Cu50
Ni50 Nb50
Au78 Si8 Ge14

ETSEIB - 08/05/2008

Tg (K)
600
690
607
623
670
875
293

Tl (K)
1600
1030
1070
1238
1219
1350
629

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Development of Bulk Metallic Glasses.

BMG: Metallic glasses with dimensions of mm.
1974 (Chen et al.) and 1982 (Duwez et al.). First Pd-Cu-Si
and Pd-Ni-P bulk amorphous alloys.
Fluxing methods to inhibit heterogeneous nucleation.

1989 (Inoue et al.). Exceptional glass forming ability of

RE-Al-(Cu,Ni) alloys.
Critical cooling rates <102 K/s.
Production of mm-cm parts by casting in Cu molds.

1990-1995. New BMG-forming families obtained:

Mg-Y-(Cu,Ni), Zr-Cu-Ni-Al.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Development of Bulk Metallic Glasses.

BMG: Metallic glasses with dimensions of mm.
1974 (Chen et al.) and 1982 (Duwez et al.). First Pd-Cu-Si
and Pd-Ni-P bulk amorphous alloys.
Fluxing methods to inhibit heterogeneous nucleation.

1989 (Inoue et al.). Exceptional glass forming ability of

RE-Al-(Cu,Ni) alloys.
Critical cooling rates <102 K/s.
Production of mm-cm parts by casting in Cu molds.

1990-1995. New BMG-forming families obtained:

Mg-Y-(Cu,Ni), Zr-Cu-Ni-Al.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Development of Bulk Metallic Glasses.

Easier production methods for BMGs.

Lower cooling rates allow easier

BMG production.
Arc melting.
Suction casting.
Severe deformation - Superplastic
flow.

Rapid solidification by arc melting.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Development of Bulk Metallic Glasses.

Easier production methods for BMGs.

Lower cooling rates allow easier

BMG production.
Arc melting.
Suction casting.
Severe deformation - Superplastic
flow.

Rapid solidification by arc melting.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

Bulk metallic glass compositions.

Table: Values of Tg , Tx and Tl of some representative BMG alloys.

Composition
Zr46.75 Ti8.25 Cu7.5 Ni10 Be27.5
Zr41.2 Ti13.8 Cu12.5 Ni10 Be22.5
Nd60 Al10 Ni10 Cu20
Pd40 Ni10 Cu30 P20
Pd40 Ni40 P20
Ce70 Al10 Ni10 Cu10
La55 Al25 Ni20
Mg65 Cu25 Y10
Ca50 Mg20 Cu30

ETSEIB - 08/05/2008

Tg (K)
622
623
438
576
590
359
491
425
389

Tx (K)
727
672
478
656
671
377
555
479
408

Tl (K)
1185
996
755
836
991
714
941
771
684

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Early developments
Production of bulk metallic glasses

BMG alloys at present.

New families constantly appearing.

Use of common metals.
Use of classical foundry production
methods.

Parts of BMG produced at the Institute

of Physics of the Chinese Academy of Science

Commercial applications: Sports

goods, jewelry, naval and war
industries.

(W.H. Wang, Mater. Sci. Eng. R 2004)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Glass formation ability (GFA).

The Time-TemperatureTransformatin diagram defines
the Glass Forming Ability of a
material.
1: low cooling rates produce
crystalline materials.
2: critical cooling rate.
3: fast cooling rates produce
amorphous materials.
Time-Temperature-Transformation diagram of glass forming
materials

ETSEIB - 08/05/2008

Traditional Silicate glasses

have very low critical cooling
rates.

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Glass formation ability (GFA).

The Time-TemperatureTransformatin diagram defines
the Glass Forming Ability of a
material.
1: low cooling rates produce
crystalline materials.
2: critical cooling rate.
3: fast cooling rates produce
amorphous materials.
Time-Temperature-Transformation diagram of glass forming
materials

ETSEIB - 08/05/2008

Traditional Silicate glasses

have very low critical cooling
rates.

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Amorphous metals with high GFA.

Some BMG-alloys have GFA similar to

silicate glasses.

(W.H. Wang, Mat. Sci. Eng. R

2004)

Best GFA is found in Pd40 Ni10 Cu30 P20 ,

with Rc = 0.10K/s and D = 10cm.
Large supercooled liquid region
Tx Tg = 135 K is found in
ZrTiCuNiBe alloys.

