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Metallic Glasses: July 2012
Metallic Glasses: July 2012
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Metallic Glasses
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the late 1980s, metallic glasses have also been the nearest neighbor distances or the coordina-
produced in a bulk form with section thick- tion number in these noncrystalline materials.
nesses reaching up to 72 mm. During the Each atom in the noncrystalline solid will have
2000s, exciting developments took place on the different nearest neighbors and coordination
synthesis, characterization, and applications of number. Consequently, X-ray diffraction pat-
metallic glasses both in bulk and ribbon form. terns from amorphous solids do not have sharp
Traditionally, solid materials are classified peaks; instead they show diffuse intensity max-
into two major groups—crystalline and amor- ima. But, it can be safely stated that the nearest
phous—on the basis of the arrangement of neighbor distances are longer and the coordina-
atoms inside them. Metallic materials are tradi- tion numbers smaller in a noncrystalline solid in
tionally considered crystalline in nature, pos- comparison to its crystal counterpart, assuming
sessing translational symmetry, i.e., their that a solid can exist in both the crystalline and
constituent atoms are arranged in a regular and noncrystalline states. This suggests that there is
periodic manner in three dimensions. Further- no unique description of the ‘‘structure’’ of a
more, the concept of a space lattice requires that noncrystalline solid and that there is no limit to
every atom in the crystal has identical surround- the possible atomic arrangements in these
ings. That is, the nearest neighbor distances and materials. This poses a serious problem in de-
the coordination number are the same for any scribing the structure of noncrystalline
atom. Thus, for a face-centered cubic structure, materials.
the first nearest neighbor distance is aH2/2, A revolution in the concept of metals was
where a is the lattice parameter of the crystal brought about in 1960 when POL DUWEZ synthe-
and the coordination number is 12. Because of sized thin foils of an Au–25 at% Si alloy in the
the constraints of symmetry on the different glassy state by rapidly solidifying the liquid at
ways in which the constituent atoms can be rates approaching a million degrees celsius per
arranged, only a limited number of arrange- second [1]. Since these amorphous materials are
ments are possible in the three-dimensional based on metals, these were referred to as glassy
space. Thus, we have only seven crystal sys- metals or metallic glasses. Subsequently,
tems, 14 Bravais lattices, 230 space groups, etc. hundreds and thousands of alloys of different
Different metals with the same Bravais lattice compositions have been prepared in the glassy
can have different lattice parameters and inter- state. A number of metallic glasses with a large
axial angles and therefore new structures could section thickness have been produced since the
be generated. In addition, by placing different late 1980s. These are referred to as bulk metallic
numbers of atoms at each lattice point in a given glasses (BMGs). The present consensus appears
Bravais lattice, it is again possible to generate a to be that a glassy material is considered bulk,
new crystal structure. Thus, the actual number only when the section thickness is at least a few
of crystal structures is, of course, unlimited. But, millimeters. This number is left very vague and
every one of these theoretically infinite number depending on who defines it, it ranges from
of arrangements can be described in terms of 1 mm up to as large as 10 mm.
one of the 14 Bravais lattices. All crystalline The terms ‘‘noncrystalline’’, ‘‘amorphous’’,
solids produce X-ray diffraction patterns with or ‘‘glassy’’ refer to similar (random) atomic
sharp intensity maxima, the positions of which arrangements in solid materials, and therefore
correspond to the lattice spacings and the inten- they are used interchangeably. While ‘‘noncrys-
sity to the atomic distribution inside the unit talline’’ is a generic term to describe any solid
cell. material that does not possess crystallinity, a
Any solid in which the regular arrangement noncrystalline solid formed by continuous cool-
of atoms, i.e., periodicity, is absent is considered ing from the liquid state is known as a ‘‘glass’’;
noncrystalline. That is, these materials do not but when it is obtained by any other process,
possess any crystallinity. ‘‘Amorphous’’ and e.g., vapor deposition or solid-state processing
‘‘glassy’’ are the other terms normally used to methods, it is referred to as an ‘‘amorphous’’
describe such an arrangement of atoms. Since material. It has also been occasionally empha-
the atomic arrangement is random, and there is sized that the presence of a glass transition
no periodicity, it will be difficult to define either temperature, Tg, is the hall-mark of a true glass.
Metallic Glasses 3
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- of the glass also depends on the extent to which
ing methods, then the undercooling achieved structural relaxation has occurred during subse-
could be a few hundred degrees. Another way of quent heating to higher temperatures, but below
increasing the amount of undercooling achieved the crystallization temperature, Tx. The higher
is to increase the imposed solidification rate; the the structural relaxation the closer it moves
higher the solidification rate the larger the towards a ‘‘true’’ or ‘‘ideal’’ glass.
amount of undercooling. The variation of specific heat, Cp, and vis-
The situation in the case of glass-forming cosity, h, with temperature is shown in Figure 2.
liquids is different. The difference between a The Cp of the undercooled liquid increases with
normal metal and a glass-forming metallic decreasing temperature and the difference be-
material is that, in the case of the glass-forming tween the Cp of the undercooled liquid and the
liquid, the liquid can be significantly under- crystal continues to increase till Tg. At Tg, there
cooled, either due to the imposition of a high is a sudden drop in the Cp value of the under-
solidification rate, or removal of heterogeneous cooled liquid, a manifestation of the fewer
nucleating sites, or other reasons. The volume degrees of freedom as a result of freezing of
decreases even in the undercooled region and its the liquid. Once the glass had formed, there is
viscosity continues to increase with decreasing very little difference in the Cp between the
temperature. At some temperature, designated crystal and the glass.
as the glass transition temperature, Tg, the vis- Metallic glasses often exhibit a reversible
cosity of the undercooled liquid becomes so glass–liquid transition at Tg, which is mani-
high (about 1012 Pa s) that the liquid gets ‘‘fro- fested in significant changes in Cp or h. During
zen-in’’, and this ‘‘frozen-in liquid’’ (it is like a reheating of the glassy samples, there is a sud-
solid for all practical purposes) is referred to as den increase in Cp and simultaneously there is a
glass. decrease in the viscosity at Tg. These observed
As described above, Tg is dependent upon reversible changes suggest, that similar to other
several factors—the imposed cooling rate and types of glasses, metallic glasses can revert to
the magnitude of undercooling, among others. the supercooled liquid state without crystalliza-
In other words, the glass ‘‘transition’’ is not a tion. This reversibility also suggests that the
true thermodynamic phase transition, but is structure (atomic arrangement) of the glass is
kinetic in nature. Thus, the Tg and the structure closely related to the atomic arrangements pres-
of the glass are cooling rate dependent. The ent in the liquid state.
faster the alloy is solidified from the liquid state Glasses (and even more true for metallic
the higher is the Tg value (Fig. 1). The structure glasses) are not in a thermodynamically stable
Metallic Glasses 5
(equilibrium) state. From a physics point of initially no rigorous scientific basis for choosing
view, glasses are in an excited state, and at any the alloy compositions which could be formed
given temperature, provided sufficient time as glasses. Many glasses were produced more or
(may be a few minutes to thousands of years, less by trial and error. In fact, the very first
depending on the type of glass and the way it is synthesis of a metallic glass in the Au–25 at% Si
made) is provided, they will relax and eventu- alloy by rapid solidification processing (RSP)
ally transform to the crystalline ground state. So, methods in 1960 by POL DUWEZ and his stu-
the question frequently asked is whether the dents [1] was by accident in more than one way.
principles of thermodynamics, where the func- To produce metallic glasses in large quanti-
tions are defined for equilibrium states, are ties and in a reproducible way, understanding
applicable to systems which are far from the basic reasons for glass formation from the
equilibrium. liquid is essential. The ability of a metallic
This aspect has been dealt with in some liquid alloy to transform into the glassy state is
detail [3, 4] based on the concepts of under- defined as the glass-forming ability (GFA).
cooling developed by TURNBULL [5]. It is true
that the thermodynamic principles are, strictly
speaking, applicable only to the system which is 4.1. Critical Cooling Rate
in equilibrium. But, they can also be used when
the system under consideration is an under- The most important criterion to achieve glass
cooled liquid. formation is to solidify the molten alloy at a rate
As mentioned earlier, metallic liquids can be higher than the critical cooling rate, Rc. This
significantly undercooled for extended periods criterion has to be obeyed irrespective of wheth-
of time without crystallization occurring [5]. er we are dealing with ribbon or bulk glasses,
This is because the critical size of the nucleus to with the realization that Rc is dependent on the
form the solid crystalline phase, at the freezing alloy system. Thus, if Rc is higher, the section
temperature, Tm, is infinitely large. Put differ- thickness of the glass is small and so the material
ently, the time scale for the nucleation of the could be synthesized only in a ribbon form. On
crystalline phase is a function of the degree of the other hand, if it is low, then bulk glasses can
undercooling experienced by the melt. It is be synthesized.
exceedingly long at the freezing temperature A solid is considered glass only when the
and decreases with increasing amount of under- volume fraction of crystal nuclei formed is
cooling. When the time scale for nucleation is below the detection level, typically taken as
sufficiently long so that the liquid phase can still 106. Such a situation can be realized only when
explore the different possible phases in which it the melt is undercooled significantly to below
could exist, one can still define the entropy and Tg, which can be obtained by rapidly solidifying
other thermodynamic functions of the liquid. the melt. The value of Rc can be calculated from
That is, the liquid is in a metastable state for isothermal crystallization kinetics by knowing
which entropy, free energy, and other thermo- the viscosity of the supercooled liquid, h,
dynamic parameters can be defined. In this entropy of fusion, DSf, etc. It has been shown
sense, one can use the thermodynamic princi- that Rc decreases with increasing h, DSf, and
ples that are applicable to equilibrium systems decreasing liquidus temperature, Tl.
in these situations also. The best way to experimentally determine
Rc is by constructing the time–temperature–
transformation (T-T-T) diagrams. Figure 3A
4. Glass-Forming Ability shows a schematic T-T-T diagram for a hypo-
thetical alloy. If the alloy is cooled from the
A metallic melt needs to be significantly under- liquid state under equilibrium conditions, i.e.,
cooled to a temperature below Tg for it to extremely slowly, solidification will require a
transform into the glassy state. Even though very long time and the product of solidification
some basic empirical rules and some of the would always be a crystalline solid. Even if the
thermodynamic conditions that need to be sat- liquid alloy is cooled a little more rapidly
isfied to form a glass were known, there was (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 typical of the solid state. In other words, the
time, t1, and the product is still a crystalline undercooled liquid is now frozen-in and a glassy
solid. A similar situation would be obtained phase has formed. The cooling rate represented
even if the alloy were to be solidified at a higher by curve ‘‘2’’ is referred to as the ‘‘critical
solidification rate. If the liquid alloy is solidified cooling rate’’, and is commonly designated by
at a rate faster than the cooling rate represented the symbol, Rc. Thus, the simplest and most
by curve ‘‘2’’, which represents a tangent to the logical criterion one could think of to predict
T-T-T-curve at its nose, then crystal formation glass formation is that the liquid alloy should be
will not take place. Instead, the liquid will be cooled at a rate faster than Rc and to a tempera-
retained in the undercooled condition. If the ture below Tg.
temperature of this undercooled liquid is further The form of the T-T-T curve and the temper-
decreased to below Tg, the viscosity of the liquid ature and time at the nose are determined by the
will increase to a value of 1012 Pa s, which is competition between the increasing driving
Metallic Glasses 7
force for nucleation (due to increased under- are some phase diagrams in which the liquidus
cooling) and the decreased atomic mobility (due curves drop very steeply with solute content. An
to lowering of temperature). It is possible to alloy system exhibiting a eutectic temperature
theoretically calculate the critical cooling rates that is significantly lower than the melting
for different alloy systems using the theory of points of the individual components is
isothermal crystallization kinetics. Addition of referred to as a ‘‘deep’’ eutectic. In such cases,
the majority of the alloying elements shifts the the Trg (¼ Tg/Tl) value around the ‘‘deep’’
T-T-T curve to the right. That is, the liquid can be eutectic composition is a strong function of the
retained in the undercooled condition for a alloy composition and exhibits the highest value
longer period of time at any temperature and at the eutectic composition [7]. Therefore, it
therefore the value of Rc for glass formation is should be possible to quench this alloy easily
lower. The farther the T-T-T curve is shifted to into the glassy state. Thus, the Turnbull criterion
the right the lower the value of Rc. This is the of high Trg and deep eutectics converge at the
concept used in synthesizing BMGs, which deep eutectic compositions.
