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Metallic Glasses

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Metallic Glasses
CHALLAPALLI SURYANARAYANA, University of Central Florida, Department of
Mechanical, Materials, and Aerospace Engineering, Orlando, FL, United States
32816-2450
AKIHISA INOUE, Institute for Materials Research, Tohoku University, Aoba-ku, Sendai,
Japan 980-8577

1. Introduction. . . . . . . . . . . . . . . . . . . . . 1 7.4. Electrical Resistivity . . . . . . . . . . . . 24

2. Classification of Metallic Glasses . . . . . 3 7.5. Specific Heat . . . . . . . . . . . . . . . . . . 25
3. The Concepts of Glass Formation . . . . 3 7.6. Viscosity. . . . . . . . . . . . . . . . . . . . . . 25
4. Glass-Forming Ability . . . . . . . . . . . . . 5 8. Corrosion Behavior . . . . . . . . . . . . . . 27
4.1. Critical Cooling Rate . . . . . . . . . . . . 5 8.1. Effect of Alloying Additions. . . . . . . 28
4.2. Reduced Glass Transition 8.2. Influence of Structural Changes. . . . 30
Temperature . . . . . . . . . . . . . . . . . . 7 9. Mechanical Properties . . . . . . . . . . . . 30
4.3. Deep Eutectics . . . . . . . . . . . . . . . . . 7 9.1. Deformation Behavior . . . . . . . . . . . 30
4.4. Topological Models . . . . . . . . . . . . . 7 9.1.1. Inhomogeneous Deformation . . . . . . . 31
4.5. Inoue Criteria . . . . . . . . . . . . . . . . . 9 9.1.2. Homogeneous Deformation . . . . . . . . 31
4.6. New Criteria . . . . . . . . . . . . . . . . . . 9 9.2. Deformation Maps . . . . . . . . . . . . . . 32
5. Synthesis of Metallic Glasses . . . . . . . 10 9.3. Temperature Rise at Shear Bands . . 32
5.1. Principles of Rapid Solidification 9.4. Strength . . . . . . . . . . . . . . . . . . . . . . 33
Processing . . . . . . . . . . . . . . . . . . . . 10 9.5. Ductility . . . . . . . . . . . . . . . . . . . . . . 34
5.2. General Techniques to Achieve High 9.6. Fatigue. . . . . . . . . . . . . . . . . . . . . . . 35
Rates of Solidification . . . . . . . . . . . 10 9.6.1. Fatigue Crack Growth Rate . . . . . . . . 36
5.3. Melt Spinning . . . . . . . . . . . . . . . . . 11 9.6.2. Improvement of Fatigue Resistance . . 36
5.4. Bulk Metallic Glasses. . . . . . . . . . . . 11 9.7. Yield Behavior . . . . . . . . . . . . . . . . . 36
5.4.1. Water Quenching Method . . . . . . . . . 12 9.8. BMG Composites. . . . . . . . . . . . . . . 37
5.4.2. Copper Mold Casting. . . . . . . . . . . . . 12 9.8.1. Mechanical Properties of Composites . 37
5.4.3. Metallic Glass Composites. . . . . . . . . 13 9.8.2. Initiation and Propagation of Shear
5.4.4. Metallic Glass Foams . . . . . . . . . . . . 13 Bands . . . . . . . . . . . . . . . . . . . . . . . . 38
5.5. Other Methods. . . . . . . . . . . . . . . . . 14 10. Magnetic Properties. . . . . . . . . . . . . 38
5.5.1. Mechanical Alloying . . . . . . . . . . . . . 14 10.1. Effect of Alloying Elements . . . . . . 39
5.5.2. Vapor Phase Methods . . . . . . . . . . . . 16 10.2. Effect of Annealing . . . . . . . . . . . . 40
6. Crystallization Behavior . . . . . . . . . . 16 10.3. Nanocrystalline Alloys . . . . . . . . . . 42
6.1. Crystallization Modes in Glassy 11. Applications . . . . . . . . . . . . . . . . . . . 42
Alloys . . . . . . . . . . . . . . . . . . . . . . . . 18 11.1. Mechanical Applications . . . . . . . . 42
6.2. Polymorphous Crystallization . . . . . 20 11.2. Chemical Applications . . . . . . . . . . 44
6.3. Eutectic Crystallization . . . . . . . . . . 21 11.3. Electrical Applications . . . . . . . . . . 44
6.4. Primary Crystallization . . . . . . . . . . 21 11.4. Magnetic Applications . . . . . . . . . . 44
7. Physical Properties . . . . . . . . . . . . . . 22 11.5. Miscellaneous Applications . . . . . . 45
7.1. Density . . . . . . . . . . . . . . . . . . . . . . . 22 11.5.1. Jewelry . . . . . . . . . . . . . . . . . . . . . . 45
7.2. Thermal Expansion . . . . . . . . . . . . . 22 11.5.2. Biomedical Applications . . . . . . . . . 45
7.3. Diffusion . . . . . . . . . . . . . . . . . . . . . 23 11.5.3. Other Applications. . . . . . . . . . . . . . 45

1. Introduction 1960s. These relatively novel materials have

been shown to exhibit excellent combination of
Metallic glasses are noncrystalline solids first mechanical, chemical, and magnetic properties
produced in the form of thin ribbons in the and have found commercial applications. Since

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a16_335.pub2
2 Metallic Glasses
the late 1980s, metallic glasses have also been
produced in a bulk form with section thick-
nesses reaching up to 72 mm. During the
2000s, exciting developments took place on the
synthesis, characterization, and applications of
metallic glasses both in bulk and ribbon form.
Traditionally, solid materials are classified
into two major groups—crystalline and amor-
phous—on the basis of the arrangement of
atoms inside them. Metallic materials are tradi-
tionally considered crystalline in nature, pos-
sessing translational symmetry, i.e., their
constituent atoms are arranged in a regular and
periodic manner in three dimensions. Further-
more, the concept of a space lattice requires that
every atom in the crystal has identical surround-
ings. That is, the nearest neighbor distances and
the coordination number are the same for any
atom. Thus, for a face-centered cubic structure,
the first nearest neighbor distance is aH2/2,
where a is the lattice parameter of the crystal
and the coordination number is 12. Because of
the constraints of symmetry on the different
ways in which the constituent atoms can be
arranged, only a limited number of arrange-
ments are possible in the three-dimensional
space. Thus, we have only seven crystal sys-
tems, 14 Bravais lattices, 230 space groups, etc.
Different metals with the same Bravais lattice
can have different lattice parameters and inter-
axial angles and therefore new structures could
be generated. In addition, by placing different
numbers of atoms at each lattice point in a given
Bravais lattice, it is again possible to generate a
new crystal structure. Thus, the actual number
of crystal structures is, of course, unlimited. But,
every one of these theoretically infinite number
of arrangements can be described in terms of
one of the 14 Bravais lattices. All crystalline
solids produce X-ray diffraction patterns with
sharp intensity maxima, the positions of which
correspond to the lattice spacings and the inten-
sity to the atomic distribution inside the unit
cell.
Any solid in which the regular arrangement
of atoms, i.e., periodicity, is absent is considered
noncrystalline. That is, these materials do not
possess any crystallinity. ‘‘Amorphous’’ and
‘‘glassy’’ are the other terms normally used to
describe such an arrangement of atoms. Since
the atomic arrangement is random, and there is
no periodicity, it will be difficult to define either
the nearest neighbor distances or the coordina-
tion number in these noncrystalline materials.
Each atom in the noncrystalline solid will have
different nearest neighbors and coordination
number. Consequently, X-ray diffraction pat-
terns from amorphous solids do not have sharp
peaks; instead they show diffuse intensity max-
ima. But, it can be safely stated that the nearest
neighbor distances are longer and the coordina-
tion numbers smaller in a noncrystalline solid in
comparison to its crystal counterpart, assuming
that a solid can exist in both the crystalline and
noncrystalline states. This suggests that there is
no unique description of the ‘‘structure’’ of a
noncrystalline solid and that there is no limit to
the possible atomic arrangements in these
materials. This poses a serious problem in de-
scribing the structure of noncrystalline
materials.
A revolution in the concept of metals was
brought about in 1960 when POL DUWEZ synthe-
sized thin foils of an Au–25 at% Si alloy in the
glassy state by rapidly solidifying the liquid at
rates approaching a million degrees celsius per
second [1]. Since these amorphous materials are
based on metals, these were referred to as glassy
metals or metallic glasses. Subsequently,
hundreds and thousands of alloys of different
compositions have been prepared in the glassy
state. A number of metallic glasses with a large
section thickness have been produced since the
late 1980s. These are referred to as bulk metallic
glasses (BMGs). The present consensus appears
to be that a glassy material is considered bulk,
only when the section thickness is at least a few
millimeters. This number is left very vague and
depending on who defines it, it ranges from
1 mm up to as large as 10 mm.
The terms ‘‘noncrystalline’’, ‘‘amorphous’’,
or ‘‘glassy’’ refer to similar (random) atomic
arrangements in solid materials, and therefore
they are used interchangeably. While ‘‘noncrys-
talline’’ is a generic term to describe any solid
material that does not possess crystallinity, a
noncrystalline solid formed by continuous cool-
ing from the liquid state is known as a ‘‘glass’’;
but when it is obtained by any other process,
e.g., vapor deposition or solid-state processing
methods, it is referred to as an ‘‘amorphous’’
material. It has also been occasionally empha-
sized that the presence of a glass transition
temperature, Tg, is the hall-mark of a true glass.

2. Classification of Metallic Glasses
A large variety of metallic glasses have been
developed since the 1960s. No pure metal has
been shown to transform into the glassy state,
even at very high solidification rates. First prin-
ciple calculations suggested that it may be
possible to produce a pure metal in the glassy
state if it is cooled from the liquid state at a rate
of about 1012–1013 K/s [2].
Metallic glasses (whether in ribbon form or
bulk form) can be broadly classified into two
groups as metal–metalloid and metal–metal
type, even though other classifications also
exist. In a typical metal-metalloid type glass,
the metal atoms constitute about 80% and the
metalloid atoms (typically B, C, P, and Si)
about 20%. The metal atoms may be of one
type or a combination of different metals. Simi-
larly, the metalloid atoms may be of one type or
a combination of different metalloid atoms.
Some well-investigated compositions in
this category include Pd80Si20, Pd77Cu6Si17,
Fe80B20, Fe40Ni40B20, Ni75Si8B17, Fe40-
Ni40P14B6, Fe70Cr10P13C7, Ni49Fe29B6P14Si2,
and some exotic compositions such as
W35Mo20Cr15Fe5Ni5P6B6C5Si3. In the case of
BMGs, the number of components in the alloy is
usually a minimum of three. But, frequently,
they contain a large number of components and
they are referred to as multi-component alloys.
In the metal–metal type metallic glasses,
only metal-type and no metalloid-type atoms
are involved. Some of the alloys that have been
well investigated in this category include
Ni60Nb40, Cu57Zr43, Mg70Zn30, La80Au20, and
Fe90Zr10. There is no compositional restriction
in the case of metal-metal type metallic glasses:
the second metal component can be as small as
9–10 at% or as large as nearly 50 at%. The
number of metal–metal glasses investigated in
the BMG group is relatively small.
3. The Concepts of Glass Formation
A glass is traditionally considered a noncrystal-
line solid formed by continuous cooling from
the liquid state. Thus, metallic glasses are basi-
cally not different from the silicate or oxide
glasses (! Glass, 1. Fundamentals) or organic
polymers, except that higher solidification rates
Metallic Glasses 3
Figure 1. Variation of specific volume with temperature for
a normal and a glass-forming material
are required to produce metallic alloys in the
glassy state. Figure 1 shows the variation of
specific volume (volume per unit mass) as a
function of temperature. When the temperature
of a liquid metal is reduced, its volume de-
creases with decreasing temperature up to the
freezing point, Tm. At the freezing temperature,
there is a precipitous drop in the specific volume
of the metal until it reaches the value character-
istic of the solid crystalline metal. Further de-
crease in temperature below Tm results in a slow
decrease of the volume of the metal, depending
on its coefficient of thermal expansion.
In practice a liquid normally undercools (i.e.,
the liquid state can be maintained without crys-
tallization occurring at temperatures well below
the melting temperature) before crystallization
can begin. This is because an activation energy
barrier needs to be overcome before solid nuclei
could form in the melt, and this activation
barrier is smaller the larger the value of the
undercooling. The degree of undercooling
achieved depends on several factors including
the initial viscosity of the liquid, the rate of
increase of viscosity with decreasing tempera-
ture, interfacial energy between the melt and the
crystal, temperature dependence of the free
energy difference between the undercooled melt
and the crystal phases, the imposed cooling rate,
and the efficiency of heterogeneous nucleating
agents. The actual value of undercooling is
different for different metals, but in general
practice the value is at best only a few tens of
degrees. If special efforts are made to remove
4 Metallic Glasses
Figure 2. Variation of (A) specific heat and (B) viscosity with temperature for crystal and glass formation
the heterogeneous nucleating sites, e.g., by flux-
ing methods, then the undercooling achieved
could be a few hundred degrees. Another way of
increasing the amount of undercooling achieved
is to increase the imposed solidification rate; the
higher the solidification rate the larger the
amount of undercooling.
The situation in the case of glass-forming
liquids is different. The difference between a
normal metal and a glass-forming metallic
material is that, in the case of the glass-forming
liquid, the liquid can be significantly under-
cooled, either due to the imposition of a high
solidification rate, or removal of heterogeneous
nucleating sites, or other reasons. The volume
decreases even in the undercooled region and its
viscosity continues to increase with decreasing
temperature. At some temperature, designated
as the glass transition temperature, Tg, the vis-
cosity of the undercooled liquid becomes so
high (about 1012 Pa s) that the liquid gets ‘‘fro-
zen-in’’, and this ‘‘frozen-in liquid’’ (it is like a
solid for all practical purposes) is referred to as
glass.
As described above, Tg is dependent upon
several factors—the imposed cooling rate and
the magnitude of undercooling, among others.
In other words, the glass ‘‘transition’’ is not a
true thermodynamic phase transition, but is
kinetic in nature. Thus, the Tg and the structure
of the glass are cooling rate dependent. The
faster the alloy is solidified from the liquid state
the higher is the Tg value (Fig. 1). The structure
of the glass also depends on the extent to which
structural relaxation has occurred during subse-
quent heating to higher temperatures, but below
the crystallization temperature, Tx. The higher
the structural relaxation the closer it moves
towards a ‘‘true’’ or ‘‘ideal’’ glass.
The variation of specific heat, Cp, and vis-
cosity, h, with temperature is shown in Figure 2.
The Cp of the undercooled liquid increases with
decreasing temperature and the difference be-
tween the Cp of the undercooled liquid and the
crystal continues to increase till Tg. At Tg, there
is a sudden drop in the Cp value of the under-
cooled liquid, a manifestation of the fewer
degrees of freedom as a result of freezing of
the liquid. Once the glass had formed, there is
very little difference in the Cp between the
crystal and the glass.
Metallic glasses often exhibit a reversible
glass–liquid transition at Tg, which is mani-
fested in significant changes in Cp or h. During
reheating of the glassy samples, there is a sud-
den increase in Cp and simultaneously there is a
decrease in the viscosity at Tg. These observed
reversible changes suggest, that similar to other
types of glasses, metallic glasses can revert to
the supercooled liquid state without crystalliza-
tion. This reversibility also suggests that the
structure (atomic arrangement) of the glass is
closely related to the atomic arrangements pres-
ent in the liquid state.
Glasses (and even more true for metallic
glasses) are not in a thermodynamically stable

(equilibrium) state. From a physics point of
view, glasses are in an excited state, and at any
given temperature, provided sufficient time
(may be a few minutes to thousands of years,
depending on the type of glass and the way it is
made) is provided, they will relax and eventu-
ally transform to the crystalline ground state. So,
the question frequently asked is whether the
principles of thermodynamics, where the func-
tions are defined for equilibrium states, are
applicable to systems which are far from
equilibrium.
This aspect has been dealt with in some
detail [3, 4] based on the concepts of under-
cooling developed by TURNBULL [5]. It is true
that the thermodynamic principles are, strictly
speaking, applicable only to the system which is
in equilibrium. But, they can also be used when
the system under consideration is an under-
cooled liquid.
As mentioned earlier, metallic liquids can be
significantly undercooled for extended periods
of time without crystallization occurring [5].
This is because the critical size of the nucleus to
form the solid crystalline phase, at the freezing
temperature, Tm, is infinitely large. Put differ-
ently, the time scale for the nucleation of the
crystalline phase is a function of the degree of
undercooling experienced by the melt. It is
exceedingly long at the freezing temperature
and decreases with increasing amount of under-
cooling. When the time scale for nucleation is
sufficiently long so that the liquid phase can still
explore the different possible phases in which it
could exist, one can still define the entropy and
other thermodynamic functions of the liquid.
That is, the liquid is in a metastable state for
which entropy, free energy, and other thermo-
dynamic parameters can be defined. In this
sense, one can use the thermodynamic princi-
ples that are applicable to equilibrium systems
in these situations also.
4. Glass-Forming Ability
A metallic melt needs to be significantly under-
cooled to a temperature below Tg for it to
transform into the glassy state. Even though
some basic empirical rules and some of the
thermodynamic conditions that need to be sat-
isfied to form a glass were known, there was
Metallic Glasses 5
initially no rigorous scientific basis for choosing
the alloy compositions which could be formed
as glasses. Many glasses were produced more or
less by trial and error. In fact, the very first
synthesis of a metallic glass in the Au–25 at% Si
alloy by rapid solidification processing (RSP)
methods in 1960 by POL DUWEZ and his stu-
dents [1] was by accident in more than one way.
To produce metallic glasses in large quanti-
ties and in a reproducible way, understanding
the basic reasons for glass formation from the
liquid is essential. The ability of a metallic
liquid alloy to transform into the glassy state is
defined as the glass-forming ability (GFA).
4.1. Critical Cooling Rate
The most important criterion to achieve glass
formation is to solidify the molten alloy at a rate
higher than the critical cooling rate, Rc. This
criterion has to be obeyed irrespective of wheth-
er we are dealing with ribbon or bulk glasses,
with the realization that Rc is dependent on the
alloy system. Thus, if Rc is higher, the section
thickness of the glass is small and so the material
could be synthesized only in a ribbon form. On
the other hand, if it is low, then bulk glasses can
be synthesized.
A solid is considered glass only when the
volume fraction of crystal nuclei formed is
below the detection level, typically taken as
10
6. Such a situation can be realized only when
the melt is undercooled significantly to below
Tg, which can be obtained by rapidly solidifying
the melt. The value of Rc can be calculated from
isothermal crystallization kinetics by knowing
the viscosity of the supercooled liquid, h,
entropy of fusion, DSf, etc. It has been shown
that Rc decreases with increasing h, DSf, and
decreasing liquidus temperature, Tl.
The best way to experimentally determine
Rc is by constructing the time–temperature–
transformation (T-T-T) diagrams. Figure 3A
shows a schematic T-T-T diagram for a hypo-
thetical alloy. If the alloy is cooled from the
liquid state under equilibrium conditions, i.e.,
extremely slowly, solidification will require a
very long time and the product of solidification
would always be a crystalline solid. Even if the
liquid alloy is cooled a little more rapidly
(represented by curve ‘‘1’’ in Figure 3A),
6 Metallic Glasses

