Bulk Metallic Glass and

Amorphous Materials

MM 496 Advanced Materials

Spring 2021
 Bulk Metallic Glass

Crystalline Materials
 Bulk Metallic Glass

Non-Crystalline Material
Bulk Metallic Glass
 Bulk Metallic Glass
GLASS is an amorphous or noncrystalline solid formed by continuous cooling
of a liquid (solid is any material having a viscosity greater than 1012Pa·s)

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C. Suryanarayana, A. Inoue, Bulk metallic glasses, Taylor and Francis Group, LLC, 2011, p. 548.
 Bulk Metallic Glass

High cooling rate required for glass formation in metallic materials

For glass formation

• Pure metals → 1010 K-sec-1

• Amorphous alloys → 105 – 106 K-sec-1

• Bulk metallic glasses → < 103 K-sec-1

 Bulk Metallic Glass
Evolution

• Cu based bulk metallic glasses

• Zr based bulk metallic glasses
• Ti based bulk metallic glasses
• La based bulk metallic glasses
• Fe based bulk metallic glasses
• Pd based bulk metallic glasses
 Bulk Metallic Glass
Properties and Applications of BMGs
High hardness (approaching 2000 HV)
High strength (approaching 6000 MPa)
Excellent corrosion resistance (corrosion rate < 1 μm/year, normal acid and base solutions)
Excellent soft magnetic properties (for magnetic glasses: HC < 1 A-m-1)

Golf clubs, electronic casings, optical A net shaped watch case Medical tools – Zr based BMG
hardware, ingots, 12 mm diameter rod, and
large plate (under the samples)

• D. C. Hoffman, Journal of Materials, article ID 517904, 2013.

• E. Axinte, Materials and Design, 35 (2012) 518–556
• Information available on the website of liquidmetal technologies
• C. Suryanarayana, A. Inoue, Bulk metallic glasses, Taylor and Francis Group, LLC, 2011, p. 548.
 Bulk Metallic Glass
Applications of Fe based bulk metallic glasses

BMG magnetic shielding sheets for laptops Amorphous metal cores for different applications

Fe based melt spun ribbons Fe based amorphous core choke coils

- C. Suryanarayana, A. Inoue, Bulk metallic glasses, Taylor and Francis Group, LLC, 2011, p. 548.
- Information on website www.ferritech.com
 Bulk Metallic Glass
Applications of bulk metallic glasses

- E. Axinte, Materials and Design 35 (2012) 518–556 10

 Bulk Metallic Glass

Criteria for metallic glass formation

Inoue Criteria
1. Three components
2. Significant atomic size difference
3. Negative heat of mixing

Requirements of BMGs

1. Minimum of three components

2. Critical solidification rate less than 103 K/sec
3. Minimum thickness ≥ 1 mm
4. Presence of a supercooled liquid region

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C. Suryanarayana, A. Inoue, Bulk metallic glasses, Taylor and Francis Group, LLC, 2011, p. 548.
 Bulk Metallic Glass

Schematic diagrams showing the (a) equal

Melt spinning (No BMG) channel angular pressing (ECAP) and (b)
highpressure torsion (HPT) processes.
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 Production techniques of bulk metallic glass

Melt spinning (No BMG)

High pressure die casting

Water cooled copper mold casting

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C. Suryanarayana, A. Inoue, Bulk metallic glasses, Taylor and Francis Group, LLC, 2011, p. 548.
 Bulk Metallic Glass

Suction casting

Tilt casting and cap casting

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(a) Optical micrograph and (b) XRD pattern of BMG alloy

Fe76(Si0.375B0.416P0.208)24
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DSC curve of Fe-B-Si-Nb BMG alloy

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TEM micrograph and ED pattern of Zr55Cu30Al10Ni5 BMG alloy.

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Magnetic hysteresis loop of a BMG alloy

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Some characteristics of bulk metallic glasses

1) They are structurally simpler than silicate or polymer glasses due to the metallic
bonding.
2) They are considerably more homogeneous than crystalline metals because they
do not contain faults such as grain boundaries, twins and layering errors
3) They are crystallographically isotropic
4) They maintain a metallic character

• An unusual combination of low Young’s modulus and high yield strength.

• High strength (2 to 6 GPa) and fracture toughness (low to high).
• Ferromagnetism (soft: small coercive force, high permeability; hard: permanent)
• Formability (limited) at low temperatures but good between Tg and TX.
• High corrosion resistance and abrasion resistance.
• Resistant to high doses of radiation.
 Bulk Metallic Glass
Criteria of glass formingability

Turnbull Criteria (Reduced glass transition temperature)

Formation of Deep Eutectics

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Bulk Metallic Glass
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Physical Properties Density
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Physical Properties Thermal Expansion
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Physical Properties Electrical Resistance

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Viscosity
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Corrosion Resistance
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Corrosion Resistance
 Mechanical Properties

The deformation behavior of metallic glasses can be described as

inhomogeneous at low temperatures and high stresses and strain rates, and as
homogeneous at high temperatures and high strain rates.