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 4.4. Topological Models
of a large number of alloying elements, glassy
phases are formed at rates as low as 1 to 100 K/s, The above empirical criteria (high values of Trg
and sometimes even slower. and deep eutectics) have been extensively
employed in synthesizing micrometer-thick
metallic glasses by RSP techniques. There have
4.2. Reduced Glass Transition also been some theoretical formulations to
Temperature explain glass formation in alloy systems that
deal with the atomic sizes of the constituent
TURNBULL [6] suggested, purely on the kinetics elements and their topological arrangement.
of crystal nucleation and the viscosity of melts, Several topological models have been pro-
that the ratio of Tg to the liquidus temperature of posed to explain the structure of metallic
the alloy, Tl, should be a good indicator of GFA glasses. One of the earliest models was devel-
of the alloy. The higher this ratio, the higher the oped initially for liquid structures by BERNAL [8].
viscosity, and therefore the alloy melt could be This model refers to the dense random packing
easily solidified into the glassy state at a low (DRP) of hard spheres and was shown to contain
critical cooling rate. The ratio of these two a number of different polyhedra such as tetra-
temperatures, Tg/Tl, has been designated as the hedra, octahedra, and others, and the atoms are
reduced glass transition temperature, Trg. Based supposed to be occupying the corners of such
on the nucleation theory, it was suggested that at polyhedra. The radial distribution functions
Trg 2/3, homogeneous nucleation of the crys- generated from such an arrangement of atoms
talline phase is completely suppressed. Most showed reasonable agreement with those ob-
typically, a minimum value of Trg ffi 0.4 has tained from diffraction experiments. However,
been found to be necessary for an alloy to there have been difficulties in applying this
become a glass, but the higher the Trg value, model for metallic glasses. Taking the clue that
the easier it is for the glass to form. The Trg value these models show the presence of polyhedra, it
is reasonably high for all glass-forming alloys, was suggested that the metal atoms in a metal–
and is in fact about 0.6 for most of the alloy metalloid type glass form the tetrahedra and that
compositions studied. the metalloid atom occupies the central hole
(they ‘‘stuff’’ the voids in the Bernal DRP
structure). Consequently, the typical alloy com-
4.3. Deep Eutectics position at which the metallic glass forms is
approximately A4B (where A represents the
The value of Tg changes slowly with solute metal and B the metalloid), and this explains
content and the value of Tl usually decreases the frequently observed composition at which
with increasing solute content. However, there metallic glasses form.
8 Metallic Glasses
This model has been criticized and subse- beyond a critical solute concentration, the
quently modified [9] by stating that the actual glassy alloy becomes energetically more favor-
size of the voids in the metal tetrahedra in the able than the corresponding crystalline lattice.
Bernal structure is too small for any metalloid They also noted that a minimum solute concen-
atom to be accommodated there. It was also tration, CBmin , was necessary, which is inversely
shown that the concentration of ‘‘holes’’ of the correlated with the atomic volume mismatch
required sizes to accommodate the metalloid (VAVB)/VA (where VA and VB are the atomic
atoms was too low to account for the observed volumes of the solvent and solute, respectively)
glass compositions [10]. However, it has been according to the relationship:
shown [11] that the effective size of the metal-
ðVA VB Þ min
loid atom depends on the nature of the metal in C ¼ l
V B
A
which it is dissolved.
Irrespective of the actual size of the voids and The value of l was noted to be 0.1. This
whether the above model is valid or not, it is of model was later extended to calculate the l
interest to note that the metal-metalloid-type value in the case of multi-component alloy
binary phase diagrams exhibit deep eutectics at systems [14, 15] and it was noted that the
around a composition of 15–25 at% metalloid. diameter of the rod which could be cast into a
Some typical examples are Fe–B (17 at% B), fully glassy state increased with increasing val-
Au–Si (18.6 at% Si), and Pd–Si (17.2 at% Si). ue of l, and at the maximum possible diameter
Therefore, the concepts of deep eutectics and the l value approached 0.18.
structural models also seem to converge in One of the assumptions made by EGAMI and
obtaining glasses in the (transition or noble) WASEDA [13] in calculating the lattice strain was
metal-metalloid types. that the solute atoms, irrespective of their sizes,
occupy lattice sites of the solvent structure.
Atomic Size Mismatch. Analysis of a large Assuming that the solute atoms occupy the
amount of data on binary metallic glasses has interstitial sites if the reduced radius R ¼ RB/RA
shown that the atomic size ratios of the majority is less than 0.8, MIRACLE and SENKOV [16] calcu-
to the minority atoms varies between 0.79 and lated the strain induced by solute atoms and
1.41, with many of the glasses in the range of showed that the crystalline lattice becomes de-
0.85 to 1.15. This has been termed the anti- stabilized when it reaches a critical value of
Hume-Rothery criterion [7], since HUME- 0.054. The minimum solute concentration
ROTHERY had earlier pointed out that the radius required to achieve this critical strain was also
mismatch should not exceed 15% to form calculated [16].
extensive solid solutions in alloy systems based The minimum solute concentration required
on noble metals. Thus, it appears that the sizes of to destabilize the crystalline lattice is normally
constituent atoms have a significant role to play small. But, in the case of BMGs, it is noted that
in glass formation. the total solute content is usually in the range of
One of the ways by which a crystalline about 20 to 40 at%. This was explained on the
metallic material can become glassy is by the basis that the optimum concentration of an
introduction of lattice strain. The lattice strain individual alloying element in a BMG is less
introduced disturbs the crystal lattice and once a than the minimum solute concentration of an
critical strain is exceeded, the crystal becomes element with the same atomic size in a binary
destabilized and becomes glassy. In fact, EGAMI alloy. Therefore, the destabilizing effect of each
takes pains to state that ‘‘In general, alloying solute element was suggested to be additive in
makes glass formation easier, not because these models. A topological efficient cluster
alloying stabilizes a glass, but because it desta- packing (ECP) model was also proposed to
bilizes a crystal’’ [12]. Using the atomic scale explain glass formation and it was shown that,
elasticity theory, EGAMI and WASEDA [13] cal- irrespective of the number of chemically dis-
culated the atomic level stresses in the solid tinct solute species, the BMGs contain no more
solution (the solute atoms are assumed to occu- than three topologically distinct solutes [17].
py the substitutional lattice sites in the solid The presence of solute-centered structural enti-
solution) and the glassy phase and noted that ties and the fact that efficient packing of atoms
Metallic Glasses 9
reduces the energy of the system was recently parameters can only be obtained after the
verified based on systematic experimental and glass has been synthesized and the transfor-
computational analyses [18]. This was further mation temperatures are measured.
modified and it was called the modified ECP 2. Thermodynamic Modeling. The thermody-
model [19]. 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
4.5. Inoue Criteria system.
3. Physical Properties of Alloys. This group
Based on the extensive data generated on the considers the physical properties of materials
synthesis of BMGs, INOUE [20, 21] formulated such as viscosity of the melt, heat capacity,
three basic empirical rules for the formation of activation energies for glass formation and
BMGs. These may be stated as: crystallization, bulk modulus, etc.
4. Computational Approaches. These methods
1. The alloy must contain at least three com- help in predicting the GFA of alloys from
ponents. The formation of glass becomes basic thermodynamic data, and without the
easier with increasing number of compo- necessity of actually conducting any experi-
nents in the alloy system. ments to synthesize the glass to determine
2. A significant atomic size difference should the GFA.
exist among the constituent elements in the
alloy. It is suggested that the atomic size Table 1 summarizes the different criteria
differences should be above about 12% proposed to explain glass formation in alloy
among the main constituent elements. systems. Amongst all the parameters that have
3. There should be negative heat of mixing been proposed, the g parameter [22] seems to be
among the (major) constituent elements in most effective. This parameter takes into ac-
the alloy system. count the stability of the liquid phase and also its
resistance to crystallization. Even though a very
Among the above criteria, the first one is large number of parameters (Trg, DTx, a, b, g,
based on the thermodynamic and kinetic aspects g m, d, f, and new b) have been proposed to
of glass formation, and the second one is based explain the formation and thermal stability of
on the topological aspects (structure and pack- the BMGs, it was concluded that no one single
ing of atoms). The third criterion is essential for parameter can satisfactorily explain the GFA of
mixing of atoms (alloying to occur) and for the
formation of a homogeneous glassy phase.
However, some apparent exceptions have been Table 1. Summary of the quantitative criteria proposed to evaluate
noted in a few alloy systems. Therefore, newer the glass-forming ability of liquid alloys
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 xT gÞ2
l 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
BMGs in all alloy systems [23]. The criteria for 1010 K/s. Thus, the basic requirements to
glass formation by other methods, e.g., mechan- achieve high solidification rates are:
ical alloying, seem to be somewhat different
[24]. 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
5. Synthesis of Metallic Glasses
heat from the liquid metal.
Metallic glasses were first produced by rapidly
Since the solidification rate achieved, R, is
solidifying metallic melts at cooling rates of
inversely proportional to the square of the thick-
about 106 K/s [1]. This early excitement of
ness of the solidified molten layer, it is critical
being able to produce the normally crystalline
that the section thickness of the ribbon is very
metals in a glassy state, and their excellent
small. For example, the solidification rate
mechanical, chemical, and magnetic properties,
achieved is approximately 105 K/s for a foil
led to the development of a number of different
thickness of 100 mm and 109 K/s for 1 mm
techniques to obtain metallic glasses in different
thickness. The typical thickness of a rapidly
sizes and shapes (ribbons, wires, powders, etc.).
solidified ribbon is about 50 mm and therefore
Some of these techniques have been described
it would have solidified at a rate of approximate-
in [25–27]. The commercial requirements of
ly 106 K/s. These examples serve to illustrate
large size sheets for different applications
that it is necessary to have as small a section
resulted in the development of the planar flow
thickness as possible to achieve high solidifica-
casting method wherein rapidly solidified sheets
tion rates.
of at least 30 cm in width could be produced [28].
The quest for glassy alloys with larger section
thickness for industrial applications eventually 5.2. General Techniques to Achieve
culminated in the discovery of BMGs [29].
High Rates of Solidification
BMGs have been produced in the form of rods,
sheets, pipes, powder, and spheres, at relatively
The cross section of the solidified metal layer
slow solidification rates of about 102 K/s or less.
obtained by the ‘‘gun’’ technique of rapid solid-
Rapidly solidified ribbons of BMGs are often
ification is not uniform because of the free flow
used to study their properties and crystallization
of the liquid metal under pressure. Hence, it was
behavior before proceeding to investigate the
very difficult to determine the physical and
synthesis and characterization of BMGs.
mechanical properties of these novel materials.
To overcome this deficiency, a number of other
techniques were developed to improve upon the
5.1. Principles of Rapid Solidification uniformity of cross section of the solidified
Processing layers. These include the piston-and-anvil [31]
and twin-piston [32] methods in which the
POL DUWEZ and his colleagues first synthesized molten metal is rapidly flattened between two
an Au–25 at% Si alloy in the glassy state by impacting substrates and consequently the drop-
rapidly solidifying their metallic melts using the let solidifies rapidly. The greatest advantage of
so-called ‘‘gun’’ technique [30]. In this tech- these methods over the ‘‘gun’’ technique is the
nique, a small quantity of the molten metal is uniformity of section thickness. Attempts have
ejected using a shock wave to atomize and also been made to increase the solidification
rapidly solidify it on a conducting substrate. rates by using diamond (! Carbon, 2. Dia-
The molten metal spreads in the form of a thin mond) as a substrate [33], since it is known that
layer, typically a few tens of micrometers (usu- diamond at liquid nitrogen temperature has a
ally about 20–50 mm) in thickness, and the heat much higher thermal conductivity than copper
is extracted rapidly by the conducting copper at room temperature.
substrate. Consequently, the molten alloy soli- The most significant milestone in this direc-
difies very rapidly, at solidification rates of up to tion was the development of the chill block melt
Metallic Glasses 11
1 to 7 between the Pd-alloy and the salt, a number of alloy systems [56, 57]. In this
porosity of about 65% was obtained in the alloy. process, a mixture of the blended elemental or
The pores in the foam had a polyhedral shape pre-alloyed powders is loaded, under inert at-
with sizes of 125 to 250 mm, corresponding to mosphere conditions, into the milling container
the shape and size of the salt crystals. High along with the grinding medium (usually stain-
pressure helium and/or hydrogen gas has also less steel, tungsten carbide, or other hard ma-
been used to produce a significant amount of terials. This container is then placed inside the
porosity with a uniform pore size [54b]. mill and the whole mass is violently agitated for
the desired length of time. Depending on the
5.5. Other Methods type of mill used, the powder is subjected to
shear, impact, or other types of mechanical
forces.