Figure 3. A) Schematic time–temperature–transformation (T-T-T) diagram for a hypothetical alloy system. The cooling rate
represented by curve ‘‘2’’ is referred to as the critical cooling rate, Rc. B) Position of the T-T-T curves with the addition of a large
number of alloying elements. The C-curve shifts to the right with increasing number of alloying elements and consequently, the
glassy phase can be synthesized at slow solidification rates.

solidification occurs at a temperature, T1, and
time, t1, and the product is still a crystalline
solid. A similar situation would be obtained
even if the alloy were to be solidified at a higher
solidification rate. If the liquid alloy is solidified
at a rate faster than the cooling rate represented
by curve ‘‘2’’, which represents a tangent to the
T-T-T-curve at its nose, then crystal formation
will not take place. Instead, the liquid will be
retained in the undercooled condition. If the
temperature of this undercooled liquid is further
decreased to below Tg, the viscosity of the liquid
will increase to a value of 1012 Pa s, which is
typical of the solid state. In other words, the
undercooled liquid is now frozen-in and a glassy
phase has formed. The cooling rate represented
by curve ‘‘2’’ is referred to as the ‘‘critical
cooling rate’’, and is commonly designated by
the symbol, Rc. Thus, the simplest and most
logical criterion one could think of to predict
glass formation is that the liquid alloy should be
cooled at a rate faster than Rc and to a tempera-
ture below Tg.
The form of the T-T-T curve and the temper-
ature and time at the nose are determined by the
competition between the increasing driving

force for nucleation (due to increased under-
cooling) and the decreased atomic mobility (due
to lowering of temperature). It is possible to
theoretically calculate the critical cooling rates
for different alloy systems using the theory of
isothermal crystallization kinetics. Addition of
the majority of the alloying elements shifts the
T-T-T curve to the right. That is, the liquid can be
retained in the undercooled condition for a
longer period of time at any temperature and
therefore the value of Rc for glass formation is
lower. The farther the T-T-T curve is shifted to
the right the lower the value of Rc. This is the
concept used in synthesizing BMGs, which
contain a large number of alloying elements
(Fig. 3B). Since the T-T-T curve for solidifica-
tion is shifted far to the right due to the presence
of a large number of alloying elements, glassy
phases are formed at rates as low as 1 to 100 K/s,
and sometimes even slower.
4.2. Reduced Glass Transition
Temperature
TURNBULL [6] suggested, purely on the kinetics
of crystal nucleation and the viscosity of melts,
that the ratio of Tg to the liquidus temperature of
the alloy, Tl, should be a good indicator of GFA
of the alloy. The higher this ratio, the higher the
viscosity, and therefore the alloy melt could be
easily solidified into the glassy state at a low
critical cooling rate. The ratio of these two
temperatures, Tg/Tl, has been designated as the
reduced glass transition temperature, Trg. Based
on the nucleation theory, it was suggested that at
Trg  2/3, homogeneous nucleation of the crys-
talline phase is completely suppressed. Most
typically, a minimum value of Trg ffi 0.4 has
been found to be necessary for an alloy to
become a glass, but the higher the Trg value,
the easier it is for the glass to form. The Trg value
is reasonably high for all glass-forming alloys,
and is in fact about 0.6 for most of the alloy
compositions studied.
4.3. Deep Eutectics
The value of Tg changes slowly with solute
content and the value of Tl usually decreases
with increasing solute content. However, there
Metallic Glasses 7
are some phase diagrams in which the liquidus
curves drop very steeply with solute content. An
alloy system exhibiting a eutectic temperature
that is significantly lower than the melting
points of the individual components is
referred to as a ‘‘deep’’ eutectic. In such cases,
the Trg (¼ Tg/Tl) value around the ‘‘deep’’
eutectic composition is a strong function of the
alloy composition and exhibits the highest value
at the eutectic composition [7]. Therefore, it
should be possible to quench this alloy easily
into the glassy state. Thus, the Turnbull criterion
of high Trg and deep eutectics converge at the
deep eutectic compositions.
4.4. Topological Models
The above empirical criteria (high values of Trg
and deep eutectics) have been extensively
employed in synthesizing micrometer-thick
metallic glasses by RSP techniques. There have
also been some theoretical formulations to
explain glass formation in alloy systems that
deal with the atomic sizes of the constituent
elements and their topological arrangement.
Several topological models have been pro-
posed to explain the structure of metallic
glasses. One of the earliest models was devel-
oped initially for liquid structures by BERNAL [8].
This model refers to the dense random packing
(DRP) of hard spheres and was shown to contain
a number of different polyhedra such as tetra-
hedra, octahedra, and others, and the atoms are
supposed to be occupying the corners of such
polyhedra. The radial distribution functions
generated from such an arrangement of atoms
showed reasonable agreement with those ob-
tained from diffraction experiments. However,
there have been difficulties in applying this
model for metallic glasses. Taking the clue that
these models show the presence of polyhedra, it
was suggested that the metal atoms in a metal–
metalloid type glass form the tetrahedra and that
the metalloid atom occupies the central hole
(they ‘‘stuff’’ the voids in the Bernal DRP
structure). Consequently, the typical alloy com-
position at which the metallic glass forms is
approximately A4B (where A represents the
metal and B the metalloid), and this explains
the frequently observed composition at which
metallic glasses form.
8 Metallic Glasses
This model has been criticized and subse-
quently modified [9] by stating that the actual
size of the voids in the metal tetrahedra in the
Bernal structure is too small for any metalloid
atom to be accommodated there. It was also
shown that the concentration of ‘‘holes’’ of the
required sizes to accommodate the metalloid
atoms was too low to account for the observed
glass compositions [10]. However, it has been
shown [11] that the effective size of the metal-
loid atom depends on the nature of the metal in
which it is dissolved.
Irrespective of the actual size of the voids and
whether the above model is valid or not, it is of
interest to note that the metal-metalloid-type
binary phase diagrams exhibit deep eutectics at
around a composition of 15–25 at% metalloid.
Some typical examples are Fe–B (17 at% B),
Au–Si (18.6 at% Si), and Pd–Si (17.2 at% Si).
Therefore, the concepts of deep eutectics and
structural models also seem to converge in
obtaining glasses in the (transition or noble)
metal-metalloid types.
Atomic Size Mismatch. Analysis of a large
amount of data on binary metallic glasses has
shown that the atomic size ratios of the majority
to the minority atoms varies between 0.79 and
1.41, with many of the glasses in the range of
0.85 to 1.15. This has been termed the anti-
Hume-Rothery criterion [7], since HUME-
ROTHERY had earlier pointed out that the radius
mismatch should not exceed 15% to form
extensive solid solutions in alloy systems based
on noble metals. Thus, it appears that the sizes of
constituent atoms have a significant role to play
in glass formation.
One of the ways by which a crystalline
metallic material can become glassy is by the
introduction of lattice strain. The lattice strain
introduced disturbs the crystal lattice and once a
critical strain is exceeded, the crystal becomes
destabilized and becomes glassy. In fact, EGAMI
takes pains to state that ‘‘In general, alloying
makes glass formation easier, not because
alloying stabilizes a glass, but because it desta-
bilizes a crystal’’ [12]. Using the atomic scale
elasticity theory, EGAMI and WASEDA [13] cal-
culated the atomic level stresses in the solid
solution (the solute atoms are assumed to occu-
py the substitutional lattice sites in the solid
solution) and the glassy phase and noted that
beyond a critical solute concentration, the
glassy alloy becomes energetically more favor-
able than the corresponding crystalline lattice.
They also noted that a minimum solute concen-
tration, CBmin , was necessary, which is inversely
correlated with the atomic volume mismatch
(VA
VB)/VA (where VA and VB are the atomic
volumes of the solvent and solute, respectively)
according to the relationship:




ðVA
VB Þ
min


C ¼ l

V
B
A
The value of l was noted to be 0.1. This
model was later extended to calculate the l
value in the case of multi-component alloy
systems [14, 15] and it was noted that the
diameter of the rod which could be cast into a
fully glassy state increased with increasing val-
ue of l, and at the maximum possible diameter
the l value approached 0.18.
One of the assumptions made by EGAMI and
WASEDA [13] in calculating the lattice strain was
that the solute atoms, irrespective of their sizes,
occupy lattice sites of the solvent structure.
Assuming that the solute atoms occupy the
interstitial sites if the reduced radius R ¼ RB/RA
is less than 0.8, MIRACLE and SENKOV [16] calcu-
lated the strain induced by solute atoms and
showed that the crystalline lattice becomes de-
stabilized when it reaches a critical value of
0.054. The minimum solute concentration
required to achieve this critical strain was also
calculated [16].
The minimum solute concentration required
to destabilize the crystalline lattice is normally
small. But, in the case of BMGs, it is noted that
the total solute content is usually in the range of
about 20 to 40 at%. This was explained on the
basis that the optimum concentration of an
individual alloying element in a BMG is less
than the minimum solute concentration of an
element with the same atomic size in a binary
alloy. Therefore, the destabilizing effect of each
solute element was suggested to be additive in
these models. A topological efficient cluster
packing (ECP) model was also proposed to
explain glass formation and it was shown that,
irrespective of the number of chemically dis-
tinct solute species, the BMGs contain no more
than three topologically distinct solutes [17].
The presence of solute-centered structural enti-
ties and the fact that efficient packing of atoms
 Metallic Glasses 9

reduces the energy of the system was recently
verified based on systematic experimental and
computational analyses [18]. This was further
modified and it was called the modified ECP
model [19].
4.5. Inoue Criteria
Based on the extensive data generated on the
synthesis of BMGs, INOUE [20, 21] formulated
three basic empirical rules for the formation of
BMGs. These may be stated as:
1. The alloy must contain at least three com-
ponents. The formation of glass becomes
easier with increasing number of compo-
nents in the alloy system.
2. A significant atomic size difference should
exist among the constituent elements in the
alloy. It is suggested that the atomic size
differences should be above about 12%
among the main constituent elements.
3. There should be negative heat of mixing
among the (major) constituent elements in
the alloy system.
Among the above criteria, the first one is
based on the thermodynamic and kinetic aspects
of glass formation, and the second one is based
on the topological aspects (structure and pack-
ing of atoms). The third criterion is essential for
mixing of atoms (alloying to occur) and for the
formation of a homogeneous glassy phase.
However, some apparent exceptions have been
noted in a few alloy systems. Therefore, newer
parameters can only be obtained after the
glass has been synthesized and the transfor-
mation temperatures are measured.
2. Thermodynamic Modeling. The thermody-
namic parameters such as heat of mixing are
used in this group to predict the glass forma-
tion and evaluate GFA in a given alloy
system.
3. Physical Properties of Alloys. This group
considers the physical properties of materials
such as viscosity of the melt, heat capacity,
activation energies for glass formation and
crystallization, bulk modulus, etc.
4. Computational Approaches. These methods
help in predicting the GFA of alloys from
basic thermodynamic data, and without the
necessity of actually conducting any experi-
ments to synthesize the glass to determine
the GFA.
Table 1 summarizes the different criteria
proposed to explain glass formation in alloy
systems. Amongst all the parameters that have
been proposed, the g parameter [22] seems to be
most effective. This parameter takes into ac-
count the stability of the liquid phase and also its
resistance to crystallization. Even though a very
large number of parameters (Trg, DTx, a, b, g,
g m, d, f, and new b) have been proposed to
explain the formation and thermal stability of
the BMGs, it was concluded that no one single
parameter can satisfactorily explain the GFA of
Table 1. Summary of the quantitative criteria proposed to evaluate
the glass-forming ability of liquid alloys

criteria have been proposed. Criterion/parameter Equation

Tg
Reduced glass transition temperature Trg ¼ Tl

4.6. New Criteria DTx parameter DTx ¼ Tx
Tg

a parameter a ¼ TTxl

All the new criteria that have been proposed in b parameter b ¼ 1þ TTxl ¼ 1þa
T T
recent years to explain the high GFA of BMGs New b parameter b ¼ ðT x
T gÞ2
l x

can be broadly grouped into the following g parameter g ¼ TgTþT

x
l
categories: g m parameter gm ¼
2Tx
Tg
Tl
d parameter d¼ Tx
Tl
Tg
1. Transformation Temperatures of Glasses. In T
T
this group, the GFA is explained on the basis Kgl parameter Kgl ¼ Tmx
Tgx
 0:143
of characteristic transformation tempera- f parameter f ¼ Trg DT Tg
x

tures of the glasses such as Tg, Tx, and Tl, Trx parameter Trx ¼ TTxs
and different combinations of these three T 2T
v parameter v ¼ Tgx
Tg þT
g

parameters. The values of all these l

10 Metallic Glasses
BMGs in all alloy systems [23]. The criteria for
glass formation by other methods, e.g., mechan-
ical alloying, seem to be somewhat different
[24].
5. Synthesis of Metallic Glasses
Metallic glasses were first produced by rapidly
solidifying metallic melts at cooling rates of
about 106 K/s [1]. This early excitement of
being able to produce the normally crystalline
metals in a glassy state, and their excellent
mechanical, chemical, and magnetic properties,
led to the development of a number of different
techniques to obtain metallic glasses in different
sizes and shapes (ribbons, wires, powders, etc.).
Some of these techniques have been described
in [25–27]. The commercial requirements of
large size sheets for different applications
resulted in the development of the planar flow
casting method wherein rapidly solidified sheets
of at least 30 cm in width could be produced [28].
The quest for glassy alloys with larger section
thickness for industrial applications eventually
culminated in the discovery of BMGs [29].
BMGs have been produced in the form of rods,
sheets, pipes, powder, and spheres, at relatively
slow solidification rates of about 102 K/s or less.
Rapidly solidified ribbons of BMGs are often
used to study their properties and crystallization
behavior before proceeding to investigate the
synthesis and characterization of BMGs.
5.1. Principles of Rapid Solidification
Processing
POL DUWEZ and his colleagues first synthesized
an Au–25 at% Si alloy in the glassy state by
rapidly solidifying their metallic melts using the
so-called ‘‘gun’’ technique [30]. In this tech-
nique, a small quantity of the molten metal is
ejected using a shock wave to atomize and
rapidly solidify it on a conducting substrate.
The molten metal spreads in the form of a thin
layer, typically a few tens of micrometers (usu-
ally about 20–50 mm) in thickness, and the heat
is extracted rapidly by the conducting copper
substrate. Consequently, the molten alloy soli-
difies very rapidly, at solidification rates of up to
1010 K/s. Thus, the basic requirements to
achieve high solidification rates are:
1. Formation of a thin layer (film or ribbon) of
the molten metal, and
2. Intimate thermal contact with a good heat-
conducting substrate to rapidly extract the
heat from the liquid metal.
Since the solidification rate achieved, R, is
inversely proportional to the square of the thick-
ness of the solidified molten layer, it is critical
that the section thickness of the ribbon is very
small. For example, the solidification rate
achieved is approximately 105 K/s for a foil
thickness of 100 mm and 109 K/s for 1 mm
thickness. The typical thickness of a rapidly
solidified ribbon is about 50 mm and therefore
it would have solidified at a rate of approximate-
ly 106 K/s. These examples serve to illustrate
that it is necessary to have as small a section
thickness as possible to achieve high solidifica-
tion rates.
5.2. General Techniques to Achieve
High Rates of Solidification
The cross section of the solidified metal layer
obtained by the ‘‘gun’’ technique of rapid solid-
ification is not uniform because of the free flow
of the liquid metal under pressure. Hence, it was
very difficult to determine the physical and
mechanical properties of these novel materials.
To overcome this deficiency, a number of other
techniques were developed to improve upon the
uniformity of cross section of the solidified
layers. These include the piston-and-anvil [31]
and twin-piston [32] methods in which the
molten metal is rapidly flattened between two
impacting substrates and consequently the drop-
let solidifies rapidly. The greatest advantage of
these methods over the ‘‘gun’’ technique is the
uniformity of section thickness. Attempts have
also been made to increase the solidification
rates by using diamond (! Carbon, 2. Dia-
mond) as a substrate [33], since it is known that
diamond at liquid nitrogen temperature has a
much higher thermal conductivity than copper
at room temperature.
The most significant milestone in this direc-
tion was the development of the chill block melt
 Metallic Glasses 11

spinning technique and several of its variants.

This has been the most popular technique of
RSP since its introduction because (i) it is
possible to produce ribbons of uniform cross
section, (ii) its process parameters have been
optimized, and (iii) melt spinners are commer-
cially available.