At low temperatures, lower than about 0.5 Tg, deformation is mostly

concentrated in a few very thin “shear bands” that form approximately on the
planes of maximum resolved shear stress

It is the inhomogeneous deformation in the metallic glass that renders it

mechanically unstable at high stresses. Consequently, it fails catastrophically.

At temperatures, greater than about 0.5 Tg, metallic glasses undergo viscous
flow in which plastic strain is distributed continuously, but not necessarily
equally, between different volume elements within the material. This type of
deformation is referred to as “homogeneous” deformation.
 Mechanical Properties
Strain Softening

An increase in strain makes the material softer and allows the material to be
deformed at lower stresses and higher rates.

Shear band formation or shear localization has been considered a direct

consequence of strain softening.

Shear softening and formation of shear bands in metallic glasses have been
attributed to a local decrease in the viscosity of the glass.

Causes

- Local production of free volume due to flow

- Redistribution of internal stresses

- Local heating
Mechanical Properties
 Mechanical Properties

An optical micrograph showing the formation of multiple shear bands in an Ni50Pd30P20 BMG
specimen subjected to compression testing.
 Mechanical Properties

Temperature rise, ΔT in the shear bands at the time of fracture for different
BMG alloys plotted against the glass transition temperature, Tg.
 Mechanical Properties

Scanning electron micrograph of the surface of Zr41.2Ti13.8Cu12.5Ni10Be22.5 BMG,

which was originally coated with a tin coating. During deformation, the
“fusible coating” had melted near the shear bands.
Bulk Metallic Glass
 Bulk Metallic Glass

Competition between plastic flow and brittle failure in metals

S=μ/K

Materials with a high solidity index, S, favored brittleness and those with a low
value behaved in a ductile manner

BMGs with a μ/B value of over 0.41–0.43 are brittle

Under plane strain conditions GC = K2 / E (1-ν)2

For isotropic materials μ = E/2(1+ν)

K = E/3(1-2v)

S = [μ / B] = [ 3(1-2v) / 2(1+v) ]
Mechanical Properties
 Mechanical Properties

The correlation of fracture energy, G with (a) the ratio of μ/B and (b) Poisson’s ratio, ν for
oxide glasses, melt-spun ribbons and BMGs. The divide between tough and brittle regimes is
in the range of 0.41–0.43 for (μ/B) and 0.31–0.32 for ν.
 Mechanical Properties

Extended elongation in a 3 mm diameter BMG rod of La55Al25Ni20 alloy

superplastically deformed in the supercooled liquid region at 500 K and a strain rate
of 10-1s-1.
 Mechanical Properties

A critical requirement for a structural engineering material is that it should

have an optimum combination of strength, ductility, toughness, and
predictable
and a non-catastrophic failure.
Two types of BMG composites
1. In situ BMG Matrix Composites
2. Ex situ BMG Matrix Composites

In the ex situ composites, a crystalline phase is added separately to the melt

prior to casting into the composite.

In the in situ composite, the alloy composition is designed in such a way that
the second crystalline phase forms as dendrites during solidification

Mechanical behavior of conventional crystalline materials could be improved

by introducing metallic glass ribbons into them.

By adding tungsten and 1080 steel wires into the Zr41.25Ti13.75Cu12.5Ni10Be22.5 matrix the
compressive strain to failure increased by 900% compared to the unreinforced
BMG alloy.
 Mechanical Properties
The BMG melt can also be infiltrated into a preform of crystalline particles or
fibers, or one could also make glass/crystalline laminates

Scanning electron micrographs of a Zr-based glass matrix composites prepared by the melt infiltration
method. (a) W-fiber–reinforced composite showing the formation of a metastable W5Zr3 phase at the
interface between the W fiber and Zr55Cu30 Al10Ni5 BMG.
(b) Absence of any reaction product at the interface in the W-fiber-reinforced composite when the BMG
contained Nb in it (Zr47Ti13Cu11Ni10Nb3Be16).

The strengthening effect observed in the composites is associated with the

nature, size, shape, and volume fraction of the reinforcement

σC = VRσR + VMσM
 Mechanical Properties

Typical microstructures of the Zr56.2Ti13.8Nb5Cu6.9Ni5.6Be12.5 alloy processed by two different

techniques. (a) Optical micrograph obtained from an alloy produced by quenching directly
from the liquid state.
(b) Scanning electron micrograph from an alloy obtained by quenching the alloy first into the
mushy (liquid + solid) state, holding there for some time and then casting into the copper mold.

Room temperature compression stress–strain curves

of a monolithic BMG alloy with the composition
Zr41.2Ti13.8Cu12.5Ni10Be22.5, S1 (Zr56.2Ti13.8Nb5Ni5.6Be12.5 BMG
composite with the second phase present as spherical
particles), and S2 (Zr60Ti14.7Nb5.3Cu5.6Ni4.4Be10 alloy with
the second phase as spherical particles) alloys. Note
that the ductility of the S2 is higher than that of S1,
which is higher than that of Vit 1.