Metallic glasses have also been synthesized by
As depicted in Figure 6A, the powder parti-
other methods. Since metallic glasses are non-
cles get trapped between two grinding balls and
equilibrium phases, any method capable of
go through a process akin to rolling. But, there
processing materials at far-from equilibrium
could be compressive, shear, and impact forces
conditions should, in principle, be able to pro-
exerting on the surfaces of the powder particles.
duce metallic glasses. (The true definition of a
Under the action of mechanical forces, the soft
glass is that it is a liquid that has been cooled into
individual powder particles are flattened into a
a state of rigidity without crystallizing. Accord-
pancake shape, and if the powder particle is
ingly, purists reserve the term ‘‘glass’’ only to
brittle, it gets comminuted and the particle size
those noncrystalline materials that have been
becomes smaller (Fig. 6B). Due to the random
obtained directly from the liquid state. Noncrys-
talline materials synthesized by other methods, process, the flat soft particles get stacked and
form a layered structure. On continued milling,
such as starting from the solid or vapor states,
these layered structures get convoluted. This
are referred to as amorphous materials).
process of convolution continues with milling
Amorphous alloys have also been synthe-
time and the layer spacing is significantly re-
sized by a number of other nonequilibrium
duced. In addition, the milled powder particles
processing techniques [55]. These include
also contain a high density of crystal defects
mechanical alloying [56, 57], irradiation meth-
(dislocations, stacking faults, grain boundaries,
ods, ion implantation and ion mixing, laser
etc.). Thus, the combination of small particle
processing, plasma processing, physical and
size, reduced diffusion distances across the
chemical vapor deposition methods, electrolytic
lamellar structure, fresh surfaces and interfaces,
deposition, thermal spray processes [58], appli-
coupled with a slight rise in temperature, all
cation of high pressures [59], interdiffusion and
contribute to increased atomic diffusivity and
reaction methods, and others. In all these meth-
therefore alloying occurs. Depending on the
ods, the common theme has been to bring the
milling conditions, nature of the constituent
material into a far-from equilibrium condition
elements present, and the proportion of the
by raising the temperature, pressure, input of
elements, different types of alloy phases are
mechanical energy, or by other means and
produced. These include supersaturated solid
subsequently quenching the material to either
solutions, intermetallic phases, quasicrystalline
retain the metastable phase or use it as an
phases, or even amorphous phases. The choice
intermediate step to achieve the desired micro-
of the phase formed depends on the thermody-
structure and/or properties. Amongst the solid-
namic stability of the different competing
state processing methods, mechanical alloying
phases. The kinetics of microstructural refine-
has been the most popular to synthesize metallic
glasses including BMGs. 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
5.5.1. Mechanical Alloying milling is carried out.
The milled powder particles experience hea-
Amorphous phases have been produced by vy plastic deformation and generate a variety of
mechanical alloying (MA) methods in a large 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 phases have been formed in a number of binary,
than that of a hypothetical amorphous phase, ternary and higher-order systems by this
and consequently, the crystalline phase be- method [56, 57].
comes destabilized and an amorphous phase Amorphous alloy powders of multi-
forms [55–57]. The first report of formation of component bulk metallic glass compositions
an amorphous phase by mechanical milling was have also been produced by MA in several alloy
in an Y-Co intermetallic compound [60] and systems including those based on Fe, Mg, and
that by mechanical alloying in a Ni-Nb Zr. These powders can be conveniently consol-
powder blend [61]. Subsequently, amorphous idated into bulk in the supercooled liquid region.
16 Metallic Glasses
A clear advantage of this approach to synthesize films crystallize when heated to room
monolithic BMGs is that the size limitations temperature.
imposed by the solidification processing meth- The earliest report of formation of an amor-
ods will not apply here. phous phase in a metal is by vapor deposition
A major difference between MA and the methods. The physicists produced amorphous
solidification techniques described earlier is that metals by the vapor deposition route to study
while a bulk glassy alloy (either monolithic or their superconducting properties. According to
composite) is produced in one single step using the available reports [68], amorphous Sb was
the solidification methods, MA produces the synthesized by first evaporating the Sb metal
amorphous phase in a powder form and this and allowing it to condense on a cold substrate.
needs to be consolidated by some of the con- Subsequently, thin films of Bi, Ga, and Sn-Bi
ventional or innovative methods through appli- alloys were synthesized by the vapor deposition
cation of pressure and/or temperature. Howev- process [69], and though initially believed to be
er, one of the biggest advantages of the MA ultrafine-grained, it became clear later that the
method is that this technique could be used to films were actually amorphous.
easily produce amorphous phases in those sys- Several variants of the vapor deposition
tems where conventional melting and casting method can be used to synthesize amorphous
methods prove difficult or impossible. Further- alloys. These include, for example, plasma
more, MA has a clear advantage in producing sputtering, chemical vapor deposition, and elec-
BMG composites. A very large number of tron beam evaporation. One of the most popular
oxide-, carbide-, and other ceramic-dispersed among these is the sputtering method, in which
composites have been produced by MA. Be- atoms from the surface of the material are
cause of the heavy deformation involved and the knocked off using high-energy ions, and the
powder kneading that takes place, the ceramic atoms so removed from the surface are subse-
phase becomes uniformly dispersed in the metal quently allowed to deposit onto a cold sub-
matrix. In fact, the technique of MA was strate [70]. Vapor deposition methods are used
developed to satisfy an industrial necessity of mainly to produce small quantities for mostly
producing oxide-dispersion strengthened nickel- scientific investigations and for electronic and
based superalloys (! Nickel Alloys). Further- magnetic applications. Another problem with
more, it has been demonstrated that using MA, these methods is that the samples are very
one should be able to produce a composite sensitive to the presence of impurities. The
containing a very high volume fraction of even presence of impurity atoms such as oxygen has
nanometer-sized ceramic particles [62]. been identified as the reason for the formation of
Other solid-state methods to synthesize amor- amorphous phases in some materials, including
phous alloys include hydrogen-induced amor- pure metals.
phization [63], multilayer amorphization [64], Another technique that has been extensively
pressure-induced amorphization [59], amorphi- used to prepare amorphous alloys, again mostly
zation by irradiation [65], severe plastic defor- thin films, is to implant high-energy solute ions
mation [66], and accumulative roll bonding [67]. into metallic surfaces. This technique has come
to be known as ion implantation. In a related
5.5.2. Vapor Phase Methods technique, referred to as ion mixing, successive-
ly vapor-deposited layers of different elements
In these methods, starting from the vapor phase, are mixed together and alloyed by means of the
metal wires are evaporated and the vapor is thermal energy of injected rare-gas ions. Several
allowed to condense on to a cold substrate amorphous and metastable crystalline phases
usually maintained at liquid nitrogen or even have been produced by these methods [71].
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- 6. Crystallization Behavior
tained at very low temperatures, formation of
amorphous phases is relatively easy. An occa- Metallic glasses, whether produced in the form
sional problem encountered is that these thin of ribbons by the melt-spinning technique at
Metallic Glasses 17
high solidification rates or in bulk rod form by of crystals into an isotropic medium. Further-
conventional solidification methods at relative- more, this process also offers a chance to test the
ly slow solidification rates, are in a high energy classical nucleation and growth theories at large
(metastable) state. Consequently, they lower undercoolings.
their energy by transforming into the crystalline If the crystallization reaction is temperature-
state, a process referred to as crystallization or dependent, i.e., if it possesses an activation
devitrification. energy, then the position of the peak varies with
When a metallic glassy alloy is heated con- the heating rate employed assuming that all
tinuously at a constant heating rate, typically other experimental conditions are maintained
between 5 and 20 K/s, the transformations that constant. The transformation temperatures are
take place in the sample are indicated by higher at faster heating rates. It was also shown
deflections or peaks in the differential scanning that the peak temperature, Tp corresponds to the
calorimeter (DSC) or a differential thermal temperature at which the reaction rate is a
analyzer (DTA) curve. On continuous heating, maximum. Using this concept of variation of
the glassy alloy exhibits a glass transition tem- Tx (or Tp) with heating rate (b), the activation
perature Tg, one or more crystallization peaks energy for crystallization of metallic glasses has
(exothermic), Tx, and then an endothermic peak been determined using the Kissinger equation:
corresponding to the melting, Tl of the alloy. !
b Q
Crystallization of metallic glasses is ln ¼ þA
T 2p RT p
expected to take place at or above Tx. It is,
however, not a thermodynamic parameter like where A is a constant and R is the universal
the melting temperature of a metal. It is a gas constant. Thus, by plotting lnðb=T 2p Þ against
function of the heating rate employed and the 1/Tp a straight line is obtained whose slope is
higher the heating rate, the higher is the Tx. Q/R, from which the activation energy for the
Therefore, given sufficient time, crystallization transformation, Q, can be calculated. It is also
of metallic glasses can occur at temperatures possible to evaluate the individual activation
lower than Tx also. The crystallization tempera- energies for the nucleation and growth stages of
tures of metallic glasses are in the range of 0.4 to the transformation, from which information
0.7 Tm. The actual values range from as low as about the mechanism of transformation could
383 K for an Au55Cu25Si20 glass to as high as be ascertained.
982 K for a Co43Fe20Ta5.5B31.5 alloy, and From a technological point of view, the
higher for refractory metal-based alloys. crystallization temperature of metallic glasses
At a temperature Tx, which is higher than Tg, provides a real upper limit to the safe use of
the supercooled liquid crystallizes into the crys- metallic glasses without losing their interesting
talline phase(s) and the temperature interval combination of properties. But, it should be
between Tx and Tg is referred to as the width realized that Tx cannot be taken as an indicator
of the supercooled liquid region, i.e., DTx ¼ of the safe operating temperature of a metallic
TxTg. The value of DTx is different for differ- glass. For example, even though many Fe-based
ent glasses, and is usually taken as an indication metallic glasses have Tx in the region of 700 K,
of the thermal stability of the glass produced. In their maximum long-term operating tempera-
the case of BMGs this temperature interval is tures are only of the order of 420 K [73].
usually quite large and values of over 120 K An important point to be remembered is that
have been reported; the highest reported to-date Tx is the same whether measured on a ribbon or
is 131 K in a Pd43Cu27Ni10P20 BMG alloy [72]. rod of the same composition, i.e., it is indepen-
In the case of rapidly-solidified thin ribbon dent of the section thickness. The factors that
glasses, and marginal glass-formers, the value affect the value of Tx in metallic glasses are not
of DTx is very small, if observed at all. clear. A number of different possibilities have
Crystallization studies of alloys are impor- been proposed, the chief among them being the
tant from both scientific and technological atomic size. It was suggested that the Tx value is
points of view. Since crystallization of metallic higher when the atomic size of the alloying
glasses occurs by a nucleation and growth pro- element is larger than that of the solvent atom.
cess, it offers an opportunity to study the growth Reasons for a change in the Tx value were
18 Metallic Glasses
suggested to be reduction in free volume and force for crystallization is the difference in the
diffusivity, electron-to-atom ratio, and differ- free energy between the glassy phase and the
ences in electronegativity [74]. corresponding crystalline phase(s) of the same
Studies on the crystallization behavior of composition. The crystalline phases formed as a
metallic glasses also provide an opportunity to result of crystallization may be either equilibri-
study the kinetics of crystallization and the um phases or, as is frequently noted, metastable
micromechanisms of crystallization. Such phases, which may also form in the initial stages
results will provide a clear understanding of the of decomposition and will eventually transform
way the metallic glass transforms into the crys- to equilibrium phases. Therefore, it should be
talline state and offers a means to impede or possible to understand the crystallization behav-
control the crystallization behavior. In other ior of metallic glasses with reference to a
words, one could tailor the microstructure to hypothetical free energy vs. composition
obtain a glass þ nanocrystal or an ultrafine- diagram [79].
grained composite, or a completely crystalline Metallic glasses are in a nonequilibrium state
material of different grain sizes by controlling with respect to thermodynamic stability. But,
the time and temperature of crystallization [75]. they are also not in configurational equilibrium.
It has also been possible to obtain composites Accordingly, on annealing, the as-synthesized
of a fine crystalline phase dispersed in the glass slowly transforms towards an ‘‘ideal’’
glassy matrix by partial crystallization of the glass of lower energy through structural relaxa-
glass. Such composites exhibit interesting me- tion. A real crystalline material can be consid-
chanical properties, substantially high strength ered as an ideal material containing a variety of
values [76] and increased ductility [77, 78]. defects, whose character can be identified and
Furthermore, it should be possible to produce well quantified. The as-synthesized glass can be
a fully nanocrystalline material by controlled similarly considered as an ‘‘ideal’’ or ‘‘perfect’’
crystallization of the metallic glassy alloys of glass containing defects. However, the nature of
suitable compositions. As a result, the mechan- defects present in the glass is presently un-
ical and other properties could be optimized known. Thus, structural relaxation of a
through a proper understanding of the crystalli- quenched glass results in the formation of an
zation behavior of metallic glasses. It is not ideal glass. The mechanism(s) by which struc-
possible to obtain such novel and unique micro- tural relaxation occurs in glasses is through
structures by any other means and in other types annihilation of ‘‘defects’’ or free volume, or
of materials unless one starts with a fully glassy recombination of defects of opposing character,
material. or by changes in both topological and composi-
Glassy phases give rise to broad and diffuse tional short-range order [80].