5.3. Melt Spinning

Development of the melt spinning technique has

been mostly responsible for the accelerated
progress of RSP technology since the 1970s.
The melt spinning process derives its name from
the fact that it involves the extrusion of molten
metal to produce fine fibers in a way akin to that
used for the manufacture of synthetic textile
fibers. In this process, a small quantity of the
alloy is melted inside a crucible or by levitation
methods, and then ejected by pressurization
through a fine nozzle onto a cold, fast-rotating
heat sink (usually a copper wheel) where the jet
is reshaped and allowed to solidify. The jet, on
impingement with the heat sink, forms a melt
puddle of thickness approximately equal to and
width about double that of the jet. As solidifica-
tion begins, the ribbon is expelled from the
surface of the fast-rotating heat sink. The
products of melt spinning include filaments,
ribbons, tapes, or wires. The process is referred
to as free-flight melt spinning (FFMS) if the
melt is allowed to solidify in flight or chill-block
melt spinning (CBMS) if it is allowed to solidify
against a chill (substrate). It is the CBMS pro-
cess that is most commonly used by researchers.
Figure 4 shows a schematic illustration of the
melt spinning process. The size, shape, and
thickness of the ribbon can be altered by chang-
ing the process parameters.
The solidification rates achieved in this pro-
cess are typically about 105–106 K/s. Typical
dimensions of the very long ribbons produced
are about 2 to 5 mm in width and the thickness is
in the range of 20 to 50 mm. Because of the high
solidification rates, it is possible to produce
most alloys of appropriate composition in the
glassy state by this technique. The downside is
that the section thickness is limited. The width
of the ribbons can, however, be increased, up to
about 30 cm, by using the planar flow casting
method, in which the nozzle has a rectangular
Figure 4. Schematic illustration of the melt-spinning
process
cross-section. Occasionally more than one noz-
zle is also used to ensure overlap of the melt
puddle to increase the width of the ribbon [28].
However, the thickness cannot be increased
significantly by any of the known melt-spinning
methods.
5.4. Bulk Metallic Glasses
Metallic glasses with a section thickness of
>1 mm were synthesized in the early
1970s [34]. The work of DREHMAN et al. [35]
clearly showed that removal of heterogeneous
nucleation sites is very important in suppressing
the nucleation of crystalline phases. Therefore,
by removing impurities from the melt by the flux
melting technique, 10-mm size glass was pro-
duced in 1984 in a Pd40Ni40P20 alloy [36]. The
flux melting method involves heating and cool-
ing the molten metal while it is immersed in a
molten oxide flux. After gravity segregation, the
impurities present in the alloy are dissolved in
the molten oxide flux. If the flux containing the
impurities from the alloy is maintained in the
liquid state at the glass transition temperature of
12 Metallic Glasses
the alloy, then glass formation can be achieved
at slower solidification rates. Slow solidification
rates translate to large section thicknesses. The
thickness/diameter of the fully glassy alloy
could be increased by an intelligent choice of
the alloy composition and processing method.
For example, by replacing part of Ni with
Cu in the Pd–Ni–P alloy to a composition
Pd40Ni10Cu30P20, the diameter of the glassy rod
was increased to 40 mm [37]. By subjecting this
Pd40Ni10Cu30P20 alloy to a flux melting treat-
ment, the diameter of the bulk metallic glassy
alloy was further increased to 72 mm [38].
If one wishes to obtain bulk glassy samples, it
is necessary that the critical cooling rate for
glass formation is very low. Consequently,
simple methods such as water quenching and
copper mold casting can be used to synthesize
BMGs.
5.4.1. Water Quenching Method
This is the simplest of the quenching methods
used for centuries to harden steel. The cooling
rates achieved are inherently dependent on the
heat transfer efficiency of the quenching medi-
um, the size of the specimen, and its heat
transfer properties. This technique has been
used by many researchers to produce BMGs in
different alloy systems.
The technique of water quenching is quite
simple. The alloys are made by conventional
methods such as in an arc furnace or by induc-
tion melting. These prepared alloys are then
placed inside a quartz tube, given the flux
treatment (adding of an oxide such as B2O3,
which is known to improve the GFA of alloys by
removing impurities from the alloys), if neces-
sary, and heated to a temperature above the
liquidus temperature of the alloy to completely
melt it. The quartz tube containing the molten
alloy is then quenched into flowing or agitated
water. The diameter of the quartz tube may be
varied to obtain glassy rods of different dia-
meters and also to determine the maximum
diameter of the rod which could be quenched
into the glassy state. The wall thickness of the
quartz tube is typically about 1 mm. The length
of the quartz tubes can be a few centimeters in
length (up to 15). The cooling rate achieved is
typically 102 K/s and so this technique could
Figure 5. Photograph of the 72-mm diameter glassy cylin-
der of Pd40Cu30Ni10P20 produced by water quenching. Note
the smooth appearance of the cylinder, which is typical of
glassy alloys
be used to produce glassy rods only in those
systems which have a high GFA, i.e., those
alloys that possess low critical cooling rates for
the formation of the glassy phase. Figure 5
shows a photograph of the 72-mm diameter
cylinder of a Pd40Cu30Ni10P20 alloy produced
by water quenching. The cylinder possesses
good luster, typical of glassy samples, and its
external appearance is smooth. A distinct ad-
vantage of the water quenching method is that
due to the slow solidification rates, the cast
specimen contains much less residual stresses.
5.4.2. Copper Mold Casting
This appears to be perhaps the most common
and popular method to produce BMGs in dif-
ferent alloy systems. In this technique [39, 40],
the alloy is melted and poured into a copper
mold where it solidifies quickly because of the
rapid heat extraction by the metal mold. The
most common and simple form of the mold has a
cylindrical or rod-shaped cavity of a predeter-
mined length. In this case, molds with cavities of
different internal diameters must be used to
determine the maximum diameter of the sample
that could be produced in a fully glassy state.
The necessity of using molds of different
internal diameters could be avoided by using
a wedge- or cone-shaped mold. The advantage
of using the wedge-shaped mold is that
specimens of different diameters can be
obtained in one experiment, and this will help

in determining the maximum diameter of the
rod that could be produced in the glassy state.
Other methods have also been commonly
employed to produce BMGs. These include
high-pressure die casting [41] in which a plung-
er pushes the molten alloy, contained in a sleeve,
by hydraulic pressure into the copper mold.
High solidification rates (103 K/s), high pro-
ductivity, and the absence of casting defects
such as shrinkage holes are the clear advantages
of this method. In the cap-cast technique [42],
where high solidification rates can be achieved,
the molten alloy is poured into a copper mold
and allowed to solidify quickly from the top by
bringing a metallic cap into contact with the
molten metal, while applying pressure. Speci-
mens as large as 40 mm in diameter have been
produced by this method. In the suction casting
method [43, 44] the molten alloy is sucked into a
mold/die cavity by use of a pressure differential
between the melting chamber and the casting
chamber. The technique is referred to as ‘‘drop
casting’’ if the molten alloy is just dropped into
the mold instead of sucking it in through a
pressure differential. Drop casting is typically
used to process materials with diameters larger
than 6 mm [44, 45], while suction casting is
used for casting of materials with diameters
smaller than 6 mm (where the viscosity of the
molten alloy hinders flow into the mold). There
have been instances where large rods of 30 mm
diameter have been produced by suction cast-
ing, and rods with diameters below 6 mm have
been produced by drop casting. The squeeze
casting process involves solidification of the
molten metal under a high pressure within a
closed die by utilizing a hydraulic press [46],
and can produce bulk glassy sheets with dimen-
sions of 2.5 mm in thickness, 35 mm in width,
and 80 mm in length. Arc melting and unidi-
rectional zone melting methods have also been
used to synthesize metallic glassy alloys [47].
The application of electromagnetic vibra-
tions, induced by the interaction of alternating
electric and stationary magnetic fields that could
act as powerful vibrating forces in the melt, was
shown to eliminate the presence of clusters
which could act as nucleation sites for the
formation of crystalline phases, thus increasing
the GFA of alloys [48]. Mg65Cu25Y10 alloy
samples with a diameter of 2 mm and a length
of 12 mm were produced by this method.
Metallic Glasses 13
5.4.3. Metallic Glass Composites
In addition to the monolithic BMGs, composites
containing a glassy phase and a crystalline rein-
forcement were also synthesized since it has
been known that the presence of crystalline
inclusions can increase the ductility of BMG
alloys. The BMG composites have been classi-
fied as in-situ (when the crystalline phase pre-
cipitates out of the metallic glass either during
casting or subsequent processing) or ex-situ
(when the reinforcement phase is added sepa-
rately during the casting/processing of the alloy).
The crystalline reinforcement could also be
aligned. Zr-based alloy BMG composites con-
taining silicon carbide and carbon, and continu-
ous metal wires, such as tungsten, carbon steel,
stainless steel, molybdenum, tantalum, nickel,
copper, and titanium, were fabricated [49].
5.4.4. Metallic Glass Foams
Metallic foams are industrially important ma-
terials, and have interesting combinations of
properties such as high stiffness in conjunction
with very low specific weight, high gas perme-
ability combined with high thermal conductivi-
ty, high mechanical energy absorption, and
good acoustic damping [50, 51].
The actual process to produce amorphous
metallic foam was first demonstrated in
2003 [52]. Hydrated B2O3 was used to
create gas bubbles in the liquid melt of
Pd43Ni10Cu27P20, a very good glass former.
Water vapor is released during decomposition
of the hydrated B2O3, which is entrapped by the
melt. These bubbles expand when the pressure
is decreased, resulting in a low-density closed-
cell foam. Bubbles were obtained that varied in
diameter between 0.1 and 1 mm and had a very
uniform bubble distribution. Densities as low as
1.4 g/cm3 were obtained corresponding to a
bubble volume fraction of 84%.
Metallic glass foams were also produced by
infiltrating the molten Zr57Nb5Cu15.4Ni12.6Al10
alloy into a sintered BaF2 pattern followed by
rapid quenching [53]. BaF2 was leached out in a
bath of 2 N nitric acid. Solid NaCl and liquid
Pd42.5Cu30Ni7.5P20 alloy were mixed in a silica
tube and this mixture was water quenched [54a].
The salt was later leached out by warm water
at 353 K. By maintaining a volume fraction of
14 Metallic Glasses
1 to 7 between the Pd-alloy and the salt, a
porosity of about 65% was obtained in the alloy.
The pores in the foam had a polyhedral shape
with sizes of 125 to 250 mm, corresponding to
the shape and size of the salt crystals. High
pressure helium and/or hydrogen gas has also
been used to produce a significant amount of
porosity with a uniform pore size [54b].
5.5. Other Methods
Metallic glasses have also been synthesized by
other methods. Since metallic glasses are non-
equilibrium phases, any method capable of
processing materials at far-from equilibrium
conditions should, in principle, be able to pro-
duce metallic glasses. (The true definition of a
glass is that it is a liquid that has been cooled into
a state of rigidity without crystallizing. Accord-
ingly, purists reserve the term ‘‘glass’’ only to
those noncrystalline materials that have been
obtained directly from the liquid state. Noncrys-
talline materials synthesized by other methods,
such as starting from the solid or vapor states,
are referred to as amorphous materials).
Amorphous alloys have also been synthe-
sized by a number of other nonequilibrium
processing techniques [55]. These include
mechanical alloying [56, 57], irradiation meth-
ods, ion implantation and ion mixing, laser
processing, plasma processing, physical and
chemical vapor deposition methods, electrolytic
deposition, thermal spray processes [58], appli-
cation of high pressures [59], interdiffusion and
reaction methods, and others. In all these meth-
ods, the common theme has been to bring the
material into a far-from equilibrium condition
by raising the temperature, pressure, input of
mechanical energy, or by other means and
subsequently quenching the material to either
retain the metastable phase or use it as an
intermediate step to achieve the desired micro-
structure and/or properties. Amongst the solid-
state processing methods, mechanical alloying
has been the most popular to synthesize metallic
glasses including BMGs.
5.5.1. Mechanical Alloying
Amorphous phases have been produced by
mechanical alloying (MA) methods in a large
number of alloy systems [56, 57]. In this
process, a mixture of the blended elemental or
pre-alloyed powders is loaded, under inert at-
mosphere conditions, into the milling container
along with the grinding medium (usually stain-
less steel, tungsten carbide, or other hard ma-
terials. This container is then placed inside the
mill and the whole mass is violently agitated for
the desired length of time. Depending on the
type of mill used, the powder is subjected to
shear, impact, or other types of mechanical
forces.
As depicted in Figure 6A, the powder parti-
cles get trapped between two grinding balls and
go through a process akin to rolling. But, there
could be compressive, shear, and impact forces
exerting on the surfaces of the powder particles.
Under the action of mechanical forces, the soft
individual powder particles are flattened into a
pancake shape, and if the powder particle is
brittle, it gets comminuted and the particle size
becomes smaller (Fig. 6B). Due to the random
process, the flat soft particles get stacked and
form a layered structure. On continued milling,
these layered structures get convoluted. This
process of convolution continues with milling
time and the layer spacing is significantly re-
duced. In addition, the milled powder particles
also contain a high density of crystal defects
(dislocations, stacking faults, grain boundaries,
etc.). Thus, the combination of small particle
size, reduced diffusion distances across the
lamellar structure, fresh surfaces and interfaces,
coupled with a slight rise in temperature, all
contribute to increased atomic diffusivity and
therefore alloying occurs. Depending on the
milling conditions, nature of the constituent
elements present, and the proportion of the
elements, different types of alloy phases are
produced. These include supersaturated solid
solutions, intermetallic phases, quasicrystalline
phases, or even amorphous phases. The choice
of the phase formed depends on the thermody-
namic stability of the different competing
phases. The kinetics of microstructural refine-
ment depends on the mechanical properties of
the powder, type of the mill used, ball-to-pow-
der weight ratio, and the temperature at which
milling is carried out.
The milled powder particles experience hea-
vy plastic deformation and generate a variety of
crystal defects. These defects raise the free
 Metallic Glasses 15

Figure 6. A) Ball–powder–ball collision of a powder mixture during mechanical alloying; B) Deformation characteristics of
representative constituents of starting powders in mechanical alloying. Note that the ductile metal powders (metals A and B) get
flattened, while the brittle intermetallic and dispersoid particles get fragmented into smaller particles

energy of the crystalline system to a level higher
than that of a hypothetical amorphous phase,
and consequently, the crystalline phase be-
comes destabilized and an amorphous phase
forms [55–57]. The first report of formation of
an amorphous phase by mechanical milling was
in an Y-Co intermetallic compound [60] and
that by mechanical alloying in a Ni-Nb
powder blend [61]. Subsequently, amorphous
phases have been formed in a number of binary,
ternary and higher-order systems by this
method [56, 57].
Amorphous alloy powders of multi-
component bulk metallic glass compositions
have also been produced by MA in several alloy
systems including those based on Fe, Mg, and
Zr. These powders can be conveniently consol-
idated into bulk in the supercooled liquid region.
16 Metallic Glasses
A clear advantage of this approach to synthesize
monolithic BMGs is that the size limitations
imposed by the solidification processing meth-
ods will not apply here.
A major difference between MA and the
solidification techniques described earlier is that
while a bulk glassy alloy (either monolithic or
composite) is produced in one single step using
the solidification methods, MA produces the
amorphous phase in a powder form and this
needs to be consolidated by some of the con-
ventional or innovative methods through appli-
cation of pressure and/or temperature. Howev-
er, one of the biggest advantages of the MA
method is that this technique could be used to
easily produce amorphous phases in those sys-
tems where conventional melting and casting
methods prove difficult or impossible. Further-
more, MA has a clear advantage in producing
BMG composites. A very large number of
oxide-, carbide-, and other ceramic-dispersed
composites have been produced by MA. Be-
cause of the heavy deformation involved and the
powder kneading that takes place, the ceramic
phase becomes uniformly dispersed in the metal
matrix. In fact, the technique of MA was
developed to satisfy an industrial necessity of
producing oxide-dispersion strengthened nickel-
based superalloys (! Nickel Alloys). Further-
more, it has been demonstrated that using MA,
one should be able to produce a composite
containing a very high volume fraction of even
nanometer-sized ceramic particles [62].
Other solid-state methods to synthesize amor-
phous alloys include hydrogen-induced amor-
phization [63], multilayer amorphization [64],
pressure-induced amorphization [59], amorphi-
zation by irradiation [65], severe plastic defor-
mation [66], and accumulative roll bonding [67].
5.5.2. Vapor Phase Methods
In these methods, starting from the vapor phase,
metal wires are evaporated and the vapor is
allowed to condense on to a cold substrate
usually maintained at liquid nitrogen or even
liquid helium temperatures. Since the cooling
rate achieved in these methods is typically of the
order of 1012 K/s, and the substrate is main-
tained at very low temperatures, formation of
amorphous phases is relatively easy. An occa-
sional problem encountered is that these thin
films crystallize when heated to room
temperature.
The earliest report of formation of an amor-
phous phase in a metal is by vapor deposition
methods. The physicists produced amorphous
metals by the vapor deposition route to study
their superconducting properties. According to
the available reports [68], amorphous Sb was
synthesized by first evaporating the Sb metal
and allowing it to condense on a cold substrate.
Subsequently, thin films of Bi, Ga, and Sn-Bi
alloys were synthesized by the vapor deposition
process [69], and though initially believed to be
ultrafine-grained, it became clear later that the
films were actually amorphous.
Several variants of the vapor deposition
method can be used to synthesize amorphous
alloys. These include, for example, plasma
sputtering, chemical vapor deposition, and elec-
tron beam evaporation. One of the most popular
among these is the sputtering method, in which
atoms from the surface of the material are
knocked off using high-energy ions, and the
atoms so removed from the surface are subse-
quently allowed to deposit onto a cold sub-
strate [70]. Vapor deposition methods are used
mainly to produce small quantities for mostly
scientific investigations and for electronic and
magnetic applications. Another problem with
these methods is that the samples are very
sensitive to the presence of impurities. The
presence of impurity atoms such as oxygen has
been identified as the reason for the formation of
amorphous phases in some materials, including
pure metals.
Another technique that has been extensively
used to prepare amorphous alloys, again mostly
thin films, is to implant high-energy solute ions
into metallic surfaces. This technique has come
to be known as ion implantation. In a related
technique, referred to as ion mixing, successive-
ly vapor-deposited layers of different elements
are mixed together and alloyed by means of the
thermal energy of injected rare-gas ions. Several
amorphous and metastable crystalline phases
have been produced by these methods [71].
6. Crystallization Behavior
Metallic glasses, whether produced in the form
of ribbons by the melt-spinning technique at

high solidification rates or in bulk rod form by
conventional solidification methods at relative-
ly slow solidification rates, are in a high energy
(metastable) state. Consequently, they lower
their energy by transforming into the crystalline
state, a process referred to as crystallization or
devitrification.
When a metallic glassy alloy is heated con-
tinuously at a constant heating rate, typically
between 5 and 20 K/s, the transformations that
take place in the sample are indicated by
deflections or peaks in the differential scanning
calorimeter (DSC) or a differential thermal
analyzer (DTA) curve. On continuous heating,
the glassy alloy exhibits a glass transition tem-
perature Tg, one or more crystallization peaks
(exothermic), Tx, and then an endothermic peak
corresponding to the melting, Tl of the alloy.
Crystallization of metallic glasses is
expected to take place at or above Tx. It is,
however, not a thermodynamic parameter like
the melting temperature of a metal. It is a
function of the heating rate employed and the
higher the heating rate, the higher is the Tx.
Therefore, given sufficient time, crystallization
of metallic glasses can occur at temperatures
lower than Tx also. The crystallization tempera-
tures of metallic glasses are in the range of 0.4 to
0.7 Tm. The actual values range from as low as
383 K for an Au55Cu25Si20 glass to as high as
982 K for a Co43Fe20Ta5.5B31.5 alloy, and
higher for refractory metal-based alloys.
At a temperature Tx, which is higher than Tg,
the supercooled liquid crystallizes into the crys-
talline phase(s) and the temperature interval
between Tx and Tg is referred to as the width
of the supercooled liquid region, i.e., DTx ¼
Tx
Tg. The value of DTx is different for differ-
ent glasses, and is usually taken as an indication
of the thermal stability of the glass produced. In
the case of BMGs this temperature interval is
usually quite large and values of over 120 K
have been reported; the highest reported to-date
is 131 K in a Pd43Cu27Ni10P20 BMG alloy [72].
In the case of rapidly-solidified thin ribbon
glasses, and marginal glass-formers, the value
of DTx is very small, if observed at all.
Crystallization studies of alloys are impor-
tant from both scientific and technological
points of view. Since crystallization of metallic
glasses occurs by a nucleation and growth pro-
cess, it offers an opportunity to study the growth
Metallic Glasses 17
of crystals into an isotropic medium. Further-
more, this process also offers a chance to test the
classical nucleation and growth theories at large
undercoolings.
If the crystallization reaction is temperature-
dependent, i.e., if it possesses an activation
energy, then the position of the peak varies with
the heating rate employed assuming that all
other experimental conditions are maintained
constant. The transformation temperatures are
higher at faster heating rates. It was also shown
that the peak temperature, Tp corresponds to the
temperature at which the reaction rate is a
maximum. Using this concept of variation of
Tx (or Tp) with heating rate (b), the activation
energy for crystallization of metallic glasses has
been determined using the Kissinger equation:
!  
b Q
ln ¼
þA
T 2p RT p
where A is a constant and R is the universal
gas constant. Thus, by plotting lnðb=T 2p Þ against
1/Tp a straight line is obtained whose slope is