BMG-alloys allow to study viscosity,

relaxation and diffusion in amorphous
metals.
The factors influencing the GFA are not
clearly determined.
(A. Inoue, Acta Mater. 2000)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Amorphous metals with high GFA.

Some BMG-alloys have GFA similar to

silicate glasses.

(W.H. Wang, Mat. Sci. Eng. R

2004)

Best GFA is found in Pd40 Ni10 Cu30 P20 ,

with Rc = 0.10K/s and D = 10cm.
Large supercooled liquid region
Tx Tg = 135 K is found in
ZrTiCuNiBe alloys.

BMG-alloys allow to study viscosity,

relaxation and diffusion in amorphous
metals.
The factors influencing the GFA are not
clearly determined.
(A. Inoue, Acta Mater. 2000)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Amorphous metals with high GFA.

Some BMG-alloys have GFA similar to

silicate glasses.

(W.H. Wang, Mat. Sci. Eng. R

2004)

Best GFA is found in Pd40 Ni10 Cu30 P20 ,

with Rc = 0.10K/s and D = 10cm.
Large supercooled liquid region
Tx Tg = 135 K is found in
ZrTiCuNiBe alloys.

BMG-alloys allow to study viscosity,

relaxation and diffusion in amorphous
metals.
The factors influencing the GFA are not
clearly determined.
(A. Inoue, Acta Mater. 2000)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Factors influencing GFA.

Confusion principle. Increase of GFA with the number of
elements.
Inoues guiding principles.
Number of elements > 3.
Differences in atomic radii > 12%
Negative heats of mixing.

Inhibition of crystal nucleation. Kinetic and thermodynamic

effects.


G
I = AD exp
,
kT

ETSEIB - 08/05/2008

G =

16 3
2

3 (Gls )

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Factors influencing GFA.

Confusion principle. Increase of GFA with the number of
elements.
Inoues guiding principles.
Number of elements > 3.
Differences in atomic radii > 12%
Negative heats of mixing.

Inhibition of crystal nucleation. Kinetic and thermodynamic

effects.


G
I = AD exp
,
kT

ETSEIB - 08/05/2008

G =

16 3
2

3 (Gls )

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Factors influencing GFA.

Confusion principle. Increase of GFA with the number of
elements.
Inoues guiding principles.
Number of elements > 3.
Differences in atomic radii > 12%
Negative heats of mixing.

Inhibition of crystal nucleation. Kinetic and thermodynamic

effects.


G
I = AD exp
,
kT

ETSEIB - 08/05/2008

G =

16 3
2

3 (Gls )

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Thermodynamic factors.

Z
Gls = Hf Sf Tm

Tm

Cpls (T ) dT +

Z
T

Tm

Cpls (T )
dT
T

Small heat of fusion (Dense packing).

Large entropy of fusion
(Multicomponent liquids).
Rapid stabilization of Gls (T ) on
cooling.
Small free volume in the liquid.
Tendency to generate short range
order in the liquid state.
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Thermodynamic factors.

Z
Gls = Hf Sf Tm

Tm

Cpls (T ) dT +

Z
T

Tm

Cpls (T )
dT
T

Small heat of fusion (Dense packing).

Large entropy of fusion
(Multicomponent liquids).
Rapid stabilization of Gls (T ) on
cooling.
Small free volume in the liquid.
Tendency to generate short range
order in the liquid state.
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Kinetic factors.

Low mobility hinders crystal

nucleation.
Viscosity of BMG-alloys at melting
point: 2 5 Pas.
Viscosity of common metals at
melting point: 103 Pas.

Crystal nucleation and crystal

growth are separated in
temperature.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Kinetic factors.

Low mobility hinders crystal

nucleation.
Viscosity of BMG-alloys at melting
point: 2 5 Pas.
Viscosity of common metals at
melting point: 103 Pas.