halos in their diffraction patterns. It is desirable The glass prepared by solidification from the
to confirm the formation of the glassy phase melt (whether at slow rates or faster rates)
using direct transmission electron microscopy contains an excess quenched-in free volume
(TEM) techniques. Figure 7 shows the TEM and its amount increases with increasing solidi-
images and electron diffraction pattern of a fication rate. On reheating the glassy sample to a
Zr55Cu30Al10Ni5 glassy alloy. The TEM image temperature below Tg, structural relaxation
(Fig. 7A) is characterized by a complete lack of occurs through compositional short range order
contrast, while the electron diffraction pattern (CSRO) and topological short range order
(Fig. 7B) displays a very diffuse and broad halo. (TSRO). CSRO involves variation in chemical
The high-resolution TEM image (Fig. 7C) composition from point to point (slight changes
shows the so-called salt-and-pepper contrast. in the local chemical environment) and is some-
times reversible. On the other hand, in TSRO the
atomic configuration is different due to collec-
6.1. Crystallization Modes in Glassy tive motion of groups of atoms and is an irre-
Alloys versible process. This means that the process of
structural relaxation is associated with the re-
Crystallization of metallic glasses occurs by distribution and reduction of excess quenched-
nucleation and growth processes. The driving 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 in electrical resistivity (by about 2%), Curie
density. In a fully relaxed glass, that has attained temperature (by as much as 40 K), enthalpy (by
the ‘‘equilibrium’’ free volume concentration, it about 800–1200 kg/mol), superconductivity,
is possible to separate the effects due to CSRO and several other structure-sensitive proper-
and TSRO. ties [80]. Another important property that
Structural relaxation in metallic glasses is changes on structural relaxation is the density.
achieved by a low-temperature annealing pro- A small increase in density (about 0.5% for
cess, which does not cause crystallization. How- melt-spun ribbons [81] and a smaller value of
ever, significant changes in physical properties about 0.1 to 0.15% for BMG alloys [82, 83]) was
(and mechanical properties in some cases) have also reported to occur due to structural relaxa-
been reported. For example, relaxed glasses tion in metallic glasses. The relaxed glass is the
exhibit a decreased specific heat, reduced dif- starting point for all the transformations to be
fusivity, reduced magnetic anisotropy, in- studied.
creased elastic constants (by about 7%), signifi- The relaxed glass will transform first into the
cantly increased viscosity (by more than five supercooled liquid state at Tg, provided that one
orders of magnitude), and loss of (bend) ductili- is able to differentiate between the Tg and Tx
ty in some glassy ribbons, in addition to changes temperatures. This is the case in all BMGs, and
20 Metallic Glasses
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
glasses, where it was reported to be about 125 observed at all, and therefore it was not possible
106 K1. The CTE values in the glassy state to study the diffusion behavior in the super-
are usually larger than those of the crystalline cooled liquid condition. The advent of BMGs,
pure metals on which they are based. In com- which show a significantly large DTx range, has
parison to the as-quenched glassy state, the CTE changed the situation significantly; detailed
value of the glass in the structurally relaxed diffusion studies have been conducted in the
condition is higher. The CTE values are much supercooled liquid region in BMGs [98]. Such
higher in the supercooled liquid condition and temperature regimes were previously not
they are lower in the crystallized condition than accessible.
even in the glassy state [93]. The diffusion behavior of melt-spun glassy
Structural relaxation will also have an effect ribbons is known to be sensitive to structural
on the thermal expansion of the material [94]. relaxation. Accordingly, in the as-quenched
The relative length change during annealing of a ribbon (i.e., in the unrelaxed sample), the dif-
metallic glass sample is directly related to the fusivity decreases as a function of time due to
annihilation of excess quenched-in free volume structural relaxation and annealing out of excess
and therefore this occurs due to TSRO. The free volume. The diffusivity reaches a constant
disappearance of free volume will lead to a value only when the sample is fully relaxed.
decrease in the length of the sample and there- Such a situation is not obtained in the BMG
fore in the CTE as well. This is a nonreversible alloy samples due to the relatively slow solidi-
process. However, when the glassy sample is fication rates at which these glassy alloys are
heated to temperatures below Tg, where struc- produced. Therefore, whenever diffusion stud-
tural relaxation also occurs but through CSRO, ies are carried out on thin ribbon specimens,
the process is reversible. That is, the same value they are given a pre-annealing relaxation treat-
of CTE is obtained during thermal cycling by ment before the diffusion measurements are
cooling and through subsequent reheating, but made.
only up to temperatures just below Tg. The CTE Although the diffusion coefficient increases
value appears to be independent of the heating with increasing temperature, the variation of
rate at which the sample is heated to high logarithm of diffusivity with reciprocal of
temperatures [95]. temperature in BMG alloys is not linear, but
shows a ‘‘kink’’. The diffusion data can be
divided into two subsets, each described by a
7.3. Diffusion different Arrhenius equation. The first region is
for temperatures below the ‘‘kink’’ tempera-
Studies of diffusion are very important in the ture, and the other is for temperatures above the
field of metallic glasses. It is scientifically ‘‘kink’’. This kink temperature, which repre-
interesting to determine whether the mecha- sents the change in the temperature depen-
nism of diffusion in metallic glasses is dence of diffusivity, is frequently identified as
different from that in crystalline materials. the glass transition temperature. Accordingly,
More specifically, it is important to decide the pre-exponential factor Do and the activa-
whether the single atom jumps observed in tion energy for diffusion, QD are different in
crystalline materials are true in metallic glasses these two regions. The diffusivity in the super-
as well. The processes of structural relaxation, cooled liquid phase is much higher than that
phase separation, and crystallization during obtained by extrapolation from the low-
annealing of a quenched glass involve diffu- temperature data in the glassy phase [99]. This
sion and therefore the thermal stability of behavior is in contrast to melt-spun ribbons
metallic glasses is determined by their diffu- which show a single straight line described by a
sion behavior. unique Arrhenius equation. The small values in
Diffusion studies were conducted on melt- the glassy state suggest a single jump motion of
spun metallic glass ribbons [96, 97], but mostly the atoms, while the larger values in the
in the glassy state, at temperatures below Tx. supercooled liquid state might reflect a highly
The width of the supercooled liquid region is cooperative motion of a number of atoms
very small in these melt-spun metallic glasses, if [98].
24 Metallic Glasses
Figure 11. Variation of TCR with Cu content in melt-spun Pd40Ni40xCuxP20 glassy alloy with x ¼ 0, 10, 20, 30, and 40
at% Cu)
transition temperatures were quite low (<9 K) crystallization takes place by eutectic or
and the critical fields and flux pinning ability primary modes, this value is the lower limit
were also quite low due to the homogeneous of the thermodynamic driving force for
glassy structure. The latter property could be crystallization.
improved by incorporating flux pinning centers
through crystallization [106, 107]. By subject-
ing the melt-spun glassy alloy phase to high 7.6. Viscosity
pressures during crystallization, a metastable
cubic Nb3Si superconducting phase could be Viscosity is perhaps the most important physi-
synthesized [108]. cal property of a liquid alloy that determines its
GFA and flow behavior. Several studies have
been conducted to evaluate the viscosity of
7.5. Specific Heat alloys as a function of temperature, shear rate,
and alloy constituents and composition. The
Like other physical properties, the specific heat formation of the glassy phase is related to a
of metallic glasses, measured using DSC, can significant increase in the viscosity of the under-
also provide valuable information about struc- cooled melt at Tg. Whereas the viscosity of
tural relaxation. By calculating the difference in simple alloys is typically about 103 Pa s at
the specific heats between the liquid and crys- the melting point, it increases to about 1012 Pa s
talline states, other thermodynamic parameters at Tg, a value that is taken as a measure to define
such as enthalpy and entropy can be estimated. Tg.
From these parameters, the Gibbs free energy The variation of viscosity with temperature is
difference between the crystal and the liquid of great importance in understanding the for-
phases, DGlx can be calculated. Knowledge of mation of metallic glasses, realizing that the
the free energy difference between the crystal higher the viscosity at the melting temperature,
and the liquid phases can provide information the easier it is for the glass to form. The variation
about the GFA of alloys. In general, the lower of viscosity with temperature in the supercooled
the DGlx(T) value, the better is the GFA. In liquid region is usually expressed by the Vogel–
addition, the smaller the entropy of fusion, the Fulcher–Tammann (VFT) equation:
higher is the GFA. The free energy difference
B
between the crystal and the liquid phases is h ¼ ho exp
TT o
the driving force for crystallization in the case
of polymorphous crystallization of metallic where To is referred to as the VFT temperature
glasses. However, in those cases where (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 glasses, they are unstable with respect to crys-
thus the barrier to viscous flow would become tallization. That is, the GFA of the alloy
infinite, ho is the high temperature limit of increases with the fragility parameter. Accord-
viscosity, and B is a fitting parameter. The value ingly, the value of D* is of the order of 2 for the
of To is found to lie near, but below Tg. The value most fragile liquids, while it is 100 for the
of ho can be expressed as: strongest glass former such as SiO2. Figure 12
shows a typical Angell plot.
NA h
ho ¼ The variation of viscosity with temperature
V
of a Pd40Ni10Cu30P20 BMG alloy at a heating
where NA represents the Avogadro’s number, h rate of 20 K/min and a compressive stress of 20
the Planck’s constant, and V the molar vol- kPa is shown in Figure 13A [111]. The viscosity
ume [109]. ANGELL [110] has modified the remains almost constant up to near Tg, at which
equation for viscosity as: temperature it starts to decrease slowly first and
then very rapidly reaching a minimum. The
D* T o minimum temperature (of 675 K in the present
h ¼ ho exp
TT o
case) corresponds to the onset temperature of
where the parameter D*, referred to as the crystallization. After crystallization, the viscos-
fragility parameter, controls how closely the ity increases steeply with increasing tempera-
system obeys the Arrhenius behavior (D* ¼ ¥). ture and then reaches a steady-state value on
Liquids with very large and very small values completion of crystallization. It has been sug-
of D* are known as strong and fragile liquids, gested [112] that the absolute value of hmin is an
respectively. Strong liquids show the Arrhenius indication of the thermal stability of the super-
behavior for temperature dependence of viscos- cooled liquid. The value of 8.3 105 Pa s for
ity, have a high viscosity at the melting point, the Pd40Ni10Cu30P20 BMG alloy is two to three
and form stable glasses. Fragile liquids have a orders of magnitude lower than that (about
low viscosity at the melting temperature, but the 108 Pa s) for the Pd77.5Cu6Si16.5 alloy [91],
viscosity rises sharply as the liquid approaches suggesting that the supercooled liquid of the
the glass transition temperature. Such liquids Pd–Ni–Cu–P alloy has a higher resistance
are marginal glass formers and if they form against crystallization than the Pd-Cu-Si alloy.
Metallic Glasses 27
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 distilled water, and dried in air. After immersion
is appropriate for secondary working through in the corrosion medium for the desired length
viscous flow in the supercooled liquid region. of time, the specimens are again washed in
Furthermore, it has been noted that the viscosity distilled water, dried and then weighed to deter-
decreases with increasing heating rate em- mine the weight loss.
ployed as shown in Figure 13B. It has also been The corrosion behavior of metallic glassy
suggested that measurement of viscosity at high alloy ribbons (about 20 to 50 mm in thickness)
heating rates is one effective way of reducing produced by melt spinning was evaluated start-
the oxygen contamination from the measuring ing from 1974 [114, 115]. It was reported that
environment [113]. Cr-containing Fe-based Fe80xCrxP13C7 glassy
ribbons exhibited much higher corrosion resis-
tance than the crystalline Fe–Cr alloys.
8. Corrosion Behavior Figure 14A shows that while the crystalline
Fe–Cr alloys corroded at a rate of about 0.5 to
The corrosion behavior of metallic glasses be- 1 mm/a, the glassy Fe–Cr–P–C alloy did not
comes important when these materials need to show any measurable corrosion rate under iden-
be used in aggressive and hostile environments tical conditions of exposure in 1 M NaCl solu-
(high temperatures, oxidizing atmospheres, and tion at 303 K. Another important observation
corrosive media). Knowledge of the corrosion made was that the minimum amount of Cr
behavior becomes crucial when these novel required to achieve this corrosion resistance in
materials are considered for biomedical appli- the glassy alloy was only 8 at%, much less than
cations and for decorative applications, or when that required (>12 at%) in the crystalline state.
surface appearance assumes importance. Figure 14B shows that the glassy alloy did not
The corrosion behavior of a number of glassy exhibit any measurable weight change with the
alloys has been investigated by either weight concentration of HCl (from 0.01 N to 1 N) on
loss measurements and/or electrochemical exposure for 1 week at 373 K. On the other
methods. Before actually conducting the corro- hand, the corrosion rate of the crystalline 18-8
sion tests, the specimens are mechanically po- austenitic stainless steel (Fe-18 wt% Cr-8 wt%
lished in cyclohexane with silicon carbide paper Ni) increased from 103 mm/a in 0.01 N HCl to
up to grit 2000, degreased in acetone, washed in 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 Fe80xCrxP13C7 alloy
pitting corrosion occurred in the range of 0.5 to 1 . The glassy phase does not contain any crystal
N HCl in the crystalline alloy. defects such as grain boundaries, dislocations,
X-ray photoelectron spectroscopy studies and second-phase precipitates, which could
indicated that the passive film on the glassy act as galvanic cells to initiate localized
alloy consisted mainly of hydrated chromium corrosion.
oxyhydroxide, which is also a common major . Since passive films form uniformly on the
constituent of passive films on crystalline stain- glassy alloy surfaces, lower amounts of pas-
less steels. An important difference is that the Cr sivating alloying elements are needed than in
content in the passive layer of the glassy alloy a crystalline alloy to achieve a similar stability
was much higher than that on a conventional of the passive film.
austenitic stainless steel. Thus, it was concluded
that the extremely high corrosion resistance High corrosion resistance has been reported
of the glassy alloy was only partially attributed in a number of melt-spun ribbons or BMG alloy
to the formation of a protective hydrated chro- specimens [117–120]. The corrosion behavior
mium oxyhydroxide film [116], and that other of the glassy alloys is not dependent on the
factors also play an important role. section thickness. Accordingly, the corrosion
Since metallic glasses are in a thermodynam- behavior of melt-spun ribbons and BMGs of the
ically metastable state, they are expected to same composition is similar.
exhibit higher corrosion rates. The improved
and superior corrosion resistance of the glassy
alloys, in comparison with the crystalline alloys 8.1. Effect of Alloying Additions
of similar composition, has been attributed to
the following factors: The passivating ability and hence the corrosion
resistance of metal–metalloid glasses are sig-
. Metallic glasses do not contain any second nificantly different with different metalloid ele-
phase particles or precipitates. Furthermore, ments. The beneficial effect of the metalloid
the segregation patterns are also completely elements in improving the corrosion resistance
avoided. Therefore, metallic glasses can be decreased in the order P, C, Si, and B. When the
considered as chemically homogeneous. metallic glassy alloy is not covered by a stable
Metallic Glasses 29
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
30 Metallic Glasses
resistance is always lower than that of the tion behavior. Since metallic glasses are non-
crystalline pure metal component with the high- crystalline in nature, and therefore they do not
est corrosion resistance or the highest passivat- contain any crystalline defects, including dis-
ing ability [121]. locations, metallic glasses are expected to ex-
hibit the high theoretical strength.