Q/R, from which the activation energy for the
transformation, Q, can be calculated. It is also
possible to evaluate the individual activation
energies for the nucleation and growth stages of
the transformation, from which information
about the mechanism of transformation could
be ascertained.
From a technological point of view, the
crystallization temperature of metallic glasses
provides a real upper limit to the safe use of
metallic glasses without losing their interesting
combination of properties. But, it should be
realized that Tx cannot be taken as an indicator
of the safe operating temperature of a metallic
glass. For example, even though many Fe-based
metallic glasses have Tx in the region of 700 K,
their maximum long-term operating tempera-
tures are only of the order of 420 K [73].
An important point to be remembered is that
Tx is the same whether measured on a ribbon or
rod of the same composition, i.e., it is indepen-
dent of the section thickness. The factors that
affect the value of Tx in metallic glasses are not
clear. A number of different possibilities have
been proposed, the chief among them being the
atomic size. It was suggested that the Tx value is
higher when the atomic size of the alloying
element is larger than that of the solvent atom.
Reasons for a change in the Tx value were
18 Metallic Glasses
suggested to be reduction in free volume and
diffusivity, electron-to-atom ratio, and differ-
ences in electronegativity [74].
Studies on the crystallization behavior of
metallic glasses also provide an opportunity to
study the kinetics of crystallization and the
micromechanisms of crystallization. Such
results will provide a clear understanding of the
way the metallic glass transforms into the crys-
talline state and offers a means to impede or
control the crystallization behavior. In other
words, one could tailor the microstructure to
obtain a glass þ nanocrystal or an ultrafine-
grained composite, or a completely crystalline
material of different grain sizes by controlling
the time and temperature of crystallization [75].
It has also been possible to obtain composites
of a fine crystalline phase dispersed in the
glassy matrix by partial crystallization of the
glass. Such composites exhibit interesting me-
chanical properties, substantially high strength
values [76] and increased ductility [77, 78].
Furthermore, it should be possible to produce
a fully nanocrystalline material by controlled
crystallization of the metallic glassy alloys of
suitable compositions. As a result, the mechan-
ical and other properties could be optimized
through a proper understanding of the crystalli-
zation behavior of metallic glasses. It is not
possible to obtain such novel and unique micro-
structures by any other means and in other types
of materials unless one starts with a fully glassy
material.
Glassy phases give rise to broad and diffuse
halos in their diffraction patterns. It is desirable
to confirm the formation of the glassy phase
using direct transmission electron microscopy
(TEM) techniques. Figure 7 shows the TEM
images and electron diffraction pattern of a
Zr55Cu30Al10Ni5 glassy alloy. The TEM image
(Fig. 7A) is characterized by a complete lack of
contrast, while the electron diffraction pattern
(Fig. 7B) displays a very diffuse and broad halo.
The high-resolution TEM image (Fig. 7C)
shows the so-called salt-and-pepper contrast.
6.1. Crystallization Modes in Glassy
Alloys
Crystallization of metallic glasses occurs by
nucleation and growth processes. The driving
force for crystallization is the difference in the
free energy between the glassy phase and the
corresponding crystalline phase(s) of the same
composition. The crystalline phases formed as a
result of crystallization may be either equilibri-
um phases or, as is frequently noted, metastable
phases, which may also form in the initial stages
of decomposition and will eventually transform
to equilibrium phases. Therefore, it should be
possible to understand the crystallization behav-
ior of metallic glasses with reference to a
hypothetical free energy vs. composition
diagram [79].
Metallic glasses are in a nonequilibrium state
with respect to thermodynamic stability. But,
they are also not in configurational equilibrium.
Accordingly, on annealing, the as-synthesized
glass slowly transforms towards an ‘‘ideal’’
glass of lower energy through structural relaxa-
tion. A real crystalline material can be consid-
ered as an ideal material containing a variety of
defects, whose character can be identified and
well quantified. The as-synthesized glass can be
similarly considered as an ‘‘ideal’’ or ‘‘perfect’’
glass containing defects. However, the nature of
defects present in the glass is presently un-
known. Thus, structural relaxation of a
quenched glass results in the formation of an
ideal glass. The mechanism(s) by which struc-
tural relaxation occurs in glasses is through
annihilation of ‘‘defects’’ or free volume, or
recombination of defects of opposing character,
or by changes in both topological and composi-
tional short-range order [80].
The glass prepared by solidification from the
melt (whether at slow rates or faster rates)
contains an excess quenched-in free volume
and its amount increases with increasing solidi-
fication rate. On reheating the glassy sample to a
temperature below Tg, structural relaxation
occurs through compositional short range order
(CSRO) and topological short range order
(TSRO). CSRO involves variation in chemical
composition from point to point (slight changes
in the local chemical environment) and is some-
times reversible. On the other hand, in TSRO the
atomic configuration is different due to collec-
tive motion of groups of atoms and is an irre-
versible process. This means that the process of
structural relaxation is associated with the re-
distribution and reduction of excess quenched-
in free volume which will result in a decrease in
 Metallic Glasses 19

Figure 7. TEM images and electron diffraction pattern from a glassy alloy
A) Low-resolution TEM image showing the absence of any contrast; B) Electron diffraction pattern showing the presence of a
broad and diffuse halo; C) High-resolution TEM image showing the typical salt-and-pepper contrast; All these features are
typical of a fully glassy phase

volume, and consequently an increase in
density. In a fully relaxed glass, that has attained
the ‘‘equilibrium’’ free volume concentration, it
is possible to separate the effects due to CSRO
and TSRO.
Structural relaxation in metallic glasses is
achieved by a low-temperature annealing pro-
cess, which does not cause crystallization. How-
ever, significant changes in physical properties
(and mechanical properties in some cases) have
been reported. For example, relaxed glasses
exhibit a decreased specific heat, reduced dif-
fusivity, reduced magnetic anisotropy, in-
creased elastic constants (by about 7%), signifi-
cantly increased viscosity (by more than five
orders of magnitude), and loss of (bend) ductili-
ty in some glassy ribbons, in addition to changes
in electrical resistivity (by about 2%), Curie
temperature (by as much as 40 K), enthalpy (by
about 800–1200 kg/mol), superconductivity,
and several other structure-sensitive proper-
ties [80]. Another important property that
changes on structural relaxation is the density.
A small increase in density (about 0.5% for
melt-spun ribbons [81] and a smaller value of
about 0.1 to 0.15% for BMG alloys [82, 83]) was
also reported to occur due to structural relaxa-
tion in metallic glasses. The relaxed glass is the
starting point for all the transformations to be
studied.
The relaxed glass will transform first into the
supercooled liquid state at Tg, provided that one
is able to differentiate between the Tg and Tx
temperatures. This is the case in all BMGs, and
20 Metallic Glasses

is also true in some melt-spun ribbon samples, 6.2. Polymorphous Crystallization

notably those based on Pd and Pt [84, 85]. The
supercooled liquid can then undergo a variety of
transformations. For example, it can undergo
phase separation, i.e., transform into two differ-
ent glassy phases with two different composi-
tions, manifested by the presence of two Tgs in
the DSC curve of the glassy alloy and by the
appearance of an interconnected structure in
electron micrographs. It is also important to
realize that phase separation does not occur in
all metallic glasses.
Figure 8 shows the hypothetical free energy
vs. composition diagram for the glass and dif-
ferent crystalline phases in the Fe-rich Fe–B
system. In this diagram, the variation of free
energy with composition is presented for the
glassy phase, the Fe-rich a-Fe solid solution, the
equilibrium Fe2B phase, and the frequently
detected metastable Fe3B phase. The stable
equilibrium between the a-Fe and Fe2B phases
is indicated by the solid common tangent line
and the metastable equilibrium between the a-
Fe and glassy phases or a-Fe and Fe3B phases is
denoted by the dashed common tangent lines.
Depending on the composition of the glassy
alloy, the metallic glass could crystallize into
the stable equilibrium phases in one of the three
following ways:
In this mode of transformation, the glassy
phase will transform into a single crystalline
phase without any change in composition. The
polymorphous crystallization will occur only
in composition ranges where the glassy phase
had formed at a composition corresponding to
either a stable or metastable crystalline solid
solution or an intermetallic phase. With refer-
ence to Figure 8, polymorphous crystallization
is possible when the glassy phase transforms
into the a-Fe solid solution (reaction 1), or the
Fe3B phase (reaction 4), or the Fe2B phase.
Since Fe3B (formed by reaction 4) is a meta-
stable phase, it will subsequently transform
into the equilibrium a-Fe and Fe2B phases on
further annealing. Similarly, the supersaturat-
ed a-Fe (formed by reaction 1) will also trans-
form to the equilibrium constitution on further
annealing. During polymorphous crystalliza-
tion, the growth of crystals is linear with time
and the growth rate has an Arrhenius depen-
dence on temperature. Such transformations
have been least common among the glass–
crystal transformations. Figure 9A shows a
bright-field TEM micrograph showing poly-
morphous crystallization in a Ti50Ni25Cu25
BMG alloy.

Figure 8. Hypothetical free energy vs. composition diagram for the Fe-rich Fe–B alloy system.
The variation of free energy with composition is represented for the equilibrium a-Fe solid solution and the Fe2B phases and the
metastable Fe3B phase. The solid common tangent line represents the stable equilibrium between a-Fe and Fe2B phases, while
the dotted common tangent line represents the metastable equilibrium between a-Fe and Fe3B phases.
 Metallic Glasses 21

Figure 9. TEM images showing the microstructures obtained after polymorphous, eutectic, or primary crystallization of BMG
alloys.
A) Polymorphous crystallization in a Ti50Ni25Cu25 BMG alloy on annealing for 28 min at 709 K; B) Eutectic crystallization in a
Zr62.5Cu22.5Al10Fe5 glassy alloy annealed for 10 min at 713 K; C) Primary crystallization in a Ti50Ni20Cu23Sn7 alloy on heating
the glass in a DSC at 40 K/min up to 787 K

6.3. Eutectic Crystallization reactions the crystal growth rate is independent

In this mode of crystallization, the glassy phase
transforms simultaneously into two (or more)
crystalline phases by a discontinuous reaction.
For example, through reaction 3 in Figure 8, the
glassy phase can form a mixture of a-Fe and
Fe3B or through reaction 5 it can form a mixture
of a-Fe and Fe2B phases. This mode of crystal-
lization has the largest driving force and can
occur in the whole concentration range between
the two stable or metastable phases.
Like polymorphous crystallization the
eutectic crystallization is a discontinuous reac-
tion; the overall composition of the crystal and
the glass are the same. The composition of the
glassy matrix remains unchanged until the
glass–crystal interface sweeps past it. For such
of time until hard impingement with another
crystal occurs.
Figure 9B shows a bright-field TEM image
from a Zr62.5Cu22.5Al10Fe5 BMG alloy annealed
for 10 min at 713 K, when eutectic crystalliza-
tion had occurred.
6.4. Primary Crystallization
In this mode, a supersaturated solid solution,
e.g., a-Fe, forms first from the glassy phase,
indicated by reaction 2. Since the concentration
of the solute in the a-Fe phase is lower than that
in the glassy phase, the solute (boron) atoms are
rejected into the glassy phase and consequently
the remaining glassy phase becomes enriched in
22 Metallic Glasses
B until further crystallization is stopped. At this
stage a metastable equilibrium is established
between a-Fe and the glassy Fe–B phase, with
the new composition. This B-enriched Fe–B
glassy phase can transform later or at higher
temperatures by one of the mechanisms
described above. For example, if the B concen-
tration is close to 33 at%, then a polymorphous
crystallization event could occur resulting in the
formation of Fe2B. Alternatively, if the B
concentration in the new glassy phase is 25 at
%, then polymorphous crystallization to Fe3B
could occur. On the other hand, if the B concen-
tration is different from these two values, then
the glassy phase could crystallize in a eutectic
mode.
Primary crystallization of metallic glasses
has been observed to be the main mode of
transformation in many metallic glasses. The
crystalline phase formed could be either a ter-
minal solid solution or an intermediate phase.
The morphology of the primary crystals is high-
ly dependent on composition and ranges from
spherical to highly dendritic. Furthermore, the
growth rate of the primary crystals depends on
their morphology. In the absence of interfacial
instabilities, the growth is parabolic with time,
i.e., the mean radius of the crystals increases
linearly with the square root of time.
Figure 9C presents a bright-field TEM image
obtained on heating a Ti50Ni20Cu23Sn7 BMG
alloy in a DSC at a heating rate of 40 K/min up
to 787 K. Note the distribution of fine crystal-
lites in a glassy matrix.
Application of pressure during crystalliza-
tion is known to affect the kinetics of transfor-
mation and also the nature of the crystallization
product [86–88]. Application of pressure during
crystallization of metallic glasses may lead to
four different effects–acceleration of crystalli-
zation, retardation of crystallization, formation
of metastable phases [89], or amorphization
[90].
7. Physical Properties
Measurement of the different physical proper-
ties of metallic glasses such as density, specific
heat, viscosity, electrical resistivity, thermal
expansion, and diffusivity will greatly aid in
understanding the structural relaxation and
crystallization processes occurring in these
metastable materials and their effect on
properties.
7.1. Density
Metallic glasses are typically about 2 to 3% less
dense than their crystalline counterparts [91].
This large density difference is attributable to
the presence of free volume retained in the
glassy ribbons. On annealing the glassy ribbons
this free volume is annihilated leading to an
increase in the density. On the other hand,
BMGs are synthesized at relatively lower solid-
ification rates than melt-spun ribbons and there-
fore the free volume content in the BMG alloys
is lower. Consequently, it has been reported that
the density of the BMG alloys is about 0.5%
lower than that of the crystalline counterpart.
Since the density of a material is often a reflec-
tion of the packing state of the constituent
elements, measurement of density values can
provide an understanding of the random atomic
configurations in metallic glasses. In line with
the above presumption, the densities of
Pd40Cu30Ni10P20 glass were measured as a func-
tion of cooling rate [92] and it was noted that the
difference in density between the BMG alloy
and the crystalline alloy was very small, when
solidified at relatively slow cooling rates, but
higher when solidified at higher rates. This
observation suggests that the constituent atoms
have sufficient time to rearrange themselves
into dense atomic configurations when the melt
is solidified at relatively low cooling rates, and
that the density of the BMG is higher (and closer
to that of the crystalline alloy), the slower the
cooling rate.
7.2. Thermal Expansion
Measurement of thermal expansion in metallic
glassy alloy samples, can provide useful infor-
mation about the structural relaxation behavior
of glasses. The coefficient of thermal expansion
(CTE) has been measured in the fully glassy
state, structurally relaxed glassy state, super-
cooled liquid state, and crystallized conditions.
The CTE values of samples in the fully
glassy state are typically in the range of (10 to
15)  10
6 K
1, except in the case of Sm-based