Crystal nucleation and crystal

growth are separated in
temperature.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Kinetic factors.
What physical parameter can be related to the viscosity of a
liquid? Fragility
In strong liquids (high fragility)
follows an Arrhenius

behaviour:
E
= exp RT . Tend to be of
tetahedral network structure.
In fragile liquids (low fragility)
departs from the Arrhenius
behaviour (Vogel-Tamman-Fulcher):


= exp R(TET0 ) . Highly
coordinated ionic liquids, organic
liquids.
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Kinetic factors.
What physical parameter can be related to the viscosity of a
liquid? Fragility
In strong liquids (high fragility)
follows an Arrhenius

behaviour:
E
= exp RT . Tend to be of
tetahedral network structure.
In fragile liquids (low fragility)
departs from the Arrhenius
behaviour (Vogel-Tamman-Fulcher):


= exp R(TET0 ) . Highly
coordinated ionic liquids, organic
liquids.
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Kinetic factors.
The viscosity behaviour near the glass transition classify
BMG as strong liquids.
Table: Values of the fragility parameter for metallic glasses.
Composition
Zr46.75 Ti8.25 Cu7.5 Ni10 Be27.5
Zr41.2 Ti13.8 Cu12.5 Ni10 Be22.5
Nd60 Al10 Fe20 Co10
Pd40 Ni10 Cu30 P20
Pd40 Ni40 P20
Pd77.5 Si16.5 Cu6
Pt60 Ni15 P25
La55 Al25 Ni20
Mg65 Cu25 Y10
ETSEIB - 08/05/2008

m
44
50
33
59
54
73
68
35
45

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of BMG-alloys. Common features.

Dense random packing.

Differences with crystalline compounds ranging from 0.3%
to 1%.

Local atomic order markedly different from the competing

crystalline phases.
X-ray and neutron diffraction: No presence of pre-peak nor
second peak splitting.
Homogenous short range order and densely packed
structures.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of BMG-alloys. Common features.

Dense random packing.

Differences with crystalline compounds ranging from 0.3%
to 1%.

Local atomic order markedly different from the competing

crystalline phases.
X-ray and neutron diffraction: No presence of pre-peak nor
second peak splitting.
Homogenous short range order and densely packed
structures.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of BMG-alloys. Common features.

Dense random packing.

Differences with crystalline compounds ranging from 0.3%
to 1%.

Local atomic order markedly different from the competing

crystalline phases.
X-ray and neutron diffraction: No presence of pre-peak nor
second peak splitting.
Homogenous short range order and densely packed
structures.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metal glasses.

Icosahedric clusters of less than 8 nm.

Icosahedric configuration minimizes the volume of the
atomic clusters but does not allow long range ordering.

Tendency to primary I-phase crystallization followed by

secondary crystallization of stable phases.
Nucleation of stable phases requires long range
redistribution in a densely packed icosahedral liquid.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metal glasses.

Icosahedric clusters of less than 8 nm.

Icosahedric configuration minimizes the volume of the
atomic clusters but does not allow long range ordering.

Tendency to primary I-phase crystallization followed by

secondary crystallization of stable phases.
Nucleation of stable phases requires long range
redistribution in a densely packed icosahedral liquid.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metal glasses.

Icosahedric clusters of less than 8 nm.

Icosahedric configuration minimizes the volume of the
atomic clusters but does not allow long range ordering.

Tendency to primary I-phase crystallization followed by

secondary crystallization of stable phases.
Nucleation of stable phases requires long range
redistribution in a densely packed icosahedral liquid.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metalloid glasses.

(Fe,Co)80x (Nd,Nb)x (B,P)20 and similar glasses.

Strong Metal-Metalloid bonding.
Formation of network atomic configurations.
Trigonal prisms connected by the "glue" atoms (Nb, Zr or
Lanthanides).

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metalloid glasses.

(Fe,Co)80x (Nd,Nb)x (B,P)20 and similar glasses.

Strong Metal-Metalloid bonding.
Formation of network atomic configurations.
Trigonal prisms connected by the "glue" atoms (Nb, Zr or
Lanthanides).

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metalloid glasses.

(Fe,Co)80x (Nd,Nb)x (B,P)20 and similar glasses.

Strong Metal-Metalloid bonding.
Formation of network atomic configurations.
Trigonal prisms connected by the "glue" atoms (Nb, Zr or
Lanthanides).

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of Metal-Metalloid glasses.

(Fe,Co)80x (Nd,Nb)x (B,P)20 and similar glasses.

Strong Metal-Metalloid bonding.
Formation of network atomic configurations.
Trigonal prisms connected by the "glue" atoms (Nb, Zr or
Lanthanides).

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of (Pd,Pt)-based glasses.

Coexistence of two cluster units.

Pd-Ni-P cluster. Trigonal prism
capped with three half-octahedra.
Pd-Cu-P cluster. Tetragonal
dodecahedron.