Even though metallic glasses were synthe-
8.2. Influence of Structural Changes sized in the form of thin splats as early as
1960 [1], study of their mechanical behavior
The influence of structurally relaxing or started only in the 1970s with the synthesis of
crystallizing the metallic glassy alloys on the long ribbons by the melt spinning tech-
structure and corrosion behavior of Fe-based nique [128]. Interesting and seminal contribu-
metal–metalloid alloys has also been investigat- tions have been made regarding the deformation
ed. The effect of Cr content on the corrosion mechanisms, failure criteria, and origins of
behavior of Fe73.5Si13.5B9Nb3Cu1 BMG alloys strength, ductility and toughness and these have
in different concentrations of H2SO4 (1, 3, and been well documented in some early re-
5 N) have been studied [125, 126]. The corro- views [129–133]. It was shown that metallic
sion behavior of this alloy in three different glasses are very strong with the yield strength
conditions was investigated: (i) in the as-solidi- exceeding 1 GPa in some metal–metalloid sys-
fied fully glassy condition, (ii) by annealing it tems. It was also shown that they exhibited very
for 1 h at 813 K to obtain a nanocrystalline limited plastic strain (often less than about
structure (10–15 nm grain size), and (iii) by 0.5%) in tension and that inhomogeneous de-
fully crystallizing the samples (to achieve a formation occurred through formation of shear
grain size of 0.1–1 mm) through annealing at bands. Even though many different theories
973 K for 1 h. The corrosion resistance was were proposed to understand and explain the
higher with increasing Cr content in the range mechanical behavior of these thin ribbon speci-
studied (0 to 8 at%). However, a minimum Cr mens, the reliability of the results was poor due
concentration of 8 at% was found necessary to to the limited size of the samples and conse-
generate a stable passive layer. Among all the quently a poorly defined and ill-controlled stress
conditions studied, the glassy structure showed state during mechanical testing.
the best corrosion resistance, followed by that in The successful synthesis of BMGs in the late
the nanocrystalline state. The fully crystallized 1980s/early 1990s [29, 134] changed the situa-
alloy showed the least corrosion resistance. tion completely. As a result of this development
It was also noted that the effect of dispersion and the availability of advanced characteriza-
of nanometer-sized particles in a glassy matrix tion techniques, research on the mechanical
becomes significant, as far as corrosion resis- behavior of BMGs has been very active. Two
tance is concerned, only when the particles are comprehensive reviews on the mechanical
reasonably large, say >20 nm. If these particles behavior of BMGs have appeared recently
are extremely fine, e.g., 2–3 nm, they do not [135, 136].
seem to affect the corrosion behavior
adversely [127].
9.1. Deformation Behavior
structural defect in a glassy material in the way but at different homologous temperatures
that a dislocation is a defect in a crystal. Instead, (T/Tg).
an STZ is an event defined in a local volume and
not a feature of the glass.
9.3. Temperature Rise at Shear Bands
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 assuming that t y ¼ sy/2 and that g o ¼ 1, the
these two parameters as: above equation was rewritten as:
DTg 2 Tg To
sf ¼ 1:1sy ¼ 55 E ¼ 3R
V eE V
where sf and sy are the fracture and yield There have been other correlations in the
strength, respectively, DTg ¼ TgTo where To literature. For example, the tensile strength and
is the ambient temperature, and V is the molar hardness of BMGs have been shown to scale
volume. A linear relationship is found to exist with the Young’s modulus, as shown in
between the calculated fracture strengths and Figure 18.
the published experimental fracture strengths.
The strength data of 15 BMG alloys were
analyzed with a view to exploring the underly- 9.5. Ductility
ing physics of the linearity between strength vs.
DTg/V in terms of fundamental thermodynamic Associated with the high strength of metallic
principles [155]. A plot of room temperature glasses is their brittleness. Even though some
yield shear strength of these BMGs as a function BMGs show a small amount of plastic defor-
of (TgTo)/V showed a linear dependence, sat- mation, the majority of them fail soon after
isfying the equation: yielding. This is because metallic glasses do
not in general show work-hardening character-
Tg To istics; there have been some reports on ‘‘work
t y ¼ 3R
g o :V
hardenable’’ BMGs [157].
where R is the gas constant and g o is the critical Metallic glasses are very brittle under ten-
local shear strain leading to destabilization of sion, with almost no plastic strain to failure;
local shearing events. On the basis of the above glassy ribbons show considerable bend ductili-
equation, the authors also deduced the correla- ty. When metallic glasses are tested in compres-
tion between Young’s modulus and Tg. Since sion, they seem to exhibit some amount of
E ¼ sy/eE and the room temperature elastic plastic strain before failure. The reasons for this
strain limit of BMGs is approximately 2%, and difference may be found in the way the shear
Metallic Glasses 35
bands are nucleated and propagated. During a deformation. Metallic glasses that exhibit a
tensile test, crack initiation occurs almost im- clear fatigue limit also display serrated flow
mediately after the formation of the first shear during monotonic deformation. This is a mani-
band, and as a result metallic glasses fail cat- festation of strain aging.
astrophically and show essentially zero plastic Since metallic glasses have very high tensile
strain prior to failure. However, specimens strengths, they are expected to show very high
loaded under constrained geometries (e.g., com- fatigue limits. However, this has not been real-
pression) fail in an elastic, perfectly plastic ized. The fatigue ratio is typically in the range of
manner by the generation of multiple shear 0.4 to 0.5 in the case of crystalline alloys, but it is
bands, i.e., some plastic strain is observed be- much smaller, going down to a value of 0.04 in
fore failure. metallic glasses, even though higher values
One way of overcoming this lack of ductility have been reported occasionally. The reasons
in metallic glasses seems to be to introduce a for this significant difference in the fatigue
crystalline phase to produce a composite ratios between crystalline and glassy alloys are
either in situ or ex situ. There have been reports not clear. Furthermore, even though the propa-
of significant achievement of plasticity in gation of fatigue cracks appears to be similar
monolithic BMGs. Some typical examples between crystalline materials and glassy alloys
are the plastic strains to failure of 16% (striations are seen in both types of materials),
in Cu47.5Zr47.5Al5 [157] and 20% in reasons for the susceptibility of metallic glasses
Pt57.5Cu14.7Ni5.3P22.5 [158] glassy alloys. to crack initiation are not known, since they do
It has been suggested that materials with not contain crystalline defects. Furthermore,
a m/B, where m is the shear modulus, and B the fatigue lifetimes are dominated by the loading
bulk modulus, of over 0.3 are brittle, while those cycles needed to initiate damage rather than the
with values of <0.3 are ductile [159]. A plot of cycles needed to propagate the damage, gener-
fracture energy, Gc, against m/B, led to the ally in the form of cracks, to critical size.
suggestion that a critical value of m/B differen- Preliminary results suggest that the compo-
tiating a brittle BMG from a ductile BMG sition of the alloy can affect the fatigue behav-
appears to be in the range of 0.41–0.43 [160]; ior. Substituting 10 at% Cu with Ni seems to
BMGs with a m/B value of over 0.43 are brittle. improve the fatigue limit and fatigue ratio of
It is also suggested that metallic glasses Zr50Cu40Al10 BMG alloys [165], attributed to
are ductile when the Poisson’s ratio is high the ease of oxidation of the fresh fatigue-frac-
[158, 161]. tured surface of the Ni-free alloy. Presence of
Large amounts of ductility have been re- nanocrystalline regions in a Pd-containing
ported in other BMG alloys [162], and super- Zr50Cu40Al10 glassy alloy was found to be
plasticity could be achieved over a range of responsible for increasing the fatigue limit by
strain rates in the supercooled liquid blocking shear bands and crack propaga-
region [163]. tion [166]. Oxygen and inclusions, in small
amounts, seem to have a major effect on the
fatigue behavior of Zr-based BMG alloys [167].
9.6. Fatigue Early studies [168] have indicated that the
Zr41.2Ti13.8Cu12.5Ni10Be22.5 BMG alloy was
Fatigue is a form of failure in structures sub- highly susceptible to stress corrosion cracking
jected to dynamic and fluctuating stresses and and stress corrosion fatigue in the presence of
the mechanism of fatigue failure involves initi- aqueous NaCl solution. The obtained results
ation of cracks, their propagation, and final fast suggest that crack growth mechanisms in air
fracture [164]. The SN (stress versus number and in aqueous solutions are different [169].
of cycles to failure) plots of metallic glasses Fatigue crack propagation behavior in air seems
exhibit a well-defined fatigue limit and in this to be similar to that observed in polycrystalline
sense they are similar to crystalline alloys. The metals and is associated with alternating blunt-
occurrence of a well-defined fatigue limit in ing and re-sharpening of the crack tip, as evi-
crystalline alloys has been attributed to the denced by the presence of fatigue striations. On
occurrence of strain aging during tensile the other hand, in NaCl solution, the mechanism
36 Metallic Glasses
seems to be driven by a stress-assisted anodic strength. A more than double fatigue ratio for a
reaction at the crack tip. composite in comparison to a monolithic glassy
Fatigue behavior of composites was im- alloy has been reported [171]. On the other
proved since the presence of the crystalline hand, it has also been reported that the fatigue
phase was able to relieve the residual surface behavior of a composite is worse than that of a
stresses or accommodate any surface strains monolithic alloy [172].
such that defects do not form. Absence of The fatigue resistance of BMGs and their
microdefects also resulted in a very high fatigue composites is in general poorer than that of the
strength. crystalline materials. It has been shown [173]
that by matching the microstructural length
scales (of the second crystalline phase in a
9.6.1. Fatigue Crack Growth Rate composite) to the mechanical crack-length
scales, the fatigue resistance could be improved.
The fatigue crack grows with each cycle and Compressive stresses on the surface of speci-
therefore the time for it to reach the critical size mens are known to increase the fatigue life. But,
at which fracture occurs is determined by the shot peened BMG alloys did not show any
rate at which it grows and also the fracture improvement [174].
toughness of the material. The fatigue crack It is known that the fatigue endurance limit
growth rate is determined from the Paris power increases with an increase in the yield strength
law relationship: of the alloy in the crystalline state. However,
such a correlation is not apparent in BMG
da
¼ C ðDK Þm alloys. A preliminary correlation between the
dN
fatigue ratio and Poisson’s ratio was, however,
where da/dN represents the crack growth rate (a
reported with the fatigue ratio increasing with
is the crack length and N is the number of
increasing value of the Poisson’s ratio [175].
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
9.7. Yield Behavior
desirable situation for long fatigue life is to
achieve as small a value of m as possible. The
Crystalline materials start yielding when the
values of m and DKth for BMG alloys are similar
applied stress is above the critical shear stress,
to those typically observed in crystalline alloys.
dependent on the orientation of the single crys-
The fracture surfaces of BMGs after fatigue
tal with reference to the loading axis. The two
crack growth rate experiments seem to be quite
criteria used for determining the yield behavior
different from those of crystalline materials.
are the von Mises and the Mohr–Coulomb
The surface roughness of BMG samples has
criteria. According to these criteria, yielding is
been found to increase with increasing crack-
supposed to be symmetric, i.e., the yield stress is
growth rate. The surfaces change from a mirror-
of the same magnitude whether testing is done in
like surface in the near-threshold fatigue crack
tension or compression and therefore the angle
growth region to a rough morphology exhibiting
at which shear failure occurs is 45 both in
ridge-like features in the fast-fracture process
tension and compression. However, several me-
[170].
tallic glasses have been shown to display asym-
metry, and therefore it has been suggested that
9.6.2. Improvement of Fatigue Resistance the yield criterion in metallic glasses could be
different.