glasses, where it was reported to be about 125 
10
6 K
1. The CTE values in the glassy state
are usually larger than those of the crystalline
pure metals on which they are based. In com-
parison to the as-quenched glassy state, the CTE
value of the glass in the structurally relaxed
condition is higher. The CTE values are much
higher in the supercooled liquid condition and
they are lower in the crystallized condition than
even in the glassy state [93].
Structural relaxation will also have an effect
on the thermal expansion of the material [94].
The relative length change during annealing of a
metallic glass sample is directly related to the
annihilation of excess quenched-in free volume
and therefore this occurs due to TSRO. The
disappearance of free volume will lead to a
decrease in the length of the sample and there-
fore in the CTE as well. This is a nonreversible
process. However, when the glassy sample is
heated to temperatures below Tg, where struc-
tural relaxation also occurs but through CSRO,
the process is reversible. That is, the same value
of CTE is obtained during thermal cycling by
cooling and through subsequent reheating, but
only up to temperatures just below Tg. The CTE
value appears to be independent of the heating
rate at which the sample is heated to high
temperatures [95].
7.3. Diffusion
Studies of diffusion are very important in the
field of metallic glasses. It is scientifically
interesting to determine whether the mecha-
nism of diffusion in metallic glasses is
different from that in crystalline materials.
More specifically, it is important to decide
whether the single atom jumps observed in
crystalline materials are true in metallic glasses
as well. The processes of structural relaxation,
phase separation, and crystallization during
annealing of a quenched glass involve diffu-
sion and therefore the thermal stability of
metallic glasses is determined by their diffu-
sion behavior.
Diffusion studies were conducted on melt-
spun metallic glass ribbons [96, 97], but mostly
in the glassy state, at temperatures below Tx.
The width of the supercooled liquid region is
very small in these melt-spun metallic glasses, if
Metallic Glasses 23
observed at all, and therefore it was not possible
to study the diffusion behavior in the super-
cooled liquid condition. The advent of BMGs,
which show a significantly large DTx range, has
changed the situation significantly; detailed
diffusion studies have been conducted in the
supercooled liquid region in BMGs [98]. Such
temperature regimes were previously not
accessible.
The diffusion behavior of melt-spun glassy
ribbons is known to be sensitive to structural
relaxation. Accordingly, in the as-quenched
ribbon (i.e., in the unrelaxed sample), the dif-
fusivity decreases as a function of time due to
structural relaxation and annealing out of excess
free volume. The diffusivity reaches a constant
value only when the sample is fully relaxed.
Such a situation is not obtained in the BMG
alloy samples due to the relatively slow solidi-
fication rates at which these glassy alloys are
produced. Therefore, whenever diffusion stud-
ies are carried out on thin ribbon specimens,
they are given a pre-annealing relaxation treat-
ment before the diffusion measurements are
made.
Although the diffusion coefficient increases
with increasing temperature, the variation of
logarithm of diffusivity with reciprocal of
temperature in BMG alloys is not linear, but
shows a ‘‘kink’’. The diffusion data can be
divided into two subsets, each described by a
different Arrhenius equation. The first region is
for temperatures below the ‘‘kink’’ tempera-
ture, and the other is for temperatures above the
‘‘kink’’. This kink temperature, which repre-
sents the change in the temperature depen-
dence of diffusivity, is frequently identified as
the glass transition temperature. Accordingly,
the pre-exponential factor Do and the activa-
tion energy for diffusion, QD are different in
these two regions. The diffusivity in the super-
cooled liquid phase is much higher than that
obtained by extrapolation from the low-
temperature data in the glassy phase [99]. This
behavior is in contrast to melt-spun ribbons
which show a single straight line described by a
unique Arrhenius equation. The small values in
the glassy state suggest a single jump motion of
the atoms, while the larger values in the
supercooled liquid state might reflect a highly
cooperative motion of a number of atoms
[98].
24 Metallic Glasses
7.4. Electrical Resistivity
Since metallic glasses have liquid-like struc-
tures, they are ideal materials for testing theories
of transport in disordered systems. Furthermore,
experimental difficulties such as those associat-
ed with high temperatures and their attendant
problems are drastically reduced in the case of
metallic glasses.
Due to their intrinsic disordered structure,
metallic glasses exhibit an electrical resistivity
of about two orders of magnitude higher than
their crystalline counterparts. However, some
metallic glasses exhibit a superconducting tran-
sition at temperatures below about 9 K. These
temperatures are very low in comparison to
conventional metal superconductors (23 K),
and the novel high-temperature oxide super-
conductors with a Tc of about 100 K.
Metallic glasses are characterized by the
following typical electrical characteristics
[100]:
. The room temperature electrical resistivity is
typically in the range of 80 to 420 mWcm,
. The temperature coefficient of resistivity
(TCR), aR ¼ (1/r)(dr/dT), is very small (in
the range of  10
4 K
1) and is often
negative,
. The resistivity varies by less than 7% between
4.2 and 300 K, and
. A resistivity minimum occurs at a low tem-
perature, Tmin, below which the resistivity
increases with a decreasing temperature and
obeys the ln[T] law.
Since there is no essential change in spatial
atomic configuration during glass formation, a
liquid and a glass belong structurally and
thermodynamically to the same phase. Accord-
ingly, both the liquid and glass of the same
composition show similar magnitudes of TCR.
Figure 10 shows the variation of electrical
resistivity of some metallic glass ribbons. While
the Pd-based glasses show a positive aR, the Ni–
Nb glasses show a negative aR. A sudden drop
in resistivity is detected at the crystallization
temperature in both cases. Furthermore, the
electrical resistivity of the crystalline sample is
found to increase more rapidly upon heating and
change at the melting point, Tm. Additionally,
the resistivity values in the liquid state lie in a
Figure 10. Temperature variation of electrical resistivity of
Pd81Si19, Pd77.5Cu6Si16.5, and Ni60Nb40 alloys in the glassy,
crystalline, and liquid states
region which can be obtained from a rough
extrapolation of the glassy state data, with the
difference that the magnitude of aR in the liquid
state is slightly larger than that in the glassy
state. The relatively high resistivity of metallic
glasses originates essentially from their inherent
structural disorder, while the small value of aR
has been explained on the basis of a reduced
phonon contribution to the scattering of
electrons.
Only a limited number of investigations exist
on the electrical resistivity of the recently de-
veloped BMG alloys. Figure 11 shows a plot of
TCR of Pd40Ni40
xCuxP20 BMG alloys as a
function of Cu content. TCR is negative at low
Cu contents and it slowly becomes positive,
passing through a zero value, as the Cu content
is increased [101]. Thus, it should be possible to
obtain a zero TCR by fine-tuning the Cu content
in the BMG alloy. A similar situation of TCR
going from a negative to positive value was
reported to occur as the P content is reduced
in melt-spun ribbons of a Pd–Ni–P alloy
system [102].
Metallic glassy ribbons of La–Au alloys
were first shown in 1975 to be superconducting
below 3.5 K [103]. Since then a superconduct-
ing transition was noted in a number of Ti, Zr,
Hf, Cu, Mo, and Nb-based alloy systems [100,
104–107]. However, their superconducting

Figure 11. Variation of TCR with Cu content in melt-spun Pd40Ni40
xCuxP20 glassy alloy with x ¼ 0, 10, 20, 30, and 40
at% Cu)
transition temperatures were quite low (<9 K)
and the critical fields and flux pinning ability
were also quite low due to the homogeneous
glassy structure. The latter property could be
improved by incorporating flux pinning centers
through crystallization [106, 107]. By subject-
ing the melt-spun glassy alloy phase to high
pressures during crystallization, a metastable
cubic Nb3Si superconducting phase could be
synthesized [108].
7.5. Specific Heat
Like other physical properties, the specific heat
of metallic glasses, measured using DSC, can
also provide valuable information about struc-
tural relaxation. By calculating the difference in
the specific heats between the liquid and crys-
talline states, other thermodynamic parameters
such as enthalpy and entropy can be estimated.
From these parameters, the Gibbs free energy
difference between the crystal and the liquid
phases, DGl
x can be calculated. Knowledge of
the free energy difference between the crystal
and the liquid phases can provide information
about the GFA of alloys. In general, the lower
the DGl
x(T) value, the better is the GFA. In
addition, the smaller the entropy of fusion, the
higher is the GFA. The free energy difference
between the crystal and the liquid phases is
the driving force for crystallization in the case
of polymorphous crystallization of metallic
glasses. However, in those cases where
Metallic Glasses 25
crystallization takes place by eutectic or
primary modes, this value is the lower limit
of the thermodynamic driving force for
crystallization.
7.6. Viscosity
Viscosity is perhaps the most important physi-
cal property of a liquid alloy that determines its
GFA and flow behavior. Several studies have
been conducted to evaluate the viscosity of
alloys as a function of temperature, shear rate,
and alloy constituents and composition. The
formation of the glassy phase is related to a
significant increase in the viscosity of the under-
cooled melt at Tg. Whereas the viscosity of
simple alloys is typically about 10
3 Pa s at
the melting point, it increases to about 1012 Pa s
at Tg, a value that is taken as a measure to define
Tg.
The variation of viscosity with temperature is
of great importance in understanding the for-
mation of metallic glasses, realizing that the
higher the viscosity at the melting temperature,
the easier it is for the glass to form. The variation
of viscosity with temperature in the supercooled
liquid region is usually expressed by the Vogel–
Fulcher–Tammann (VFT) equation:
 
B
h ¼ ho exp
T
T o
where To is referred to as the VFT temperature
(or fictive temperature) and represents the
26 Metallic Glasses
Figure 12. Viscosity of glass-forming liquids as a function of inverse temperature, normalized by the glass transition
temperature, Tg
The metallic alloys are intermediate between strong network-forming liquids such as SiO2, and fragile liquids such as
o-terphenyl.
temperature at which the relaxation time and
thus the barrier to viscous flow would become
infinite, ho is the high temperature limit of
viscosity, and B is a fitting parameter. The value
of To is found to lie near, but below Tg. The value
of ho can be expressed as:
NA h
ho ¼
V
where NA represents the Avogadro’s number, h
the Planck’s constant, and V the molar vol-
ume [109]. ANGELL [110] has modified the
equation for viscosity as:
 
D* T o
h ¼ ho exp
T
T o
where the parameter D*, referred to as the
fragility parameter, controls how closely the
system obeys the Arrhenius behavior (D* ¼ ¥).
Liquids with very large and very small values
of D* are known as strong and fragile liquids,
respectively. Strong liquids show the Arrhenius
behavior for temperature dependence of viscos-
ity, have a high viscosity at the melting point,
and form stable glasses. Fragile liquids have a
low viscosity at the melting temperature, but the
viscosity rises sharply as the liquid approaches
the glass transition temperature. Such liquids
are marginal glass formers and if they form
glasses, they are unstable with respect to crys-
tallization. That is, the GFA of the alloy
increases with the fragility parameter. Accord-
ingly, the value of D* is of the order of 2 for the
most fragile liquids, while it is 100 for the
strongest glass former such as SiO2. Figure 12
shows a typical Angell plot.
The variation of viscosity with temperature
of a Pd40Ni10Cu30P20 BMG alloy at a heating
rate of 20 K/min and a compressive stress of 20
kPa is shown in Figure 13A [111]. The viscosity
remains almost constant up to near Tg, at which
temperature it starts to decrease slowly first and
then very rapidly reaching a minimum. The
minimum temperature (of 675 K in the present
case) corresponds to the onset temperature of
crystallization. After crystallization, the viscos-
ity increases steeply with increasing tempera-
ture and then reaches a steady-state value on
completion of crystallization. It has been sug-
gested [112] that the absolute value of hmin is an
indication of the thermal stability of the super-
cooled liquid. The value of 8.3  105 Pa s for
the Pd40Ni10Cu30P20 BMG alloy is two to three
orders of magnitude lower than that (about
108 Pa s) for the Pd77.5Cu6Si16.5 alloy [91],
suggesting that the supercooled liquid of the
Pd–Ni–Cu–P alloy has a higher resistance
against crystallization than the Pd-Cu-Si alloy.

Figure 13. A) Variation of viscosity with temperature for the Pd40Cu30Ni10P20 BMG alloy at a heating rate of 20 K/min under a
compressive stress of 20 kPa; B) Change in the minimum viscosity (hmin) with heating rate for the Pd40Cu30Ni10P20 BMG
alloy
This is an indication that the Pd–Ni–Cu–P glass
is appropriate for secondary working through
viscous flow in the supercooled liquid region.
Furthermore, it has been noted that the viscosity
decreases with increasing heating rate em-
ployed as shown in Figure 13B. It has also been
suggested that measurement of viscosity at high
heating rates is one effective way of reducing
the oxygen contamination from the measuring
environment [113].
8. Corrosion Behavior
The corrosion behavior of metallic glasses be-
comes important when these materials need to
be used in aggressive and hostile environments
(high temperatures, oxidizing atmospheres, and
corrosive media). Knowledge of the corrosion
behavior becomes crucial when these novel
materials are considered for biomedical appli-
cations and for decorative applications, or when
surface appearance assumes importance.
The corrosion behavior of a number of glassy
alloys has been investigated by either weight
loss measurements and/or electrochemical
methods. Before actually conducting the corro-
sion tests, the specimens are mechanically po-
lished in cyclohexane with silicon carbide paper
up to grit 2000, degreased in acetone, washed in
Metallic Glasses 27
distilled water, and dried in air. After immersion
in the corrosion medium for the desired length
of time, the specimens are again washed in
distilled water, dried and then weighed to deter-
mine the weight loss.
The corrosion behavior of metallic glassy
alloy ribbons (about 20 to 50 mm in thickness)
produced by melt spinning was evaluated start-
ing from 1974 [114, 115]. It was reported that
Cr-containing Fe-based Fe80
xCrxP13C7 glassy
ribbons exhibited much higher corrosion resis-
tance than the crystalline Fe–Cr alloys.
Figure 14A shows that while the crystalline
Fe–Cr alloys corroded at a rate of about 0.5 to
1 mm/a, the glassy Fe–Cr–P–C alloy did not
show any measurable corrosion rate under iden-
tical conditions of exposure in 1 M NaCl solu-
tion at 303 K. Another important observation
made was that the minimum amount of Cr
required to achieve this corrosion resistance in
the glassy alloy was only 8 at%, much less than
that required (>12 at%) in the crystalline state.
Figure 14B shows that the glassy alloy did not
exhibit any measurable weight change with the
concentration of HCl (from 0.01 N to 1 N) on
exposure for 1 week at 373 K. On the other
hand, the corrosion rate of the crystalline 18-8
austenitic stainless steel (Fe-18 wt% Cr-8 wt%
Ni) increased from 10
3 mm/a in 0.01 N HCl to
over 10 mm/a in 1 N HCl solution; severe
28 Metallic Glasses
Figure 14. Variation of corrosion rate as a function of (A) Cr content and (B) concentration of HCl in crystalline Fe–Cr alloys
and rapidly solidified glassy Fe80
xCrxP13C7 alloy
pitting corrosion occurred in the range of 0.5 to 1
N HCl in the crystalline alloy.
X-ray photoelectron spectroscopy studies
indicated that the passive film on the glassy
alloy consisted mainly of hydrated chromium
oxyhydroxide, which is also a common major
constituent of passive films on crystalline stain-
less steels. An important difference is that the Cr
content in the passive layer of the glassy alloy
was much higher than that on a conventional
austenitic stainless steel. Thus, it was concluded
that the extremely high corrosion resistance
of the glassy alloy was only partially attributed
to the formation of a protective hydrated chro-
mium oxyhydroxide film [116], and that other
factors also play an important role.
Since metallic glasses are in a thermodynam-
ically metastable state, they are expected to
exhibit higher corrosion rates. The improved
and superior corrosion resistance of the glassy
alloys, in comparison with the crystalline alloys
of similar composition, has been attributed to
the following factors:
. Metallic glasses do not contain any second
phase particles or precipitates. Furthermore,
the segregation patterns are also completely
avoided. Therefore, metallic glasses can be
considered as chemically homogeneous.
. The glassy phase does not contain any crystal
defects such as grain boundaries, dislocations,
and second-phase precipitates, which could
act as galvanic cells to initiate localized
corrosion.
. Since passive films form uniformly on the
glassy alloy surfaces, lower amounts of pas-
sivating alloying elements are needed than in
a crystalline alloy to achieve a similar stability
of the passive film.
High corrosion resistance has been reported
in a number of melt-spun ribbons or BMG alloy
specimens [117–120]. The corrosion behavior
of the glassy alloys is not dependent on the
section thickness. Accordingly, the corrosion
behavior of melt-spun ribbons and BMGs of the
same composition is similar.
8.1. Effect of Alloying Additions
The passivating ability and hence the corrosion
resistance of metal–metalloid glasses are sig-
nificantly different with different metalloid ele-
ments. The beneficial effect of the metalloid
elements in improving the corrosion resistance
decreased in the order P, C, Si, and B. When the
metallic glassy alloy is not covered by a stable