The coexistence of the two cluster units

difficults rearrangement in crystalline
order.
Distinct GFA between PdNiP and
PdNiCuP alloys.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of (Pd,Pt)-based glasses.

Coexistence of two cluster units.

Pd-Ni-P cluster. Trigonal prism
capped with three half-octahedra.
Pd-Cu-P cluster. Tetragonal
dodecahedron.

The coexistence of the two cluster units

difficults rearrangement in crystalline
order.
Distinct GFA between PdNiP and
PdNiCuP alloys.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of (Pd,Pt)-based glasses.

Coexistence of two cluster units.

Pd-Ni-P cluster. Trigonal prism
capped with three half-octahedra.
Pd-Cu-P cluster. Tetragonal
dodecahedron.

The coexistence of the two cluster units

difficults rearrangement in crystalline
order.
Distinct GFA between PdNiP and
PdNiCuP alloys.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

Structure of (Pd,Pt)-based glasses.

Coexistence of two cluster units.

Pd-Ni-P cluster. Trigonal prism
capped with three half-octahedra.
Pd-Cu-P cluster. Tetragonal
dodecahedron.

The coexistence of the two cluster units

difficults rearrangement in crystalline
order.
Distinct GFA between PdNiP and
PdNiCuP alloys.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Stability of metallic glasses

Influence of the structure

GFA predictability.

Difficult determination of the structure for multicomponent

metallic glasses.
The atomic structure has been resolved just in few
well-known BMG compositions.
New BMG-forming alloys are not predicted by the existing
models.
The formation mechanism and the main factors influencing
GFA have not been clearly elucidated.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Interesting structural properties.

Absence of microstructural features such as grains or

phase boundaries. Possible use in small components.
High hardness and high yield stress.
High resilience and very low elastic loss coefficient.
Fracture toughness can be very high.
High viscosity of the liquid permits thermoplastic forming.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Unattractive structural properties.

Sever localization of plastic flow. Zero ductility in tension.

Metallic glasses can be embrittled by aging and annealing.
Fracture toughness can be very low.
Instability above the crystallization temperature.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Measurement of elastic constants.

Experimental determination of the
elastic constants, B (bulk modulus) and
G (shear modulus), by acoustic
measurements.
Mechanical spectroscopy
measurements.
Relaxation times can be calculated.
It seems that an excess wing has
been detected in some metallic
glasses.

Many of these measurements were not

possible in marginal glass-forming
alloys.
ETSEIB - 08/05/2008

Frequency dependence of the loss

shear modulus of Ce-based BMG.
Solid lines are fits using the KWW
equation.
(X. F. Liu et al., J. Non-Cryst. Solids 2006)

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Measurement of elastic constants.

Experimental determination of the
elastic constants, B (bulk modulus) and
G (shear modulus), by acoustic
measurements.
Mechanical spectroscopy
measurements.
Relaxation times can be calculated.
It seems that an excess wing has
been detected in some metallic
glasses.

Many of these measurements were not

possible in marginal glass-forming
alloys.
ETSEIB - 08/05/2008

Frequency dependence of the loss

shear modulus of Ce-based BMG.
Solid lines are fits using the KWW
equation.
(X. F. Liu et al., J. Non-Cryst. Solids 2006)

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Influence of structure on elastic constants.

The elastic constants of the glass are inherited from the
infinite frequency response of the liquid.

Bulk modulus variation in the liquid and glassy states

Shear modulus variation in the liquid and glassy states

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Influence of structure on elastic constants.

The elastic constants of the glass are inherited from the
infinite frequency response of the liquid.

Shear modulus variation in the liquid and glassy states

ETSEIB - 08/05/2008

Bulk modulus variation in the liquid and glassy states

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Influence of structure on elastic constants.

Densification increases the elastic
constants.
Increase of pressure and structural
relaxation give stiffer elastic constants.
The B/G ratio (equivalently the
Poissons ratio) increases under
pressure and decreases after structural
relaxation.
Decrease of B/G when reducing the
atomic dispersion of the first RDF
peak.
Increase of B/G when reducing the
mean atomic position ot the first RDF
peak.
ETSEIB - 08/05/2008

Elastic moduli as a function of the mean

atomic position s and the atomic
dispersion of the first-neighbour
shell. Calculation performed using
interatomic pair potentials.
(E. Pineda, Phys. Rev. B 2006)

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Influence of structure on elastic constants.