It is now accepted that fatigue crack initiation is By measuring the yield strength of
the critical part in determining the fatigue lives Pd40Ni40P20 metallic glass ribbons undergoing
of metallic glasses. Once a fatigue crack forms, low-temperature, localized plastic flow in uni-
it can grow easily due to lack of microstructure. axial compression, plane-strain compression,
Therefore, introduction of a crystalline phase by pure shear, and tension, it was demonstrated
making it a composite might prevent growth of that yielding follows the Mohr–Coulomb crite-
small fatigue cracks and improve the fatigue rion, rather than the von Mises criterion [176].
Metallic Glasses 37
Yielding according to the Mohr–Coulomb cri- Fracture occurs by a shear mode under both
terion depends not only on the applied shear tensile and compressive loading conditions.
stress, t, but also on the stress normal to the However, an important difference between the
shear displacement, sn. Since BMGs have a surface structures of specimens fractured in
very high strength (1–4 GPa), the normal stress tension and compression is that the density of
applied on the shear plane is also very high (1– shear bands is much higher in the latter. Under
2 GPa), and should therefore play an important tensile loading, one major shear band dominates
role in the yielding process. Furthermore, it has the fracture process. The fracture surfaces of
long been known that disordered materials ex- BMG composites look different and are more
perience dilatation due to plastic deformation. complex mainly because of the presence of the
In terms of the flow strength-to-modulus ratio crystalline phase.
(so/E), this value is of the order of 103 and is
negligible in crystalline materials. In the case of
BMGs, however, it can be about 0.02, and 9.8. BMG Composites
therefore pressure effects are not negligible.
Sufficient data is not available, and the avail- A critical requirement for a structural engineer-
able results are conflicting to draw any conclu- ing material is that it should have an optimum
sions on the effect of strain rate on the fracture combination of strength, ductility, toughness,
strength of metallic glasses. It has been sug- and predictable and graceful (noncatastrophic)
gested that the room temperature fracture failure. Metallic glasses are inherently brittle in
strength of the Pd80Si20 filaments decreased tension. The introduction of tungsten and 1080
with increasing strain rate or was strongly de- steel wires into a Zr41.25Ti13.75Cu12.5Ni10Be22.5
pendent on strain rate. BMG matrix caused the compressive strain to
When the surface of a glassy alloy specimen, failure to increase by 900% compared to the
fractured under uniaxial loading, is observed in unreinforced BMG alloy [177]. It was suggested
a scanning electron microscope, one observes that the compressive toughness came from re-
typically a vein pattern, as shown in Figure 19. stricting the propagation of shear bands and thus
Such microstructures are observed whether the promoting the generation of multiple shear
specimen fails in tension or compression and bands which had eventually delayed fracture.
represent fracture characteristic of pure shear The tensile toughness increased as a result of
mode. Except for the ridges forming the veins, ductile fiber delamination, fracture, and fiber
the fracture surface is flat. 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].
increasing volume fraction of the reinforce- stress concentrations will therefore promote
ment. Associated with this increase in fracture shear band initiation. In the case of composites,
strength is the plastic strain to fracture, which however, three different possibilities have been
also has been shown to be higher with increasing identified as stress concentrators. These include
volume fraction of the reinforcement. For ex- (a) thermal residual stresses (of about 400 MPa)
ample, the fracture strength (sf) and plastic generated in both the matrix and the reinforce-
strain to fracture (ep) for the monolithic ment due to mismatch of the coefficient of
Cu60Hf25Ti15 BMG have been measured to be thermal expansion, (b) stress concentrations in
2088 MPa and 1.6%, respectively. But, with the the matrix due to differences in the elastic
presence of 8 vol% of the Nb-rich solid solution properties of the matrix and the reinforcement,
precipitate, these values increased to 2232 MPa and (c) stress concentration from the plastic
and 14.1%, respectively [180]. Similar trends misfit strain between the matrix and the rein-
have been reported in many other BMG com- forcement when the crystalline phase yields
posites. The best combination of high strength before the glassy matrix.
and improved ductility is obtained when the Since it has been noted that BMG composites
reinforcement is in the form of ductile den- with dendrites exhibit higher amounts of plas-
drites [181]. When the dendritic phase is chan- ticity, it has been suggested that the stress
ged into a spherical shape, the properties appear concentration in the glassy matrix changes due
to be further improved [182]. For example, the to the dimensions of the dendrite features, which
plastic strain achieved was 12% when the sec- are typically about 10 mm, which influence the
ond phase had a spherical morphology, increas- shear band formation. It is also possible that the
ing from 8.8% for the dendritic morphology. newly formed shear bands are likely to intersect
The effect of the shape of the reinforcement a dendrite arm before propagating very far, thus
(second phase) and its volume fraction has been making the dendrite arms more effective bar-
analyzed in terms of the yield strength and riers to shear front propagation. Using this
plastic strain to fracture in both compression concept of proximity of ‘‘obstacles’’ to shear
and tension [135]. At low volume fractions of band propagation, Zr-based BMG composites
the crystalline reinforcement phase (Vr < 0.3), were designed [78] with different volume frac-
the yield stress of the composite was very close tions of the crystalline phase and it was found
to that predicted by the rule of mixtures, sug- that the plastic strain to fracture increased with
gesting that at low volume fractions, the rein- increasing volume fraction of the dendritic
forcement does not alter the macroscopic con- phase.
stitutive response of the glassy matrix. At values
of Vr > 0.3, the composite response seems to
depend on the morphology of the reinforcement. 10. Magnetic Properties
The yield strength of composites with fibers and
large particles is the same as that calculated Magnetic properties are of fundamental impor-
using the rule of mixtures. The yield strength for tance for several applications in the electrical
in-situ processed composites reinforced with and electronic industries. Ferromagnetism was
dendrites is higher than that of the rule of first reported in 1967 in metallic glassy ribbons
mixtures, and for nanocrystalline composites it of Fe75P15C10 which exhibited large saturation
is lower. From this it appears that the dendritic magnetization and a narrow hysteresis loop with
morphology is the most effective in inhibiting a low coercivity [183]. The magnetic moment
macroscopic plastic deformation of the matrix. 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
9.8.2. Initiation and Propagation of Shear glassy phase. A very large number of magnetic
Bands metallic glasses based on Fe and Co have been
subsequently synthesized and characterized. In
Plastic flow is initiated in single-phase materials fact, the most important application to which the
in some locally perturbed region. Structural melt-spun glassy ribbons have been put to is in
inhomogeneities and defects that introduce transformer core laminations based on the
Metallic Glasses 39
excellent soft magnetic properties of these 106. It can be reduced to zero by a proper
alloys. Therefore, a significant amount of effort choice of alloy composition and heat treatment.
has been spent on investigating the magnetic There have also been several investigations
properties of metallic glassy alloys, including on the magnetic properties of BMG alloys. The
the BMGs. first Fe-based BMG alloy (in the form of melt-
The possibility of occurrence of ferromag- spun ribbons) was synthesized in 1995 in the
netism in amorphous alloys was predicted in Fe72Al5Ga2P11C6B4 system [185]. This discov-
1960 [184]. It was shown that nearest-neighbor ery was immediately followed with the
interactions can give rise to ferromagnetism. synthesis of another Fe-based BMG, a
Even though metallic glasses behave like super- Fe72Al5Ge2P11C6B4 alloy [186]. The magnetic
cooled liquids rather than crystalline solids as properties of BMGs have been investigated
far as their electrical properties are concerned, mostly in Fe-based BMGs, and a few investiga-
their magnetic properties resemble those of the tions have also been reported on Co-based
crystalline counterparts. This is because the BMGs. The hard magnetic properties of Nd-
governing electronic band structure is influ- and Pr-based alloys have also been studied.
enced by short-range rather than long-range The nature of magnetic investigations in
forces. Since metallic glasses contain short- BMG alloys has followed trends very similar
range order, the magnetic properties of metallic to what were done in the case of melt-spun
glasses are not substantially different from those glassy ribbons. An important difference be-
of their crystalline counterparts. However, dif- tween the investigations on melt-spun ribbons
ferences exist between the magnetic properties and BMGs is that while both metal–metalloid
of glassy and crystalline alloys of the same and metal–metal type alloys have been investi-
composition. The magnetic properties of alloys gated as thin films, only metal–metalloid alloys
depend on the residual strain, field heat treat- have been studied as BMGs. For BMG compo-
ment, the directionality induced during solidifi- sitions, several researchers have studied the
cation, and on the alloy composition. But, it may magnetic behavior using melt-spun ribbons.
be safely stated that, in comparison to crystal- Some minor differences were noted in the mag-
line alloys, magnetic metallic glasses have a netic properties of melt-spun ribbons and bulk
lower Curie temperature, higher permeability, rods, especially in those properties that are
lower coercivity, and higher electrical resistivi- affected by structural relaxation, e.g., magneto-
ty. However, the saturation magnetization of striction and coercivity. On the other hand, it has
metallic glasses is low. been shown that the saturation magnetization of
Even though crystalline anisotropy is zero in the alloys is not any different whether measured
the glassy state, a uniaxial anisotropy, Ku has on the melt-spun ribbon form or powder or
been found to exist in metallic glasses, thought between the melt-spun ribbon and bulk rods of
to be induced by short-range ordering, and can different diameters.
have a strong influence on the low-field proper-
ties of metallic glasses.
When a ferromagnetic material is magne- 10.1. Effect of Alloying Elements
tized, its dimensions change slightly, and the
sample being magnetized either expands or The saturation magnetization of metallic glasses
contracts in the direction of magnetization. This is relatively low and ranges from 0.4 to 1.8 T,
magnetically induced reversible strain is called while crystalline steels have values ranging
magnetostriction, ls, and is of the order of 106. from 1.8 to 2.1 T. This is due to the fact that
ls is positive at low fields and negative at high a large percentage of metalloid elements is
fields for crystalline iron and it is negative for necessary for the formation of metallic glasses.
cobalt and nickel. Since metallic glasses have This results in a decrease in the fraction of atoms
high yield strengths and can withstand high with magnetic moments due to the occupation
stresses without undergoing plastic deforma- of some of the d-states of the transition metals
tion, the anisotropy due to mechanical stresses by electrons from the metalloid atoms.
can be very large. For metallic glasses, ls can The mutual interactive forces of atomic di-
range from as high as 4 105 to as low as 5 poles tend to align themselves in a particular
40 Metallic Glasses
a remarkable degree of in-plane isotropy and Zr-based BMG manufactured by SRI Sports
strength. Ltd, a subsidiary of Dunlop Corporation in
The BMG alloys exhibit some interesting Japan. Liquidmetal Technologies supplies base-
mechanical properties. An important character- ball bats, tennis rackets, and other sporting
istic of BMGs is their large elastic strain limit, goods.
about 2% at room temperature, which is more The formation of complicated structures
than twice that in a crystalline material. This from BMGs in their supercooled liquid region
large value combined with the low Young’s offers many advantages, including their homo-
modulus can find useful applications in a variety geneity on a nanometer scale, very little solid-
of commercial and large-volume applications. ification shrinkage, excellent filling character-
Yet another special feature of BMGs is their istics, and highly reduced porosity. The super-
high yield (or fracture) strength and hardness. ior surface imprintability and net-shape
Because of this, BMGs could be used in appli- forming capability have also been found to be
cations where scratch and wear resistance be- very attractive in the field of micro-machines
come important. [197].
Due to their high strength and large elastic It has been possible to produce extremely
elongation limit, BMGs have found widespread small parts of complex design using BMGs.
application in sporting goods such as golf clubs, These include microgears, coil-shaped springs,
tennis rackets, baseball and softball bats, skis micro-geared motors with high torque, whose
and snowboards, bicycle parts, scuba gear, fish- wear resistance was shown to be more than 300
ing equipment, and marine applications [196]. times that of all-steel gears, automobile valve
Due to the high elastic strain limit and low springs, where the spring wires could be slim-
Young’s modulus, the modulus of resilience of mer and the springs themselves to be shorter,
BMGs is at least four times that of a crystalline diaphragms for pressure sensors, pipes for a
material. It is suggested that 99% of the impact Coriolis mass flowmeter, structural parts for
energy from a BMG golf club head is transferred aircraft, and shot peening balls to induce com-
to the ball. This value should be compared pressive stresses on the surface. Due to the
with 70% for a titanium head. Figure 22 shows possibility of achieving a very good surface
the outer shapes of the golf club heads made of a 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
Figure 22. Outer shapes of commercial golf club heads in
and controlled gaps. Lastly, since they do not
wood-, iron-, and putter-type forms where the face materials contain any binder, their shelf life is long and
are made of a Zr-based BMG alloy they are non-contaminating.