Figure 15. Corrosion rates of (Cu0.6Hf0.25Ti0.15)100
xNbx
alloys (with x ¼ 0, 2, 4, 6, and 8 at% Nb) immersed in 1 N
HCl, 3 wt% NaCl, and 1 N H2SO4 þ 0.001 N NaCl solutions
for 168 h at 298 K open to air
surface film, the P-containing glasses dissolve
most actively resulting in accumulation of the
beneficial species in the passive film; responsi-
ble for the high corrosion resistance of glassy P-
bearing alloys [121].
Addition of almost all metallic elements to
metal–metalloid glassy alloys has been shown
to improve the corrosion resistance. Cr is the
most popular alloying addition since it forms its
own passive film and improves the corrosion
resistance. Alloying elements that are more
Figure 16. Effect of additional alloying elements (Ta, Mo, or Nb) on the corrosion behavior of Cu60Zr30Ti10 BMG alloy in
1 N HCl, 0.01 N HCl, and 3 wt% NaCl solutions after exposure for 168 h and in 1 N H2SO4 and 1 N HNO3 solutions after
exposure for 336 h
Metallic Glasses 29
active or more noble than the main metallic
component of the alloy also improve the corro-
sion resistance. For example, addition of Nb, V,
Mo, or W to Fe-based metal-metalloid type
glassy alloys has been shown to improve the
corrosion resistance. Furthermore, a metal–met-
alloid glass containing only one metallic ele-
ment was shown to be less corrosion resistant
than the pure metal.
A common observation made was that the
corrosion resistance of these glassy alloys is
substantially improved by alloying them with
additional elements such as Mo, Nb, or Ta.
Amongst these alloying additions, Nb seems to
be the most effective. For example, Figure 15
presents the average corrosion rates of
(Cu0.6Hf0.25Ti0.15)100
xNbx BMG alloys as a
function of the Nb content [122]. It is clear
from the figure that while the Nb-free alloy
showed a high corrosion rate of 340 mm/a in
1 N HCl solution, addition of Nb significantly
reduced the corrosion rate to 2.6 mm/a at 6 at%
Nb level and to less than the detectable value
(1 mm/a) at 8 at% Nb [122, 123]. Improved
corrosion resistance was also obtained in alloys
modified with the addition of 1 at% Nb, 1 at%
Mo, and 0.2 at% Ta immersed in different
corrosive solutions [124] and the trend of cor-
rosion rates is presented in Figure 16.
Metal–metal type metallic glasses are in
general not corrosion resistant. Their corrosion
30 Metallic Glasses
resistance is always lower than that of the
crystalline pure metal component with the high-
est corrosion resistance or the highest passivat-
ing ability [121].
8.2. Influence of Structural Changes
The influence of structurally relaxing or
crystallizing the metallic glassy alloys on the
structure and corrosion behavior of Fe-based
metal–metalloid alloys has also been investigat-
ed. The effect of Cr content on the corrosion
behavior of Fe73.5Si13.5B9Nb3Cu1 BMG alloys
in different concentrations of H2SO4 (1, 3, and
5 N) have been studied [125, 126]. The corro-
sion behavior of this alloy in three different
conditions was investigated: (i) in the as-solidi-
fied fully glassy condition, (ii) by annealing it
for 1 h at 813 K to obtain a nanocrystalline
structure (10–15 nm grain size), and (iii) by
fully crystallizing the samples (to achieve a
grain size of 0.1–1 mm) through annealing at
973 K for 1 h. The corrosion resistance was
higher with increasing Cr content in the range
studied (0 to 8 at%). However, a minimum Cr
concentration of 8 at% was found necessary to
generate a stable passive layer. Among all the
conditions studied, the glassy structure showed
the best corrosion resistance, followed by that in
the nanocrystalline state. The fully crystallized
alloy showed the least corrosion resistance.
It was also noted that the effect of dispersion
of nanometer-sized particles in a glassy matrix
becomes significant, as far as corrosion resis-
tance is concerned, only when the particles are
reasonably large, say >20 nm. If these particles
are extremely fine, e.g., 2–3 nm, they do not
seem to affect the corrosion behavior
adversely [127].
9. Mechanical Properties
Mechanical properties of materials play a very
important role for applications. The mechanical
behavior of crystalline metallic materials is
determined by the nature and density of disloca-
tions, and their ability to move. The presence of
dislocations in crystals has also been noted to be
the reason for their low strength (compared to
the theoretical value) and their plastic deforma-
tion behavior. Since metallic glasses are non-
crystalline in nature, and therefore they do not
contain any crystalline defects, including dis-
locations, metallic glasses are expected to ex-
hibit the high theoretical strength.
Even though metallic glasses were synthe-
sized in the form of thin splats as early as
1960 [1], study of their mechanical behavior
started only in the 1970s with the synthesis of
long ribbons by the melt spinning tech-
nique [128]. Interesting and seminal contribu-
tions have been made regarding the deformation
mechanisms, failure criteria, and origins of
strength, ductility and toughness and these have
been well documented in some early re-
views [129–133]. It was shown that metallic
glasses are very strong with the yield strength
exceeding 1 GPa in some metal–metalloid sys-
tems. It was also shown that they exhibited very
limited plastic strain (often less than about
0.5%) in tension and that inhomogeneous de-
formation occurred through formation of shear
bands. Even though many different theories
were proposed to understand and explain the
mechanical behavior of these thin ribbon speci-
mens, the reliability of the results was poor due
to the limited size of the samples and conse-
quently a poorly defined and ill-controlled stress
state during mechanical testing.
The successful synthesis of BMGs in the late
1980s/early 1990s [29, 134] changed the situa-
tion completely. As a result of this development
and the availability of advanced characteriza-
tion techniques, research on the mechanical
behavior of BMGs has been very active. Two
comprehensive reviews on the mechanical
behavior of BMGs have appeared recently
[135, 136].
9.1. Deformation Behavior
Metallic glasses, including BMGs, have a very
high tensile strength, but, their weakness is the
low room temperature ductility. Metallic
glasses fail soon after yielding without showing
any signs of reasonable amount of plastic de-
formation. At high temperatures, however, the
deformation behavior is quite different.
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, <0.5 Tg,
deformation is mostly concentrated in a few
very thin ‘‘shear bands’’ which form approxi-
mately on planes of maximum resolved shear
stress, inclined close to 45 to the loading axis.
This localized deformation, referred to as ‘‘in-
homogeneous’’ deformation, makes the metal-
lic glass mechanically unstable at high stresses
and therefore it fails catastrophically.
On the other hand, at high temperatures,
>0.5 Tg, metallic glasses undergo viscous flow
in which plastic strain is distributed continu-
ously, but not necessarily equally, between
different volume elements within the material.
That is, each volume element of the specimen
contributes to the strain. This type of deforma-
tion is referred to as ‘‘homogeneous’’
deformation.
When a BMG sample is subjected to a tensile
test, the sample deforms elastically with a max-
imum elastic strain of about 2%, and then
fractures catastrophically. On the other hand,
when a BMG sample is tested under compres-
sion, the stress–strain curve consists of elasticity
followed by a small amount (up to 1%) of plastic
strain. Serrated flow is usually observed at an
early stage of compressive deformation.
9.1.1. Inhomogeneous Deformation
Metallic glasses exhibit the phenomenon 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. A number of different reasons have
been suggested for this phenomenon. These
include local production of free volume due to
flow dilatation, local evolution of structural
order due to the shear transformation zone
(STZ) operations, redistribution of internal
stresses associated with STZ operations, and
local heating.
When shear bands form and propagate, the
surrounding material recovers elastically and
arrests the shear band propagation. When this
process is repeated, serrated flow is obtained.
Serrated flow is also observed during nanoin-
dentation, but only at slow loading rates.
Figure 17 shows an optical micrograph of the
surface of a specimen deformed under compres-
Metallic Glasses 31
Figure 17. An optical microscopy image showing the
formation of multiple shear bands in an Ni50Pd30P20 BMG
specimen subjected to compression testing
sion showing the presence of shear bands [137].
However, the nature of the shear bands is not
very clear, except that they are regions where
deformation is concentrated.
9.1.2. Homogeneous Deformation
Homogeneous deformation in metallic glasses
occurs at high temperatures, e.g., >0.5 Tg and
also in the supercooled liquid state. This defor-
mation could be thought of as viscous flow of the
supercooled liquid (it can result in significant
plasticity) and is therefore of commercial im-
portance. It is possible to achieve net-shape
forming capability by working the metallic
glass in this temperature regime [138]. The
transition temperature between the inhomoge-
neous and homogeneous deformation can be
thought of as a brittle-to-ductile transition, and
is strongly dependent on the applied strain rate,
suggesting that homogeneous deformation is
associated with a rate process.
The homogeneous deformation of metallic
glasses can also be understood using the concept
of STZ [139]. It has been suggested that STZ is
essentially a local cluster of atoms (a few to
perhaps up to 100) that undergoes an inelastic
shear distortion from one relatively low energy
configuration to another low-energy configura-
tion, crossing an activation barrier [135]. These
atomic-scale STZs collectively deform under an
applied shear stress to produce macroscopic
shear deformation. However, the STZ is not a
32 Metallic Glasses
structural defect in a glassy material in the way
that a dislocation is a defect in a crystal. Instead,
an STZ is an event defined in a local volume and
not a feature of the glass.
9.2. Deformation Maps
Deformation maps help in delineating the dif-
ferent modes and mechanisms of plastic defor-
mation of a material as a function of stress,
temperature, and structure. Based on the de-
formation behavior of metallic glass ribbons,
SPAEPEN [140] introduced an empirical defor-
mation map, in which the various modes of
deformation are indicated. The temperature
region between Tx and Tl is inaccessible for
mechanical measurements since the glass crys-
tallizes at Tx. However, reasonable extrapola-
tions of the strain rate contours could be made
through this region. The map indicates the
temperature and stress regimes where the de-
formation is either homogeneous or inhomo-
geneous and the locations of these regions are
as expected from experimental observations.
Since BMGs exhibit a wide supercooled liquid
region, DTx (¼ Tx
Tg), detailed investigations
have been carried out to study the deformation
behavior of BMGs in this temperature re-
gime [141, 142].
Both the inhomogeneous and homogeneous
modes of deformation can be explained by using
the concept of STZ [135]. Therefore, instead of
a ‘‘deformation mechanism map’’, the term
‘‘deformation map’’ has been used. The most
important aspect is the stress–strain rate and/or
temperature at which transition occurs from the
homogeneous mode to inhomogeneous mode of
deformation. As such these maps look some-
what similar to the maps proposed by SPAE-
PEN [140] although he considered this transition
in terms of the free volume model. It is cau-
tioned that these deformation maps do not con-
sider the evolution of the glass structure during
deformation and that they also lack information
about fracture behavior. In spite of this, it is
suggested that these maps could be used as
semiquantitative tools, e.g., for rationalizing
observed trends with applied rate or tempera-
ture, or for comparing observed mechanical
responses for different glasses tested at a com-
mon absolute temperature (room temperature)
but at different homologous temperatures
(T/Tg).
9.3. Temperature Rise at Shear Bands
As mentioned earlier, inhomogeneous deforma-
tion at low temperatures and high stresses takes
place through formation and propagation of
shear bands. Most of the plastic strain is local-
ized in these narrow shear bands which form
approximately on planes of maximum resolved
shear stress. It has been specifically noted that in
samples loaded in uniaxial tension (under plane
stress conditions), failure occurs almost imme-
diately after the formation of the first shear
band. Because of this, metallic glasses exhibit
virtually zero plastic strain before failure in
tension. On the other hand, specimens loaded
under constrained geometries such as uniaxial
compression, bending, rolling, or under local-
ized indentation (plane strain conditions) fail in
an elastic, perfectly plastic manner by the gen-
eration of multiple shear bands. Since the shear
bands carry very large plastic strains, metallic
glasses are ductile when deformed in compres-
sion or by rolling or indentation at room tem-
perature. Consequently, catastrophic failure is
avoided and the specimens exhibit some degree
of plasticity.
It has been mentioned earlier that the inho-
mogeneous flow in metallic glasses appears to
be related to a local decrease in the viscosity in
shear bands. One of the reasons suggested for
this was the local adiabatic heating that could
lead to a substantial increase in the temperature.
The local temperature rise in the shear bands has
been variously estimated to range from less than
0.1 to a few thousand Kelvin [143–145]. This
large discrepancy is mainly due to the difficulty
of directly measuring the temperature in the
extremely small distances of the shear band
widths (ca. 10 to 20 nm) [146, 147] and short
time scales (ca. 10
5 s) for shear band propaga-
tion [148]. To avoid this problem, the tempera-
ture rise in the shear bands was calculated. By
assuming that shear occurred simultaneously
over the entire band, the predicted temperature
increase was on the order of a few Kelvin [144].
However, assuming that shear initiates at one
point in the band and then propagates progres-
sively across the sample, the temperature

increases were estimated to be over
280 K [144]. It was pointed out that since the
magnitude of the load drop during failure was
much larger than that during serrated flow, the
temperature rise could be even higher. Conse-
quently, the temperature rise during failure is
sufficient even to melt the sample locally and
this could explain why the fracture surface
contained features that resembled resolidified
droplets.
Some experimental measurements of tem-
perature rise were also made. A high-speed
infrared camera was used to capture the
dynamic shear band evolution process in a
Zr52.5Cu17.9Ni14.6Al10Ti5 BMG alloy and the
measured temperature rise of 0.25 K in a single
‘‘hot band’’ translated to an estimated tempera-
ture rise of 650 K at the initiation site, assuming
that all the heat was originally generated in a
shear band about 10 nm in width [145, 149].
The temperature rise was elsewhere measured
as 500 K [150].
It is known that on heating a metallic glass,
the viscosity drops rapidly near Tg, and therefore
significant softening can occur in the metallic
glass. This softening will result in rapid shear
band propagation, eventually leading to cata-
strophic failure. The STZ model of ARGON [139]
was used to estimate the temperature rise in a
shear band [151]. By balancing the mechanical
work and heat generation within an STZ unit
and also considering collective STZ deforma-
tion, and that the process is adiabatic, the tem-
perature rise, DT at the time of fracture was
calculated and shown that a linear relationship
exists between DT and Tg. By depositing a 50-
nm thick tin coating on a Zr41.2Ti13.8 Cu12.5-
Ni10Be22.5 BMG sample and subjecting it to
four-point bend testing, it was shown that the
coating had melted during deformation at the
places where the shear bands had intersected the
surface [152]. These observations have provid-
ed direct evidence of temperature increases of
over 200 K in the operating shear bands (i.e., the
actual temperature is about 500 K), at least near
the surface (since tin has a melting temperature
of 505 K and it had melted). As an indirect proof
for the temperature rise, some researchers have
also observed nanocrystallization near shear
bands. By conducting detailed high-resolution
TEM studies of shear bands in a melt-spun
Cu50Zr50 metallic glass ribbon, a number of
Metallic Glasses 33
nanocrystallites, 5–20 nm in size, were ob-
served inside the shear bands in the deformed
specimen [153].
9.4. Strength
One of the important attributes of metallic
glasses (both in thin ribbon form and in bulk
form) is their high strength, exceeding 1 GPa in
most cases and reaching up to about 5 GPa. The
typical strain at yield is about 2%, and it varies
from about 1.2% for Pt–P glassy ribbons to
about 2.2% for Cu–Zr glasses. However, they
suffer from lack of ductility in most of the cases,
and the plastic strain is virtually zero. By clever
design of alloy compositions or by addition of
reinforcements, it has been possible to increase
their ductility.
The theoretical shear strength of a dis-
location-free crystal is known to be of the order
of m/5, where m is the shear modulus of the
crystal. Just as the strength of a crystalline metal
is determined by the Peierls stress—the internal
frictional stress for dislocation motion—the
fracture strength of a metallic glass is expected
to be determined by the atomic bond
strength [91]. This is because a glass does not
contain any crystal defects. Therefore, it is
logical to assume that the strength of a metallic
glass is related to the physical parameters deter-
mined by the atomic cohesive energy such as Tg,
elastic modulus, and coefficient of thermal ex-
pansion. Consequently, many different attempts
have been made to correlate the strength of
metallic glasses to these parameters.
The fracture strength of metallic glasses is
shown to increase with increasing value of
Tg [154]. But, the data points were scattered
between two bounds with the slopes of 1.22
MPa/K and 2.15 MPa/K. Because of the signifi-
cant amount of scatter, the authors concluded
that Tg may not be the sole factor determining
the strength of a BMG. Plastic deformation of
metallic glasses is facilitated by movement of
STZs. The glass transition is also similarly
facilitated by movement of groups of atoms. In
this sense both these processes are similar.
However, while the thermal energy for glass
transition is spread around the entire body of the
specimen during heating, the mechanical ener-
gy of shearing is highly localized in shear bands.
34 Metallic Glasses
Figure 18. Relationship between tensile strength and Young’s modulus for some typical BMGs. The data for crystalline alloys
also are shown for comparison.
Therefore, attempts have been made to relate
these two parameters as:
DTg
sf ¼ 1:1sy ¼ 55
V eE
where sf and sy are the fracture and yield
strength, respectively, DTg ¼ Tg
To where To
is the ambient temperature, and V is the molar
volume. A linear relationship is found to exist
between the calculated fracture strengths and
the published experimental fracture strengths.
The strength data of 15 BMG alloys were
analyzed with a view to exploring the underly-
ing physics of the linearity between strength vs.
DTg/V in terms of fundamental thermodynamic
principles [155]. A plot of room temperature
yield shear strength of these BMGs as a function
of (Tg
To)/V showed a linear dependence, sat-
isfying the equation:
Tg
To
t y ¼ 3R
g o :V
where R is the gas constant and g o is the critical
local shear strain leading to destabilization of
local shearing events. On the basis of the above
equation, the authors also deduced the correla-
tion between Young’s modulus and Tg. Since
E ¼ sy/eE and the room temperature elastic
strain limit of BMGs is approximately 2%, and
assuming that t y ¼ sy/2 and that g o ¼ 1, the
above equation was rewritten as:
2 Tg
To
E ¼ 3R 
V
There have been other correlations in the
literature. For example, the tensile strength and
hardness of BMGs have been shown to scale
with the Young’s modulus, as shown in
Figure 18.
9.5. Ductility
Associated with the high strength of metallic
glasses is their brittleness. Even though some
BMGs show a small amount of plastic defor-
mation, the majority of them fail soon after
yielding. This is because metallic glasses do
not in general show work-hardening character-
istics; there have been some reports on ‘‘work
hardenable’’ BMGs [157].
Metallic glasses are very brittle under ten-
sion, with almost no plastic strain to failure;
glassy ribbons show considerable bend ductili-
ty. When metallic glasses are tested in compres-
sion, they seem to exhibit some amount of
plastic strain before failure. The reasons for this
difference may be found in the way the shear