Densification increases the elastic
constants.
Increase of pressure and structural
relaxation give stiffer elastic constants.
The B/G ratio (equivalently the
Poissons ratio) increases under
pressure and decreases after structural
relaxation.
Decrease of B/G when reducing the
atomic dispersion of the first RDF
peak.
Increase of B/G when reducing the
mean atomic position ot the first RDF
peak.
ETSEIB - 08/05/2008

Elastic moduli as a function of the mean

atomic position s and the atomic
dispersion of the first-neighbour
shell. Calculation performed using
interatomic pair potentials.
(E. Pineda, Phys. Rev. B 2006)

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Influence of structure on elastic constants.

Densification increases the elastic
constants.
Increase of pressure and structural
relaxation give stiffer elastic constants.
The B/G ratio (equivalently the
Poissons ratio) increases under
pressure and decreases after structural
relaxation.
Decrease of B/G when reducing the
atomic dispersion of the first RDF
peak.
Increase of B/G when reducing the
mean atomic position ot the first RDF
peak.
ETSEIB - 08/05/2008

Elastic moduli as a function of the mean

atomic position s and the atomic
dispersion of the first-neighbour
shell. Calculation performed using
interatomic pair potentials.
(E. Pineda, Phys. Rev. B 2006)

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Relationship between elastic constants and fragility.

The origin of a broad correlation

between fragility and Poissons ratio
is debated at present.
The elastic properties of the glass
may be linked with the viscosity
behaviour of the liquid and so with
the GFA of the alloy.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Relationship between elastic constants and fragility.

The origin of a broad correlation

between fragility and Poissons ratio
is debated at present.
The elastic properties of the glass
may be linked with the viscosity
behaviour of the liquid and so with
the GFA of the alloy.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Plastic deformation of amorphous metals.

Absence of dislocations.
Increase of free volume during
homogeneous deformation.
Localization of plastic flow in shear
bands.
Heat release and temperature rise in
shear bands.
Melting may be attained at shear
bands.
Nanocrystallization is observed at
shear bands.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Fracture mechanism of amorphous metals.

Shear bands are uncommon in
crystalline solids but appear in
granular flows under high shear.

Hays et al. Phys. Rev. Lett. 84 (2000) 2901

Fig. 5. (a) Schematic of a plane strain biaxial compression test on dry

sand. (b) Axial compressive load P vs axial compressive displacement d.
The point S marks the formation of a fully developed shear band.
Han & Drescher, Soils and Found. 33 (1993) 118.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Fracture mechanism of amorphous metals.

Shear bands are uncommon in crystalline solids but appear in
granular flows under high shear.

NMR measurement of velocity in the gap of Couette Flow of 10% w/v

cetylpyridinium chloride/sodium salicylate in brine.
Holmes et al. Europhys. Lett. 64 (2003) 274

ETSEIB - 08/05/2008

Hays et al. Phys. Rev. Lett. 84 (2000) 2901

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Brittle-ductile bulk metallic glasses.

BMG may have high ductility in

compression (Pt, Pd and Zr based).
Upto 20% of strain in
Pt57.5 Cu14.7 Ni5.3 P22.5 .

(Schroers et al.,

Phys. Rev. Let. 2004)

Ductile-brittle transition may occur

by annealing below glass transition.
The same critical value of
Poissons ratio is found for different
alloys and different relaxation
states. (Lewandowski et al., Phil. Mag. Let. 2005)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Brittle-ductile bulk metallic glasses.

BMG may have high ductility in

compression (Pt, Pd and Zr based).
Upto 20% of strain in
Pt57.5 Cu14.7 Ni5.3 P22.5 .

(Schroers et al.,

Phys. Rev. Let. 2004)

Ductile-brittle transition may occur

by annealing below glass transition.
The same critical value of
Poissons ratio is found for different
alloys and different relaxation
states. (Lewandowski et al., Phil. Mag. Let. 2005)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Annealing of bulk metallic glasses.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Annealing of bulk metallic glasses.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Change of the structure during the deformation

process.

Molecular dynamics simulations

and combination of the Reverse
Monte Carlo method with elastic
scattering measurements allow
determination of local structures.
The atomic configuration can be
described by means of relative
frequency of different Voronoi
polihedra.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Change of the structure during the deformation

process.
The decrease of free volume on
cooling is related to the increment of
icosahedral structures.
The atomic rearrangement during
plastic strain leads to more free
volume and lower number of
icosahedral environtments.
The same structural features are
responsible of both the viscosity
behaviour (and so GFA) in the liquid
and the plastic flow in the glass.