44 Metallic Glasses
suggests that linear actuators using Fe-based composites containing 6 vol% of hydroxyapa-
BMG yokes can show good acceleration and tite (HAp) after electrochemical and chemical
deceleration. In addition, the high relative per- treatments [210]. The monolithic Ti40Zr10-
meability (m) of the BMG permits the actuators Cu36Pd14 BMG alloy was found to be a good
to be driven with high-frequency current pulses, replacement for teeth and as plates and screws
leading to fine pitch control through a feedback for fixing bones.
system. Based on the high m and low Hc of Fe- BMGs have also been developed for recon-
based BMGs, it has been suggested that they are structive devices, fractured fixations, spinal im-
appropriate for low-loss magnetic cores for plants, ophthalmic surgery, and cataract sur-
choke coils [208]. Fe-based BMG alloy consol- gery. BMG surgical blades are sharper and
idated powder cores are also finding applica- longer-lasting than steel, less expensive than
tions as inductors in personal computers, etc., diamond, and more consistently manufactur-
because of higher efficiency and much lower able (since they are produced from a single
core losses in high frequency range. In 2011, mold) ready for use. Other edged tool applica-
The Alps Green Device Company in Japan was tions include knives and razor blades. These
producing several million pieces per month for glasses can be honed to superior levels of sharp-
commercial applications. ness because of the absence of microstructure.
Vitreloys (a trade name for Zr-based BMG
alloys manufactured by Liquidmetal Technolo-
11.5. Miscellaneous Applications gies) are also used for materials in knee-replace-
ment devices, pacemaker casings, etc. [21].
11.5.1. Jewelry
8 J.D. Bernal, Proc. R. Soc. London A 280 (1964) 299–322. 45 J. Shen, Q. Chen, J. Sun, H. Fan, G. Wang, Appl. Phys. Lett. 86
9 P.H. Gaskell: ‘‘Glasses and Amorphous Materials’’, Materials (2005) 151907-1–151907-3.
Science and Technology: A Comprehensive Treatment, Vol. 9, 46 R.F. Lynch, R.P. Olley, P.C.J. Gallagher, Trans. AFS 83 (1975)
VCH, Weinheim, Germany, 1991, pp. 175–278. 561–568.
10 H.J. Frost, Acta Metall. 30 (1982) 889–904. 47 A. Inoue, Y. Yokoyama, Y. Shinohara, T. Masumoto, Mater.
11 D. Turnbull, Scripta Metall. 11 (1977) 1131–1136. Trans., JIM 35 (1994) 923–926.
12 T. Egami, J. Non-Cryst. Solids 205–207 (1996) 575–582. 48 T. Tamura, K. Amiya, R.S. Rachmat, Y. Mizutani, K. Miwa,
13 T. Egami, Y. Waseda, J. Non-Cryst. Solids 64 (1984) Nat. Mater. 4 (2005) 289–292.
113–134. 49 R.B. Dandliker, R.D. Conner, W.L. Johnson, J. Mater. Res. 13
14 Z.J. Yan, J.F. Li, S.R. He, Y.H. Zhou, Mater. Res. Bull. 38 (1998) 2896–2901.
(2003) 681–689. 50 J. Banhart, Prog. Mater. Sci. 46 (2001) 559–632.
15 S. Ueno, Y. Waseda, J. Mater. Eng. 9 (1987) 199–204. 51 L.J. Gibson, M.F. Ashby: Cellular Solids: Structure and Prop-
16 D.B. Miracle, O.N. Senkov, Mater. Sci. Eng. A 347 (2003) erties, 2nd ed., Cambridge University Press, Cambridge, UK,
50–58. 1997.
17 D.B. Miracle, Nat. Mater. 3 (2004) 697–702. 52 J. Schroers, C. Veazey, W.L. Johnson, Appl. Phys. Lett. 82
18 H.W. Sheng, W.K. Luo, F.M. Alamgir, J.M. Bai, E. Ma, Nature (2003) 370–372.
439 (2006) 419–425. 53 A.H. Brothers, D.C. Dunand, Adv. Mater. 17 (2005) 484–486.
19 A.P. Wang, J.Q. Wang, E. Ma, Appl. Phys. Lett. 90 (2007) 54 (a) T. Wada, A. Inoue, Mater. Trans. 44 (2003) 2228–2231; (b)
121912-1–121912-3. T. Wada, A. Inoue, Mater. Trans. 45 (2004) 2761–2765.
20 A. Inoue, Proc. Jpn Acad. B 73 (1997) 19–24. 55 C. Suryanarayana (ed.): Non-equilibrium Processing of Mate-
21 C. Suryanarayana, A. Inoue, Bulk Metallic Glasses, CRC rials, Elsevier, Oxford, UK, 1999.
Press, Boca Raton, FL, 2011. 56 C. Suryanarayana, Prog. Mater. Sci. 46 (2001) 1–184.
22 Z.P. Lu, C.T. Liu, Acta Mater. 50 (2002) 3501–3512. 57 C. Suryanarayana: Mechanical Alloying and Milling, Marcel-
23 C. Suryanarayana, I. Seki, A. Inoue, J. Non-Cryst. Solids 355 Dekker, New York, NY, 2004.
(2009) 355–360. 58 E.J. Lavernia, Y. Wu: Spray Atomization and Deposition, John
24 S. Sharma, R. Vaidyanathan, C. Suryanarayana, Appl. Phys. Wiley & Sons, Chichester, UK, 1996.
Lett. 90 (2007) 111915-1–111915-3. 59 S.M. Sharma, S.K. Sikka, Prog. Mater. Sci. 40 (1996) 1–77.
25 C. Suryanarayana: ‘‘Processing of Metals’’, Materials Science 60 A.E. Ermakov, E.E. Yurchikov, V.A. Barinov, Phys. Met.
and Technology - A Comprehensive Treatment, Vol. 15, VCH, Metallogr. 52 (1981) no. 6, 50–58.
Weinheim, Germany, 1991, pp. 57–110. 61 C.C. Koch, O.B. Cavin, C.G. McKamey, J.O. Scarbrough, Appl.
26 H.H. Liebermann: Amorphous Metallic Alloys, Butterworths, Phys. Lett. 43 (1983) 1017–1019.
London 1983, pp. 26–41. 62 B. Prabhu, C. Suryanarayana, L. An, R. Vaidyanathan, Mater.
27 T.R. Anantharaman, C. Suryanarayana: Rapidly Solidified Sci. Eng. A425 (2006) 192–200.
Metals: A Technological Overview, Trans Tech Publications, 63 X.L. Yeh, K. Samwer, W.L. Johnson, Appl. Phys. Lett. 42
Zürich, Switzerland, 1987, pp. 25–97. (1983) 242–243.
28 M.C. Narasimhan, US Patent 4142571 (1979) . 64 R.B. Schwarz, W.L. Johnson, Phys. Rev. Lett. 51 (1983) 415–
29 A. Inoue, K. Kita, T. Zhang, T. Masumoto. Mater. Trans., JIM 418.
30 (1989) 722–725. 65 H.-J. Fecht, W.L. Johnson, J. Non-Cryst. Solids 117/118 (1990)
30 P. Duwez, R.H. Willens, Trans. Metall. Soc. AIME 227 (1963) 704–707.
362–365. 66 R.Z. Valiev, R.K. Islamgaliev, I.V. Alexandrov. Prog. Mater.
31 P. Pietrokowsky, Rev. Sci. Instrum. 34 (1963) 445–446. Sci. 45 (2000) 103–189.
32 D.R. Harbur, J.W. Anderson, W.J. Maraman, Trans. Metall. 67 N. Tsuji: Nanostructured Metals and Alloys, Woodhead
Soc. AIME 245 (1969) 1055–1061. Publishing, Cambridge, UK, 2011, pp. 40–58.
33 P. Ramachandrarao, M. Laridjani, R.W. Cahn, Z. Metallk. 63 68 J. Kramer, Z. Phys. 106 (1936) 675–691.
(1972) 43–49. 69 W. Buckel, R. Hilsch, Z. Phys. 132 (1952) 420–442.
34 H.S. Chen, Acta Metall. 22 (1974) 1505–1511. 70 S.D. Dahlgren in B. Cantor (ed.): Proc. 3rd Int. Conf. on
35 A.J. Drehman, A.L. Greer, D. Turnbull, Appl. Phys. Lett. 41 Rapidly Quenched Metals (RQ III), Vol. 2, Metals Society,
(1982) 716–717. London, UK, 1978, pp. 36–47.
36 H.W. Kui, A.L. Greer, D. Turnbull, Appl. Phys. Lett. 45 (1984) 71 B.X. Liu, W.S. Lai, Z.J. Zhang, Adv. Phys. 50 (2001) 367–429.
615–616. 72 I.-R. Lu, G. Wilde, G.P. Görler, R. Willnecker, J. Non-Cryst.
37 A. Inoue, N. Nishiyama, T. Matsuda, Mater. Trans., JIM 37 Solids 250-252 (1999) 577–581.
(1996) 181–184. 73 F.E. Luborsky in R.A. Levy, R. Hasegawa (eds.): Amorphous
38 A. Inoue, N. Nishiyama, H.M. Kimura, Mater. Trans., JIM 38 Magnetism II, Plenum Press, New York 1977, pp. 345–368.
(1997) 179–183. 74 M.G. Scott: Amorphous Metallic Alloys, Butterworths, London
39 N. Nishiyama, A. Inoue, Mater. Trans., JIM 37 (1996) 1531– 1983, pp. 144–168.
1539. 75 K. Lu, Mater. Sci. Eng. Rep. R16 (1996) 161–221.
40 E.S. Park, D.H. Kim, J. Mater. Res. 19 (2004) 685–688. 76 A. Inoue, Prog. Mater. Sci. 43 (1998) 365–520.
41 A. Inoue, T. Nakamura, N. Nishiyama, T. Masumoto, Mater. 77 A. Inoue, W. Zhang, T. Tsurui, A.R. Yavari, A.L. Greer, Phil.
Trans., JIM 33 (1992) 937–945. Mag. Lett. 85 (2005) 221–229.
42 Y. Yokoyama, E. Mund, A. Inoue, L. Schultz, Mater. Trans. 48 78 D.C. Hoffmaan, J-Y. Suh, A. Wiest, G. Duan, M-L. Lind, M.D.
(2007) 3190–3192. Demetriou, W.L. Johnson, Nature 451 (2008) 1085–1090.
43 A. Inoue, T. Zhang, Mater. Trans., JIM 36 (1995) 1184–1187. 79 U. Köster, P. Weiss, J. Non-Cryst. Solids 17 (1975) 359–368.
44 J.J. Wall, C. Fan, P.K. Liaw, C.T. Liu, H. Choo, Rev. Sci. 80 H.S. Chen: Amorphous Metallic Alloys, Butterworths, London,
Instrum. 77 (2006) 033902-1–033902-4. UK, 1983, pp. 169–186.
Metallic Glasses 47
81 H.S. Chen, J. Appl. Phys. 49 (1978) 3289–3291. 114 M. Naka, K. Hashimoto, T. Masumoto, J. Jpn Inst. Metals 38
82 O. Haruyama, H.M. Kimura, N. Nishiyama, A. Inoue, J.I. Arai, (1974) 835–841 (in Japanese).
Mater. Trans. 43 (2002) 1931–1936. 115 M. Naka, K. Hashimoto, T. Masumoto, Corrosion 32 (1976)
83 A. Inoue, T. Negishi, H.M. Kimura, T. Zhang, A.R. Yavari, 146–152.
Mater. Trans., JIM 39 (1998) 318–321. 116 K. Asami, K. Hashimoto, T. Masumoto, S. Shimodaira, Corro-
84 H.S. Chen, D. Turnbull, Acta Metall. 17 (1969) 1021–1031. sion Sci. 16 (1976) 909–914.
85 C.P.P. Chou, D. Turnbull, J. Non-Cryst. Solids 17 (1975) 169– 117 T. Masumoto, K. Hashimoto, Ann. Rev. Mater. Sci. 8 (1978)
188. 215–233.
86 W.K. Wang, H. Iwasaki, C. Suryanarayana, T. Masumoto, J. 118 K. Hashimoto: Amorphous Metallic Alloys, Butterworths,
Mater. Sci. 18 (1983) 3765–3772. London, UK, 1983, pp. 471–486.
87 F. Ye, K. Lu, Acta Mater. 47 (1999) 2449–2454. 119 K. Hashimoto: Rapidly Solidified Alloys: Processes, Structures,
88 J.Z. Jiang, J.S. Olsen, L. Gerward, S. Abdali, J. Eckert, N. Properties, Applications, Marcel Dekker, New York 1993, pp.
Schlorke-de Boer, L. Schultz, P.X. Shi, J. Appl. Phys. 87 (2000) 591–615.
2664–2666. 120 K. Hashimoto, Corrosion 58 (2002) 715–722.
89 C. Suryanarayana, W.K. Wang, H. Iwasaki, T. Masumoto, Solid 121 M. Naka, K. Hashimoto, T. Masumoto, J. Non-Cryst. Solids 30
State Commun. 34 (1980) 861–863. (1978) 29–36.