bands are nucleated and propagated. During a
tensile test, crack initiation occurs almost im-
mediately after the formation of the first shear
band, and as a result metallic glasses fail cat-
astrophically and show essentially zero plastic
strain prior to failure. However, specimens
loaded under constrained geometries (e.g., com-
pression) fail in an elastic, perfectly plastic
manner by the generation of multiple shear
bands, i.e., some plastic strain is observed be-
fore failure.
One way of overcoming this lack of ductility
in metallic glasses seems to be to introduce a
crystalline phase to produce a composite
either in situ or ex situ. There have been reports
of significant achievement of plasticity in
monolithic BMGs. Some typical examples
are the plastic strains to failure of 16%
in Cu47.5Zr47.5Al5 [157] and 20% in
Pt57.5Cu14.7Ni5.3P22.5 [158] glassy alloys.
It has been suggested that materials with
a m/B, where m is the shear modulus, and B the
bulk modulus, of over 0.3 are brittle, while those
with values of <0.3 are ductile [159]. A plot of
fracture energy, Gc, against m/B, led to the
suggestion that a critical value of m/B differen-
tiating a brittle BMG from a ductile BMG
appears to be in the range of 0.41–0.43 [160];
BMGs with a m/B value of over 0.43 are brittle.
It is also suggested that metallic glasses
are ductile when the Poisson’s ratio is high
[158, 161].
Large amounts of ductility have been re-
ported in other BMG alloys [162], and super-
plasticity could be achieved over a range of
strain rates in the supercooled liquid
region [163].
9.6. Fatigue
Fatigue is a form of failure in structures sub-
jected to dynamic and fluctuating stresses and
the mechanism of fatigue failure involves initi-
ation of cracks, their propagation, and final fast
fracture [164]. The S
N (stress versus number
of cycles to failure) plots of metallic glasses
exhibit a well-defined fatigue limit and in this
sense they are similar to crystalline alloys. The
occurrence of a well-defined fatigue limit in
crystalline alloys has been attributed to the
occurrence of strain aging during tensile
Metallic Glasses 35
deformation. Metallic glasses that exhibit a
clear fatigue limit also display serrated flow
during monotonic deformation. This is a mani-
festation of strain aging.
Since metallic glasses have very high tensile
strengths, they are expected to show very high
fatigue limits. However, this has not been real-
ized. The fatigue ratio is typically in the range of
0.4 to 0.5 in the case of crystalline alloys, but it is
much smaller, going down to a value of 0.04 in
metallic glasses, even though higher values
have been reported occasionally. The reasons
for this significant difference in the fatigue
ratios between crystalline and glassy alloys are
not clear. Furthermore, even though the propa-
gation of fatigue cracks appears to be similar
between crystalline materials and glassy alloys
(striations are seen in both types of materials),
reasons for the susceptibility of metallic glasses
to crack initiation are not known, since they do
not contain crystalline defects. Furthermore,
fatigue lifetimes are dominated by the loading
cycles needed to initiate damage rather than the
cycles needed to propagate the damage, gener-
ally in the form of cracks, to critical size.
Preliminary results suggest that the compo-
sition of the alloy can affect the fatigue behav-
ior. Substituting 10 at% Cu with Ni seems to
improve the fatigue limit and fatigue ratio of
Zr50Cu40Al10 BMG alloys [165], attributed to
the ease of oxidation of the fresh fatigue-frac-
tured surface of the Ni-free alloy. Presence of
nanocrystalline regions in a Pd-containing
Zr50Cu40Al10 glassy alloy was found to be
responsible for increasing the fatigue limit by
blocking shear bands and crack propaga-
tion [166]. Oxygen and inclusions, in small
amounts, seem to have a major effect on the
fatigue behavior of Zr-based BMG alloys [167].
Early studies [168] have indicated that the
Zr41.2Ti13.8Cu12.5Ni10Be22.5 BMG alloy was
highly susceptible to stress corrosion cracking
and stress corrosion fatigue in the presence of
aqueous NaCl solution. The obtained results
suggest that crack growth mechanisms in air
and in aqueous solutions are different [169].
Fatigue crack propagation behavior in air seems
to be similar to that observed in polycrystalline
metals and is associated with alternating blunt-
ing and re-sharpening of the crack tip, as evi-
denced by the presence of fatigue striations. On
the other hand, in NaCl solution, the mechanism
36 Metallic Glasses
seems to be driven by a stress-assisted anodic
reaction at the crack tip.
Fatigue behavior of composites was im-
proved since the presence of the crystalline
phase was able to relieve the residual surface
stresses or accommodate any surface strains
such that defects do not form. Absence of
microdefects also resulted in a very high fatigue
strength.
9.6.1. Fatigue Crack Growth Rate
The fatigue crack grows with each cycle and
therefore the time for it to reach the critical size
at which fracture occurs is determined by the
rate at which it grows and also the fracture
toughness of the material. The fatigue crack
growth rate is determined from the Paris power
law relationship:
da
¼ C ðDK Þm
dN
where da/dN represents the crack growth rate (a
is the crack length and N is the number of
cycles), DK is the stress intensity range, and
C and m are constants, noting that the larger the
value of m, the faster the crack growth rate. A
desirable situation for long fatigue life is to
achieve as small a value of m as possible. The
values of m and DKth for BMG alloys are similar
to those typically observed in crystalline alloys.
The fracture surfaces of BMGs after fatigue
crack growth rate experiments seem to be quite
different from those of crystalline materials.
The surface roughness of BMG samples has
been found to increase with increasing crack-
growth rate. The surfaces change from a mirror-
like surface in the near-threshold fatigue crack
growth region to a rough morphology exhibiting
ridge-like features in the fast-fracture process
[170].
9.6.2. Improvement of Fatigue Resistance
It is now accepted that fatigue crack initiation is
the critical part in determining the fatigue lives
of metallic glasses. Once a fatigue crack forms,
it can grow easily due to lack of microstructure.
Therefore, introduction of a crystalline phase by
making it a composite might prevent growth of
small fatigue cracks and improve the fatigue
strength. A more than double fatigue ratio for a
composite in comparison to a monolithic glassy
alloy has been reported [171]. On the other
hand, it has also been reported that the fatigue
behavior of a composite is worse than that of a
monolithic alloy [172].
The fatigue resistance of BMGs and their
composites is in general poorer than that of the
crystalline materials. It has been shown [173]
that by matching the microstructural length
scales (of the second crystalline phase in a
composite) to the mechanical crack-length
scales, the fatigue resistance could be improved.
Compressive stresses on the surface of speci-
mens are known to increase the fatigue life. But,
shot peened BMG alloys did not show any
improvement [174].
It is known that the fatigue endurance limit
increases with an increase in the yield strength
of the alloy in the crystalline state. However,
such a correlation is not apparent in BMG
alloys. A preliminary correlation between the
fatigue ratio and Poisson’s ratio was, however,
reported with the fatigue ratio increasing with
increasing value of the Poisson’s ratio [175].
9.7. Yield Behavior
Crystalline materials start yielding when the
applied stress is above the critical shear stress,
dependent on the orientation of the single crys-
tal with reference to the loading axis. The two
criteria used for determining the yield behavior
are the von Mises and the Mohr–Coulomb
criteria. According to these criteria, yielding is
supposed to be symmetric, i.e., the yield stress is
of the same magnitude whether testing is done in
tension or compression and therefore the angle
at which shear failure occurs is 45 both in
tension and compression. However, several me-
tallic glasses have been shown to display asym-
metry, and therefore it has been suggested that
the yield criterion in metallic glasses could be
different.
By measuring the yield strength of
Pd40Ni40P20 metallic glass ribbons undergoing
low-temperature, localized plastic flow in uni-
axial compression, plane-strain compression,
pure shear, and tension, it was demonstrated
that yielding follows the Mohr–Coulomb crite-
rion, rather than the von Mises criterion [176].

Yielding according to the Mohr–Coulomb cri-
terion depends not only on the applied shear
stress, t, but also on the stress normal to the
shear displacement, sn. Since BMGs have a
very high strength (1–4 GPa), the normal stress
applied on the shear plane is also very high (1–
2 GPa), and should therefore play an important
role in the yielding process. Furthermore, it has
long been known that disordered materials ex-
perience dilatation due to plastic deformation.
In terms of the flow strength-to-modulus ratio
(so/E), this value is of the order of 10
3 and is
negligible in crystalline materials. In the case of
BMGs, however, it can be about 0.02, and
therefore pressure effects are not negligible.
Sufficient data is not available, and the avail-
able results are conflicting to draw any conclu-
sions on the effect of strain rate on the fracture
strength of metallic glasses. It has been sug-
gested that the room temperature fracture
strength of the Pd80Si20 filaments decreased
with increasing strain rate or was strongly de-
pendent on strain rate.
When the surface of a glassy alloy specimen,
fractured under uniaxial loading, is observed in
a scanning electron microscope, one observes
typically a vein pattern, as shown in Figure 19.
Such microstructures are observed whether the
specimen fails in tension or compression and
represent fracture characteristic of pure shear
mode. Except for the ridges forming the veins,
the fracture surface is flat.
Figure 19. Scanning electron microscopy image of the
fractured surface of a bulk metallic glass alloy specimen.
Note the vein pattern which is typical of many metallic
glasses which fracture along a shear band. Such microstruc-
tures are obtained both in tension and compression.
Metallic Glasses 37
Fracture occurs by a shear mode under both
tensile and compressive loading conditions.
However, an important difference between the
surface structures of specimens fractured in
tension and compression is that the density of
shear bands is much higher in the latter. Under
tensile loading, one major shear band dominates
the fracture process. The fracture surfaces of
BMG composites look different and are more
complex mainly because of the presence of the
crystalline phase.
9.8. BMG Composites
A critical requirement for a structural engineer-
ing material is that it should have an optimum
combination of strength, ductility, toughness,
and predictable and graceful (noncatastrophic)
failure. Metallic glasses are inherently brittle in
tension. The introduction of tungsten and 1080
steel wires into a Zr41.25Ti13.75Cu12.5Ni10Be22.5
BMG matrix caused the compressive strain to
failure to increase by 900% compared to the
unreinforced BMG alloy [177]. It was suggested
that the compressive toughness came from re-
stricting the propagation of shear bands and thus
promoting the generation of multiple shear
bands which had eventually delayed fracture.
The tensile toughness increased as a result of
ductile fiber delamination, fracture, and fiber
pull-out. Subsequently, it was also demonstrat-
ed that the plasticity of BMGs could be en-
hanced by incorporating ductile phases formed
either by in-situ or ex-situ methods [178].
The properties of the BMG composite are
determined by the nature of the second (crystal-
line) phase, its size, volume fraction, and its
distribution in the matrix. Significant improve-
ments have been noted in the mechanical prop-
erties, especially in the toughness and ductility
of the BMG alloys [179].
9.8.1. Mechanical Properties
of Composites
The mechanical properties of the BMG compo-
sites have been shown to be much better than
their monolithic counterparts. Irrespective of
the nature of the reinforcement, the fracture
strength has been shown to increase with
38 Metallic Glasses
increasing volume fraction of the reinforce-
ment. Associated with this increase in fracture
strength is the plastic strain to fracture, which
also has been shown to be higher with increasing
volume fraction of the reinforcement. For ex-
ample, the fracture strength (sf) and plastic
strain to fracture (ep) for the monolithic
Cu60Hf25Ti15 BMG have been measured to be
2088 MPa and 1.6%, respectively. But, with the
presence of 8 vol% of the Nb-rich solid solution
precipitate, these values increased to 2232 MPa
and 14.1%, respectively [180]. Similar trends
have been reported in many other BMG com-
posites. The best combination of high strength
and improved ductility is obtained when the
reinforcement is in the form of ductile den-
drites [181]. When the dendritic phase is chan-
ged into a spherical shape, the properties appear
to be further improved [182]. For example, the
plastic strain achieved was 12% when the sec-
ond phase had a spherical morphology, increas-
ing from 8.8% for the dendritic morphology.
The effect of the shape of the reinforcement
(second phase) and its volume fraction has been
analyzed in terms of the yield strength and
plastic strain to fracture in both compression
and tension [135]. At low volume fractions of
the crystalline reinforcement phase (Vr < 0.3),
the yield stress of the composite was very close
to that predicted by the rule of mixtures, sug-
gesting that at low volume fractions, the rein-
forcement does not alter the macroscopic con-
stitutive response of the glassy matrix. At values
of Vr > 0.3, the composite response seems to
depend on the morphology of the reinforcement.
The yield strength of composites with fibers and
large particles is the same as that calculated
using the rule of mixtures. The yield strength for
in-situ processed composites reinforced with
dendrites is higher than that of the rule of
mixtures, and for nanocrystalline composites it
is lower. From this it appears that the dendritic
morphology is the most effective in inhibiting
macroscopic plastic deformation of the matrix.
9.8.2. Initiation and Propagation of Shear
Bands
Plastic flow is initiated in single-phase materials
in some locally perturbed region. Structural
inhomogeneities and defects that introduce
stress concentrations will therefore promote
shear band initiation. In the case of composites,
however, three different possibilities have been
identified as stress concentrators. These include
(a) thermal residual stresses (of about 400 MPa)
generated in both the matrix and the reinforce-
ment due to mismatch of the coefficient of
thermal expansion, (b) stress concentrations in
the matrix due to differences in the elastic
properties of the matrix and the reinforcement,
and (c) stress concentration from the plastic
misfit strain between the matrix and the rein-
forcement when the crystalline phase yields
before the glassy matrix.
Since it has been noted that BMG composites
with dendrites exhibit higher amounts of plas-
ticity, it has been suggested that the stress
concentration in the glassy matrix changes due
to the dimensions of the dendrite features, which
are typically about 10 mm, which influence the
shear band formation. It is also possible that the
newly formed shear bands are likely to intersect
a dendrite arm before propagating very far, thus
making the dendrite arms more effective bar-
riers to shear front propagation. Using this
concept of proximity of ‘‘obstacles’’ to shear
band propagation, Zr-based BMG composites
were designed [78] with different volume frac-
tions of the crystalline phase and it was found
that the plastic strain to fracture increased with
increasing volume fraction of the dendritic
phase.
10. Magnetic Properties
Magnetic properties are of fundamental impor-
tance for several applications in the electrical
and electronic industries. Ferromagnetism was
first reported in 1967 in metallic glassy ribbons
of Fe75P15C10 which exhibited large saturation
magnetization and a narrow hysteresis loop with
a low coercivity [183]. The magnetic moment
per iron atom was lower than that in pure
crystalline iron, due to the presence of about
25 at% metalloid elements required to form the
glassy phase. A very large number of magnetic
metallic glasses based on Fe and Co have been
subsequently synthesized and characterized. In
fact, the most important application to which the
melt-spun glassy ribbons have been put to is in
transformer core laminations based on the

excellent soft magnetic properties of these
alloys. Therefore, a significant amount of effort
has been spent on investigating the magnetic
properties of metallic glassy alloys, including
the BMGs.
The possibility of occurrence of ferromag-
netism in amorphous alloys was predicted in
1960 [184]. It was shown that nearest-neighbor
interactions can give rise to ferromagnetism.
Even though metallic glasses behave like super-
cooled liquids rather than crystalline solids as
far as their electrical properties are concerned,
their magnetic properties resemble those of the
crystalline counterparts. This is because the
governing electronic band structure is influ-
enced by short-range rather than long-range
forces. Since metallic glasses contain short-
range order, the magnetic properties of metallic
glasses are not substantially different from those
of their crystalline counterparts. However, dif-
ferences exist between the magnetic properties
of glassy and crystalline alloys of the same
composition. The magnetic properties of alloys
depend on the residual strain, field heat treat-
ment, the directionality induced during solidifi-
cation, and on the alloy composition. But, it may
be safely stated that, in comparison to crystal-
line alloys, magnetic metallic glasses have a
lower Curie temperature, higher permeability,
lower coercivity, and higher electrical resistivi-
ty. However, the saturation magnetization of
metallic glasses is low.
Even though crystalline anisotropy is zero in
the glassy state, a uniaxial anisotropy, Ku has
been found to exist in metallic glasses, thought
to be induced by short-range ordering, and can
have a strong influence on the low-field proper-
ties of metallic glasses.
When a ferromagnetic material is magne-
tized, its dimensions change slightly, and the
sample being magnetized either expands or
contracts in the direction of magnetization. This
magnetically induced reversible strain is called
magnetostriction, ls, and is of the order of 10
6.
ls is positive at low fields and negative at high
fields for crystalline iron and it is negative for
cobalt and nickel. Since metallic glasses have
high yield strengths and can withstand high
stresses without undergoing plastic deforma-
tion, the anisotropy due to mechanical stresses
can be very large. For metallic glasses, ls can
range from as high as 4  10
5 to as low as 5 
Metallic Glasses 39
10
6. It can be reduced to zero by a proper
choice of alloy composition and heat treatment.
There have also been several investigations
on the magnetic properties of BMG alloys. The
first Fe-based BMG alloy (in the form of melt-
spun ribbons) was synthesized in 1995 in the
Fe72Al5Ga2P11C6B4 system [185]. This discov-
ery was immediately followed with the
synthesis of another Fe-based BMG, a
Fe72Al5Ge2P11C6B4 alloy [186]. The magnetic
properties of BMGs have been investigated
mostly in Fe-based BMGs, and a few investiga-
tions have also been reported on Co-based
BMGs. The hard magnetic properties of Nd-
and Pr-based alloys have also been studied.
The nature of magnetic investigations in
BMG alloys has followed trends very similar
to what were done in the case of melt-spun
glassy ribbons. An important difference be-
tween the investigations on melt-spun ribbons
and BMGs is that while both metal–metalloid
and metal–metal type alloys have been investi-
gated as thin films, only metal–metalloid alloys
have been studied as BMGs. For BMG compo-
sitions, several researchers have studied the
magnetic behavior using melt-spun ribbons.
Some minor differences were noted in the mag-
netic properties of melt-spun ribbons and bulk
rods, especially in those properties that are
affected by structural relaxation, e.g., magneto-
striction and coercivity. On the other hand, it has
been shown that the saturation magnetization of
the alloys is not any different whether measured
on the melt-spun ribbon form or powder or
between the melt-spun ribbon and bulk rods of
different diameters.
10.1. Effect of Alloying Elements
The saturation magnetization of metallic glasses
is relatively low and ranges from 0.4 to 1.8 T,
while crystalline steels have values ranging
from 1.8 to 2.1 T. This is due to the fact that
a large percentage of metalloid elements is
necessary for the formation of metallic glasses.
This results in a decrease in the fraction of atoms
with magnetic moments due to the occupation
of some of the d-states of the transition metals
by electrons from the metalloid atoms.
The mutual interactive forces of atomic di-
poles tend to align themselves in a particular
40 Metallic Glasses
direction, which results in a permanent
magnetic moment. When the temperature is
increased, the thermal agitations perturb this
alignment of parallel arrangement of neighbor-
ing spins and the average net moment is zero at a
certain temperature, referred to as the Curie
temperature, Tc. The Tc of metallic glasses is
in the range of 500 to 800 K, and is relatively
low in comparison to their crystalline counter-
parts. It is higher or lower depending up on the
nature and amount of the alloying element. For
example, the Tc of Fe–B and Fe–B–Si alloys is
very high, while that of Fe–P alloys is very low.
The effect of metalloid elements on Tc of mag-
netic metallic glasses can be said to decrease in
the order P < C < Si < Ge. The Tc increases with
decreasing Fe content, increasing Si content,
and also increases slightly by substituting Ni for
Fe. When transition metals to the left of Fe in the
Periodic Table are added, the magnetic moment
decreases sharply, with the decrease being more
rapid for Cr and V than for Mn. Replacing Co by
Ni results in a rapid decrease in Tc of Co–Ni
magnetic glasses.
Addition of Nb to Fe- and Co-based alloys
improves their GFA [21]. Since Fe–B–Si alloys
have been known to exhibit good soft magnetic
properties, about 4 at% Nb was added to the
(Fe1
xNix)0.75B0.2Si0.05 system [187]. While the
GFA of the alloy has certainly improved, the
saturation magnetization decreased from 1.1 to
0.8 T, the coercivity decreased, and the perme-
ability increased as the Ni content increased
from x ¼ 0.1 to 0.4. This was attributed to the
high degree of amorphicity and structural ho-
mogeneity in the glassy state.
On the other hand, with increasing Fe content
from x ¼ 0.1 to 0.4 in the [(Co1
xFex)0.75B0.2-
Si0.05]96Nb4 alloys, the saturation magnetiza-
tion increased from 0.71 to 0.97 T. The Hc value
increased slightly from 0.7 to 1.8 A/m and the
permeability decreased. The magnetostriction
increased from 0.55  10
6 to 5.76  10
6. It
has been suggested that the large fractions of
metalloid and nonmagnetic refractory elements
present could also be responsible for the low
saturation magnetization observed in the multi-
component alloys.
Thus, from the above description it is clear
that the nature and amount of the alloying
addition will decide the magnitude of change
in the magnetic properties. The maximum
possible amount of Fe is required to achieve
the highest saturation magnetization value.
10.2. Effect of Annealing
Annealing of the fully glassy alloy, especially in
the temperature range between the Curie tem-
perature, Tc, and the crystallization temperature,
Tx, has been shown to significantly enhance the
soft magnetic properties of the alloys. In fact,
development of the FINEMET alloys in the late
1980s is based on this concept [188]. Annealing
of Fe–Si–B–M glassy alloys containing small
amounts of up to 1.5 at% of M (¼ Cu, Nb, Mo,
W, Ta, etc.) was shown to result in the precipi-
tation of fine (10 nm in size) a-Fe(Si,B) crys-
talline particles. Since Cu and Fe have a positive
heat of mixing, they segregate to form Fe-, Cu-,
and Nb-rich regions. Fe-rich regions become the
nuclei for the a-Fe solid solution. Since the Cu-
and Nb-rich regions have a higher crystalliza-
tion temperature, they do not crystallize. There-
fore, the microstructure consists of fine a-Fe
grains dispersed in a glassy matrix. These FI-
NEMET alloys show low coercivity, low satu-
ration magnetostriction, and low core losses in
comparison to fully glassy alloys.
Annealing of the fully glassy BMG alloys has
also been carried out to enhance the magnetic
properties of these alloys. Figure 20 shows a
bright-field TEM image of a 1.5 mm diameter
rod of a Fe62.8Co10B13.5Si10Nb3Cu0.7 glassy
alloy annealed at 873 K for 5 min. It may be
seen that the BCC a-(Fe,Co) grains with a size
between 10 and 15 nm are dispersed homo-
geneously in the glassy matrix phase. Since the
FINEMET-type alloys contain the a-Fe solid
solution phase dispersed in the glassy matrix, it
is important that the BMG alloys exhibit at least
two stages of crystallization to achieve the
desired microstructure. As such, BMGs that
show a single stage of crystallization cannot be
annealed to produce such a microstructure. The
magnetic properties of such magnetic alloys are
much better than those of the fully glassy alloy,
and they are also comparable to those of FINE-
MET and NANOPERM alloys.
The magnetic properties of the [(Fe,Co,
Ni)0.75B0.20Si0.05]96Nb4 system were investigat-
ed by measuring the saturation magnetization
and coercivity as a function of composition on