(M. Wakeda et al., Intermetallics 2006)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Change of the structure during the deformation

process.
The decrease of free volume on
cooling is related to the increment of
icosahedral structures.
The atomic rearrangement during
plastic strain leads to more free
volume and lower number of
icosahedral environtments.
The same structural features are
responsible of both the viscosity
behaviour (and so GFA) in the liquid
and the plastic flow in the glass.

(M. Wakeda et al., Intermetallics 2006)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Change of the structure during the deformation

process.
Atomistic simulation of tensile deformation in Cu4 6Zr5 4 BMG.

(Ch. E. Lekka et al., Appl. Phys. Lett. 91 (2007) 214103)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

Alloys with unconventional properties

Elastic properties
Fracture of metallic glasses

Other interesting properties of BMGs.

Most of Fe based BMGs are soft magnetic materials

(A. Inoue et al., Acta Mat. 2004 52 1631)

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Composite BMGs
BMG-dendrite composites
can be produced in Ti-Zr
alloys. The inhomogeneous
microstructure with isolated
dendrites in the BMG matrix
stabilizes the glass against
catastrophic failure due to
unlimited extension of shear
bands.
High-resolution TEM images from the alloy DH1. a,
Bright-field TEM micrograph showing a b.c.c.
dendrite in the glass matrix. b, The corresponding
dark-field micrograph of the same region. c, A high
resolution micrograph showing the interface between
the two phases, with corresponding diffraction
patterns shown in the inset.
Hofmann et al. Nature 451 (2008), 1085

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Composite BMGs

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Composite BMGs

Ashby plot. The BMG-based

composites have the highest
fracture energies of all known
engineering materials.
Hofmann et al. Nature 451

(2008), 1085

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Outline
1

Introduction to metallic glasses

Early developments
Production of bulk metallic glasses

GFA of metallic glasses

Stability of metallic glasses
Influence of the structure

Mechanical properties
Alloys with unconventional properties
Elastic properties
Fracture of metallic glasses

Open questions
New strategies for ductile BMGs
Poly-amorphism?
ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Polymorphism in crystalline structures

Polymorphism in materials
science is the ability of a
solid material to exist in more
than one form or crystal
structure.

Crystal packing of aspirin forms I (a), II (b), acetyl

group C-H O dimers (c), and S. L. Price predicted
form II (d).
Vishweshwar et al. J. Am. Chem. Soc., 127 (2005),
16802

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Polymorphism in a metallic glass

In-situ X-Ray
diffraction of
Ce55 Al45 metallic
glass

XRD-patterns of the Ce55 Al45

metallic glass in a diamond
anvill cell.
Sheng et al. Nature 6 (2007)

192

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Polymorphism in a metallic glass

In-situ X-Ray diffraction of

Ce55 Al45 metallic glass

Specific volume versus pressure for amorphous

Ce55 Al45 .
Sheng et al. Nature 6 (2007) 192

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Polymorphism in a metallic glass

In-situ X-Ray
diffraction of
Ce55 Al45 metallic
glass

Comparison of the structure

factors for the two amorphous
polymorphs of Ce55 Al45 at
comparable pressures.
Sheng et al. Nature 6 (2007)

192

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Polymorphism in a metallic glass

In-situ X-Ray diffraction

of Ce55 Al45 metallic
glass

Comparison of spin-resolved electron

density of states (DOS), obtained for the
two amorphous Ce55 Al45 phases.
Sheng et al. Nature 6 (2007) 192

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses

Introduction to metallic glasses

GFA of metallic glasses
Mechanical properties
Open questions

New strategies for ductile BMGs

Poly-amorphism?

Summary
Bulk metallic glasses have high GFA and large stability
against crystallization. They allow the study of glass
transition phenomena in metallic-bonding systems.
Application of BMG as structural materials requires
improvement of the GFA and the mechanical properties.
The atomic structure features influencing GFA may also
determine the elastic response and the brittle-ductile
beaviour of metallic glasses.
Better knowledge of the atomic structure and its evolution
during the glass transition and the plastic deformation
process is crucial for BMG development.

ETSEIB - 08/05/2008

Metallic Glasses and Bulk Metallic Glasses