Figure 20. Bright-field TEM image of the Fe62.8Co10B13.5-
Si10Nb3Cu0.7 glassy alloy annealed at 873 K for 5 min. Note
that 10–15 nm size grains of a-(Fe,Co) phase are uniformly
dispersed in the glassy matrix
melt-spun ribbons annealed for 5 min at a
temperature 50 K below the glass transition
temperature (Fig. 21A and B). The saturation
magnetization shows high values of over 1.3 T
in the Fe-rich Fe–Co–B–Si–Nb alloys and it
decreases with increasing Co and Ni contents.
However, almost all the alloys show a low value
of coercivity (<2.5 A/m) and it decreases grad-
ually with increasing Co content. The lowest
values of 1 A/m are obtained in the most Co-
rich alloys.
Irrespective of whether the BCC a-Fe solid
solution phase forms or some other crystalline
phase, the magnetic properties of glassy alloys
are generally improved on annealing. The co-
ercivity decreases and the permeability in-
creases on annealing, but there was not much
change in the saturation magnetization values.
In addition, it was noted that such samples
showed the lowest core losses [189].
The above observations make it very clear
that in order to achieve a high saturation mag-
netization, it is necessary to have as high a Fe
content as possible and decrease the other metal
and metalloid contents to the minimum value
that is necessary to obtain the glassy phase. An
optimum composition of Fe94
xNb6Bx was
determined for this alloy system upon an
Metallic Glasses 41
Figure 21. Plots showing (A) saturation magnetization and
(B) coercivity, as a function of composition in the
[(Fe1
x
yCoxNiy)0.75B0.20Si0.05]96Nb4 alloys
investigation to achieve the best soft magnetic
properties [190]. Addition of small amounts of
Cu and P was then found to optimize the com-
position as Fe84.9Nb6B8P1Cu0.1. This alloy con-
tained an a-Fe phase with an average grain size
of 10 nm dispersed in a glassy matrix and
showed excellent soft magnetic properties with
a saturation magnetization of 1.61 T, coercivity
of 4.7 A/m and permeability of 41 000. The core
losses for this alloy were very low at 0.11 W/kg.
Fe-based glassy alloys suffer from some
disadvantages which include low glass-forming
ability, necessity of an annealing treatment after
casting, and the very brittle nature of the anneal-
ing-induced nanocrystalline alloys. Further-
more, their corrosion resistance is not at the
desired level.
42 Metallic Glasses
10.3. Nanocrystalline Alloys
Since the presence of a significant amount of
metalloid elements is necessary for the forma-
tion of metallic glasses, and these reduce the
saturation magnetization value, nanocrystalline
alloys can be used, which also show a very
useful combination of soft magnetic properties.
Nanocrystalline alloys do not require the pres-
ence of metalloid elements, but they can be
included since some of them improve the mag-
netic properties.
The best soft magnetic properties are
achieved by crystallizing the glassy phase to
produce a uniform nanostructure. In FINEMET
and other alloys, the volume fraction of the
nanocrystalline phase is very large, reaching a
value of almost 90%. Since a glassy precursor is
a prerequisite to achieve this microstructure,
one has to have a minimum amount of different
metals and/or metalloids to first produce the
glassy phase. Furthermore, to achieve the large
volume fraction of the nanocrystalline phase,
the presence of metals like Cu, Nb, Mo, W, and
Ta is required. These metallic elements are
quite expensive. To overcome these difficulties,
novel Fe-based alloys have been developed
that contain only metalloids [191, 192].
The generic composition of these alloys is
Fe83.3–84.3Si4B8P3–4Cu0.7 and is based on the
Fe82Si9B9 alloy that proved most promising
among the Fe-based melt spun magnetic alloys.
The large concentration of Fe provides a high
saturation magnetization and the absence of the
metallic elements (other than Fe) ensures that
the alloys are not expensive. The magnetic
properties of these nanocrystalline alloys are
better than those of other developed alloys
(glassy, composite, or nanocrystalline) and
those of commercially important crystalline
alloys.
11. Applications
Metallic glasses, both in ribbon and rod form,
are metastable materials and they possess inter-
esting combinations of properties such as high
strength, good corrosion resistance, and mag-
netic properties. One of the greatest advantages
of BMGs is that they can be cast into large
section thicknesses. Glassy rods with diameters
of >10 mm have been produced in alloy sys-
tems based on Ca, Co, Cu, Fe, La, Mg, Ni, Pd, Pt,
Ti, Y, and Zr, the largest diameter being 72 mm
in a Pd40Cu30Ni10P20 alloy [38]. The advantages
of a large section thickness for industrial appli-
cations are limitless. Parts could be produced
not only for electronic applications or MEMS
(Micro Electro-Mechanical Systems) devices
but also for large components. The most suc-
cessful application of metallic glasses has been
for transformer core laminations in power dis-
tribution transformers.
BMGs are also characterized by a large super-
cooled liquid region. The viscosity of the BMG
is very low in this temperature regime and
therefore, it should be very easy for the BMG
to be conveniently fabricated into complex
shapes. In fact, superplastic forming (SPF) of
BMGs in this temperature interval has been
achieved.
BMGs have the ability to achieve a very high
surface finish. Since the BMGs are glassy and so
do not have microstructural features such as
grains and grain boundaries, the surface of
BMGs is very smooth, and they can also be
polished to a very high surface finish, if re-
quired. Furthermore, it has been possible to
produce BMG alloy compositions in the form
of rods, sheets, plates, spheres, pipes, etc.
11.1. Mechanical Applications
Although possessing very high strength and
hardness, metallic glasses are rarely used for
structural (and load bearing) applications as a
result of their poor fracture behavior.
Metallic glassy alloy ribbons have been used
for reinforcement of mortar, polymers, and
metallic matrix materials. It was shown that the
specific fracture work could be increased more
than 2000-fold, over that of the unreinforced
mortar, with only 1 vol% of the fiber [193].
Glassy W-based alloys have been used for
kinetic energy army penetrators as well as dial
pointers in electrical instruments [194]. The
high strength and isotropic two-dimensional
form of metallic glass ribbons suggest applica-
tions in planar composites. Indeed, high-quality
plates have been made of half-inch-wide MET-
GLAS ribbons in 0 –90 cross-ply with an
epoxy matrix [195]. These composites exhibited

a remarkable degree of in-plane isotropy and
strength.
The BMG alloys exhibit some interesting
mechanical properties. An important character-
istic of BMGs is their large elastic strain limit,
about 2% at room temperature, which is more
than twice that in a crystalline material. This
large value combined with the low Young’s
modulus can find useful applications in a variety
of commercial and large-volume applications.
Yet another special feature of BMGs is their
high yield (or fracture) strength and hardness.
Because of this, BMGs could be used in appli-
cations where scratch and wear resistance be-
come important.
Due to their high strength and large elastic
elongation limit, BMGs have found widespread
application in sporting goods such as golf clubs,
tennis rackets, baseball and softball bats, skis
and snowboards, bicycle parts, scuba gear, fish-
ing equipment, and marine applications [196].
Due to the high elastic strain limit and low
Young’s modulus, the modulus of resilience of
BMGs is at least four times that of a crystalline
material. It is suggested that 99% of the impact
energy from a BMG golf club head is transferred
to the ball. This value should be compared
with 70% for a titanium head. Figure 22 shows
the outer shapes of the golf club heads made of a
Figure 22. Outer shapes of commercial golf club heads in
wood-, iron-, and putter-type forms where the face materials
are made of a Zr-based BMG alloy
Metallic Glasses 43
Zr-based BMG manufactured by SRI Sports
Ltd, a subsidiary of Dunlop Corporation in
Japan. Liquidmetal Technologies supplies base-
ball bats, tennis rackets, and other sporting
goods.
The formation of complicated structures
from BMGs in their supercooled liquid region
offers many advantages, including their homo-
geneity on a nanometer scale, very little solid-
ification shrinkage, excellent filling character-
istics, and highly reduced porosity. The super-
ior surface imprintability and net-shape
forming capability have also been found to be
very attractive in the field of micro-machines
[197].
It has been possible to produce extremely
small parts of complex design using BMGs.
These include microgears, coil-shaped springs,
micro-geared motors with high torque, whose
wear resistance was shown to be more than 300
times that of all-steel gears, automobile valve
springs, where the spring wires could be slim-
mer and the springs themselves to be shorter,
diaphragms for pressure sensors, pipes for a
Coriolis mass flowmeter, structural parts for
aircraft, and shot peening balls to induce com-
pressive stresses on the surface. Due to the
possibility of achieving a very good surface
finish, optical mirror devices have also been
fabricated from BMG alloys [21].
Metallic glass sheets are also being used as
brazing foils [198]. The high-temperature al-
loys used for brazing are usually eutectic com-
positions formed by transition metals with
metalloid elements, which are brittle and so
cannot be produced in continuous form. Hence,
they are used in powder form or powder-filled
pastes. Metallic glass compositions are emi-
nently suited to be cast into ductile ribbon form
by the melt spinning process. Consequently,
many glassy alloys based on Ni, Ni–Pd, and Cu
are replacing many conventional brazing al-
loys that contain expensive elements such as
gold and silver. There are specific advantages
of using glassy alloy foils. Firstly, they flow
easily into the joints at relatively low tempera-
tures. Secondly, they can easily take the con-
tour and curvature of the part to be brazed
because they are ductile, and provide optimal
and controlled gaps. Lastly, since they do not
contain any binder, their shelf life is long and
they are non-contaminating.
44 Metallic Glasses
11.2. Chemical Applications
Metallic glasses exhibit remarkable corrosion
resistance in a variety of environments. An Fe-
based glassy alloy (having a high magnetic
induction) has been used for high-field, high-
gradient, filtering systems to remove paramag-
netic iron oxides from clays, oils, and waters,
that are otherwise colored [199]. Such a filter
has been claimed to increase the rate of collec-
tion of submicrometer-sized magnetic particles
by a factor of three compared with a conven-
tional ferritic stainless steel filter. Amorphous
Ni–P alloys have the potential for applications
as chemical filters of liquid sodium used in fast
breeder reactors.
Fe–Ni-based glassy alloys containing P and/
or B are two orders of magnitude more effective
in catalyzing the hydrogenation of carbon mon-
oxide to yield hydrocarbons (methane, ethylene,
ethane, propylene, and propane) than their crys-
talline counterparts [200]. This enhanced activ-
ity was maintained only at temperatures below
some critical temperature, significantly lower
than the crystallization temperature. Reports are
also available on Pd-based glassy alloys for the
oxidation of methanol, sodium formate, and
formaldehyde with activities similar to or higher
than Pt, suggesting application as an electrode
material in methanol–air fuel cells [201].
A BMG alloy with the composition
Ni60Nb15Ti15Zr10 was chosen to replace a sep-
arator substrate in fuel cells since it has very
good corrosion resistance [202]. Tests using the
prototype show that the Ni-based BMG separa-
tor generates a high voltage at the actual opera-
tion current, higher than that using a stainless
steel separator. In addition to this, the durability
test at a current density of 0.5 A/m2 shows no
degradation at 350 h. It has also been shown that
a glassy Ni–Nb–Pt–Sn alloy can be an excellent
anode material for application in fuel cells since
it has a higher catalytic activity as well as a
longer lifetime than that of polycrystalline
platinum [203].
11.3. Electrical Applications
Since the resistivity of metallic glasses is very
sensitive to structure—especially in glasses
having a negative TCR, they can be used to
monitor structural relaxation. Because of its
rapid rise in resistivity below 150 K, the
Pd73Cr7Si20 glass has been suggested for use
as an attractive metallic resistance thermometer.
Metallic glasses having a zero value of TCR
have been suggested for resistance standards.
They have also been suggested for use as mag-
netoresistance sensors for detecting the pres-
ence of magnetic fields, notably in bubble mem-
ory devices. Since a glassy alloy will not de-
grade under irradiation and also because of the
good combination of strength, ductility, and
superconducting properties, metallic glasses are
suggested for use as windings in superconduct-
ing magnets for use in fusion reactors [100].
11.4. Magnetic Applications
The magnetic properties of melt-spun glassy
ribbons have been exploited for a variety of
applications. The outstanding soft magnetic
properties of the Fe-based melt-spun ribbons
are used in power distribution transformers and
several other applications. Due to the noncrys-
talline structure of metallic glasses, the magnet-
ic loss in the glassy alloy core is much less than
in cold-rolled grain oriented silicon steels. Fur-
thermore, the metallic glass is already in thin
sheet form when produced. This not only re-
duces the eddy current losses, but is less costly
to produce than rolling thin crystalline ribbon
tapes to similar dimensions. The early applica-
tions of metallic glass thin ribbons have been
reviewed [204–206].
Soft-magnetic BMGs with high permeability
and low coercivity appear to be the most appro-
priate materials for magnetic yokes of linear
actuators. Fe73Ga4P11C5B4Si3 BMG plates
30 mm long, 20 mm wide, and 1 mm thick have
been produced by the squeeze casting (a com-
bined casting and forging) process [207]. This
alloy has excellent soft magnetic properties (Is
¼ 1.32 T; mmax ¼ 110 000; Hc ¼ 33 A/m) and
these are further improved by annealing (mmax
¼ 160 000 and Hc ¼ 2.7 A/m). Using this
material, a yoke and a prototype linear actuator
have been fabricated. Tests show that the force
generated by the actuator using the Fe-based
BMG yoke is higher, in the frequency range of
20–45 Hz, than when Sr-ferrite is used as a
permanent magnet. The large Lorentz force

suggests that linear actuators using Fe-based
BMG yokes can show good acceleration and
deceleration. In addition, the high relative per-
meability (m) of the BMG permits the actuators
to be driven with high-frequency current pulses,
leading to fine pitch control through a feedback
system. Based on the high m and low Hc of Fe-
based BMGs, it has been suggested that they are
appropriate for low-loss magnetic cores for
choke coils [208]. Fe-based BMG alloy consol-
idated powder cores are also finding applica-
tions as inductors in personal computers, etc.,
because of higher efficiency and much lower
core losses in high frequency range. In 2011,
The Alps Green Device Company in Japan was
producing several million pieces per month for
commercial applications.
11.5. Miscellaneous Applications
11.5.1. Jewelry
The two important material characteristics that
are important for jewelry are aesthetic appear-
ance and retention of luster and brightness, or
inertness to environment. Au- and Pt-based
BMG alloys can be cast into 5 mm thick and
16 mm thick plates, respectively, and it is easy
to form complex shapes by superplastic forming
in the supercooled liquid region [209]. Since
these alloys have high strength, they are more
scratch- and wear-resistant than the convention-
al crystalline alloys. Commercial jewelry items
include watch casings (to replace Ni and other
metals, which can cause allergic reactions),
fountain pen nibs, and finger rings.
11.5.2. Biomedical Applications
For a material to be used as an implant, the
metallic material should be biocompatible, in-
ert, and have mechanical properties which are
very similar to the part that is being replaced. Ti-
based BMG alloys have low density, excellent
biocompatibility, and corrosion resistance and
so they appear to be ideal materials for biomed-
ical applications. Ti-based BMGs without any
toxic elements have been produced. It has been
reported that a bone-like apatite film formed on
the surface of Ti40Zr10Cu36Pd14 BMG alloy
Metallic Glasses 45
composites containing 6 vol% of hydroxyapa-
tite (HAp) after electrochemical and chemical
treatments [210]. The monolithic Ti40Zr10-
Cu36Pd14 BMG alloy was found to be a good
replacement for teeth and as plates and screws
for fixing bones.
BMGs have also been developed for recon-
structive devices, fractured fixations, spinal im-
plants, ophthalmic surgery, and cataract sur-
gery. BMG surgical blades are sharper and
longer-lasting than steel, less expensive than
diamond, and more consistently manufactur-
able (since they are produced from a single
mold) ready for use. Other edged tool applica-
tions include knives and razor blades. These
glasses can be honed to superior levels of sharp-
ness because of the absence of microstructure.
Vitreloys (a trade name for Zr-based BMG
alloys manufactured by Liquidmetal Technolo-
gies) are also used for materials in knee-replace-
ment devices, pacemaker casings, etc. [21].
11.5.3. Other Applications
BMGs have been used to produce components
for liquid crystal display casings on cell phones,
and to create a Vitreloy-encased laptop that rolls
up like a piece of paper. New military applica-
tions for BMGs include composite armor, light-
weight casings for ordnance, MEMS casings
and components, thin-walled casings and com-
ponents for electronics, casings for night sights
and optical devices, missile components such as
fins, nosecones, gimbals, and bodies, aircraft
fasteners, and electromagnetic pulse and elec-
tromagnetic interference shielding [21].
Metallic glasses can also be used for decora-
tive purposes, e.g., tie-pin frames.
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