90 W.H. Wang, R.J. Wang, D.Y. Dai, D.Q. Zhao, M.X. Pan, Y.S. 122 K. Asami, H. Habazaki, A. Inoue, K. Hashimoto. Mater. Sci.
Yao, Appl. Phys. Lett. 79 (2001) 1106–1108. Forum 502 (2005) 225–230.
91 H.S. Chen, Rep. Prog. Phys. 43 (1980) 353–432. 123 C.L. Qin, W. Zhang, H. Kimura, K. Asami, N. Ohtsu, A. Inoue,
92 X. Hu, S.C. Ng, Y.P. Feng, Y. Li, Phys. Rev. B64 (2001) Acta Mater. 53 (2005) 3903–3911.
172201-1–172201-4. 124 K. Asami, C.L. Qin, T. Zhang, A. Inoue, Mater. Sci. Eng. A 375-
93 N. Mattern, U. Kühn, H. Hermann, S. Roth, H. Vinzelberg, J. 377 (2004) 235–239.
Eckert, Mater. Sci. Eng. A 375–377 (2004) 351–354. 125 A. Pardo, M.C. Merino, E. Otero, M.D. López, A. M’hich, J.
94 T. Egami, Ann. N.Y. Acad. Sci. 371 (1981) 238–251. Non-Cryst. Solids 352 (2006) 3179–3190.
95 T. Lin, X.F. Bian, J. Jiang, Phys. Lett. A353 (2006) 497–499. 126 A. Pardo, E. Otero, M.C. Merino, M.D. López, M. Vázquez, P.
96 B. Cantor, R.W. Cahn: Amorphous Metallic Alloys, Butter- Agudo, Corrosion Sci. 43 (2001) 689–705.
worths, London, UK, 1983, pp. 487–505. 127 H. Habazaki, T. Sato, A. Kawashima, K. Asami, K. Hashimoto,
97 J. Horvath: ‘‘Diffusion in Solid Metals and Alloys’’, Landolt- Mater. Sci. Eng. A 304–306 (2001) 696–700.
Börnstein, New Series, Vol. 26, Group 3, Heidelberg 1990, pp. 128 T. Masumoto, R. Maddin, Acta Metall. 19 (1971) 725–741.
437–470. 129 C.A. Pampillo, J. Mater. Sci. 10 (1975) 1194–1227.
98 F. Faupel, W. Frank, M.-P. Macht, H. Mehrer, V. Naundorf, K. 130 L.A. Davis, in J.J. Gilman, H.J. Leamy (eds.): Metallic Glasses,
Rätzke, H.R. Schober, S.K. Sharma, H. Teicher, Rev. Mod. ASM International, Materials Park, OH, 1978, pp.
Phys. 75 (2003) 237–280. 190–223.
99 K. Nonaka, Y. Kimura, K. Yamauchi, H. Nakajima, T. Zhang, 131 J.C.M. Li: Treatise on Materials Science and Technology, Vol.
A. Inoue, T. Masumoto, Defect & Diffusion Forum 143-147 20, Academic Press, New York, 1982, pp. 325–89.
(1997) 837–842. 132 H. Kimura, T. Masumoto: Amorphous Metallic Alloys, Butter-
100 C. Suryanarayana: Metallic Glasses: Production, Properties, worths, London, 1983, pp. 187–230.
and Applications, Trans Tech, Aedermannsdorf, Switzerland, 133 P. Rama Rao, V.M. Radhakrishnan: Metallic Glasses: Produc-
1984, pp. 249–267. tion, Properties, and Applications, Trans Tech, Aedermanns-
101 H.M. Kimura, A. Inoue, N. Nishiyama, K. Sasamori, O. Har- dorf, Switzerland, 1984, pp. 225–248.
uyama, T. Masumoto, Sci. Rep. RITU A43 (1997) 101–106. 134 A. Peker, W.L. Johnson, Appl. Phys. Lett. 63 (1993) 2342–
102 B.Y. Boucher, J. Non-Cryst. Solids 7 (1972) 277–284. 2344.
103 W.L. Johnson, S.J. Poon, P. Duwez, Phys. Rev. B11 (1975) 135 (a) C.A. Schuh, T.C. Hufnagel, U. Ramamurty. Acta Mater. 55
150–154. (2007) 4067–4109.
104 A. Inoue, H.M. Kimura, T. Masumoto, C. Suryanarayana, A. 136 (b) M.M. Trexler, N.N. Thadhani, Prog. Mater. Sci. 55 (2010)
Hoshi, J. Appl. Phys. 51 (1980) 5475–5482. 759–839.
105 C. Suryanarayana, A. Inoue, T. Masumoto, Scripta Metall. 14 137 K. Wang, T. Fujita, Y.Q. Zeng, N. Nishiyama, A. Inoue, M.W.
(1980) 881–885. Chen, Acta Mater. 56 (2008) 2834–2842.
106 A. Inoue, A. Hoshi, C. Suryanarayana, T. Masumoto, Scripta 138 G. Wang, S.S. Fang, X.S. Xiao, Q. Hua, H.Z. Gu, Y.D. Dong,
Metall. 14 (1980) 1077–1082. Mater. Sci. Eng. A373 (2004) 217–220.
107 A. Inoue, C. Suryanarayana, T. Masumoto, A. Hoshi, Mater. 139 A.S. Argon, Acta Metall. 27 (1979) 47–58.
Sci. Eng. 47 (1981) 59–67. 140 F. Spaepen, Acta Metall. 25 (1977) 407–415.
108 C. Suryanarayana, W.K. Wang, H. Iwasaki, T. Masumoto, Solid 141 T. Kawamura, T. Shibata, A. Inoue, T. Masumoto, Acta Mater.
State Commun. 34 (1980) 861–863. 46 (1998) 253–263.
109 S.V. Nemilov, Glass Phys. Chem. 21 (1995) 91–96. 142 T.G. Nieh, J. Wadsworth, C.T. Liu, T. Ohkubo, Y. Hirotsu, Acta
110 C.A. Angell, Science 267 (1995) 1924–1935. Mater. 49 (2001) 2887–2896.
111 A. Inoue: Bulk Amorphous Alloys: Preparation and Funda- 143 K.M. Flores, R.H. Dauskardt, J. Mater. Res. 14 (1999) 638–
mental Characteristics. Trans Tech Publications, Zürich, Swit- 643.
zerland, 1998. 144 W.J. Wright, R.B. Schwarz, W.D. Nix, Mater. Sci. Eng. A 319-
112 A.I. Taub: Rapidly Quenched Metals V, Elsevier, Amsterdam, 321 (2001) 229–232.
The Netherlands, 1985, pp. 1365–1368. 145 B. Yang, P.K. Liaw, G. Wang, M.L. Morrison, C.T. Liu, R.A.
113 S. Maeda, T. Yamasaki, Y. Yokoyama, D. Okai, T. Fukami, Buchanan, Y. Yokoyama, Intermetallics 12 (2004) 1265–1274.
H.M. Kimura, A. Inoue, Mater. Sci. Eng. A 449-451 (2007) 146 P.E. Donovan, W.M. Stobbs, Acta Metall. 29 (1981) 1419–
203–206. 1426.
48 Metallic Glasses
147 Y. Zhang, A.L. Greer, Appl. Phys. Lett. 89 (2006) 071907-1– 179 J. Eckert, J. Das, S. Pauly, C. Duhamel, J. Mater. Res. 22 (2007)
071907-3. 285–301.
148 C.A. Schuh, A.C. Lund, Nat. Mater. 2 (2003) 449–452. 180 C.L. Qin, W. Zhang, K. Asami, H.M. Kimura, X.M. Wang, A.
149 B. Yang, M.L. Morrison, P.K. Liaw, R.A. Buchanan, G.Y. Inoue, Acta Mater. 54 (2006) 3713–3719.
Wang, C.T. Liu, M. Denda, Appl. Phys. Lett. 86 (2005) 141904- 181 Z. Bian, H. Kato, C.L. Qin, W. Zhang, A. Inoue, Acta Mater. 53
1–141904-3. (2005) 2037–2048.
150 H.A. Bruck, A.J. Rosakis, W.L. Johnson, J. Mater. Res. 11 182 G.Y. Sun, G. Chen, G.L. Chen, Intermetallics 15 (2007) 632–
(1996) 503–511. 634.
151 B. Yang, C.T. Liu, T.G. Nieh, M.L. Morrison, P.K. Liaw, R.A. 183 P. Duwez, S.C.H. Lin, J. Appl. Phys. 38 (1967) 4096–4097.
Buchanan, J. Mater. Res. 21 (2006) 915–922. 184 A.I. Gubanov, Soviet Phys.–Solid State 2 (1960) 468.
152 J.J. Lewandowski, A.L. Greer, Nat. Mater. 5 (2006) 15–18. 185 A. Inoue, J.S. Gook, Mater. Trans. JIM 36 (1995) 1180–1183.
153 M.W. Chen, A. Inoue, W. Zhang, T. Sakurai, Phys. Rev. Lett. 96 186 A. Inoue, J.S. Gook, Mater. Trans. JIM 36 (1995) 1282–1285.
(2006) 245502-1–245502-4. 187 C.T. Chang, B.L. Shen, A. Inoue, Appl. Phys. Lett. 89 (2006)
154 B. Yang, C.T. Liu, T.G. Nieh, Appl. Phys. Lett. 88 (2006) 051912-1–051912-3.
221911-1–221911-3. 188 Y. Yoshizawa, S. Oguma, K. Yamauchi, J. Appl. Phys. 64
155 Y.H. Liu, C.T. Liu, W.H. Wang, A. Inoue, T. Sakurai, M.W. (1988) 6044–6046.
Chen, Phys. Rev. Lett. 103 (2009) 065504-1–065504-4. 189 M. Miglierin, R. Vittek, M. Hasiak, Mater. Sci. Eng. A 449-451
156 A. Inoue, Acta Mater. 48 (2000) 279–306. (2007) 419–422.
157 J. Das, M.B. Tang, K.B. Kim, R. Theissmann, F. Baier, W.H. 190 A. Makino, T. Bitoh, A. Inoue, T. Masumoto, Scripta Mater. 48
Wang, J. Eckert, Phys. Rev. Lett. 94 (2005) 205501-1–205501-4. (2003) 869–874.
158 J. Schroers, W.L. Johnson, Phys. Rev. Lett. 93 (2004) 255506- 191 A. Makino, H. Men, T. Kubota, K. Yubuta, A. Inoue, Mater.
1–255506-4. Trans. 50 (2009) 204–209.
159 A.H. Cottrell, MRS Bulletin 22 (1997) no. 5, 15–19. 192 A. Makino, H. Men, T. Kubota, K. Yubuta, A. Inoue, J. Appl.
160 J.J. Lewandowski, W.H. Wang, A.L. Greer, Phil. Mag. Lett. 85 Phys. 105 (2009) 07A308-1–07A308-3.
(2005) 77–87. 193 A.S. Argon, G.W. Hawkins, H.Y. Kuo, J. Mater. Sci. 14 (1979)
161 H.S. Chen, J.T. Krause, E. Coleman, J. Non-Cryst. Solids 18 1707–1716.
(1975) 157–171. 194 C. Suryanarayana, F.H. Froes: Rapidly Solidified Alloys,
162 Y. Yokoyama, K. Fujita, A.R. Yavari, A. Inoue, Phil. Mag. Lett. Marcel Dekker, New York 1993, pp. 737–754.
89 (2009) 322–334. 195 Y.T. Yeow, J. Comp. Mater. 14 (1980) 132–143.
163 T. Zhang, A.P. Tsai, A. Inoue, T. Masumoto, Boundary 7(9) 196 Liquidmetal Technologies, http://www.liquidmetal.com
(1991) 39–43. (accessed June 20, 2011) .
164 S. Suresh: Fatigue of Materials, 2nd ed., Cambridge University 197 P. Sharma, W. Zhang, K. Amiya, H.M. Kimura, A. Inoue, J.
Press, Cambridge, UK, 1998. Nanosci. Nanotechnol. 5 (2005) 416–420.
165 Y. Yokoyama, K. Fukaura, A. Inoue, Mater. Trans. 45 (2004) 198 A. Rabinkin, H.H. Liebermann: Rapidly Solidified Alloys,
1672–1678. Marcel Dekker, New York 1993, pp. 691–735.
166 G.Y. Wang, P.K. Liaw, Y. Yokoyama, W.H. Peter, B. Yang, M. 199 J.J. Gilman, J.A. Champion, R.W. Cahn, Phil. Trans. R. Soc.
Freels, R.A. Buchanan, C.T. Liu, C.R. Brooks, J. Alloys Com- London A322 (1987) 425–438.
pounds 434-435 (2007) 68–70. 200 A. Yokoyama, H. Komiyama, H. Inoue, T. Masumoto, H.M.
167 V. Keryvin, Y. Nadot, Y. Yokoyama, Scripta Mater. 57 (2007) Kimura, J. Catal. 68 (1981) 355–361.
145–148. 201 A. Kawashima, K. Hashimoto: Rapidly Quenched Metals IV,
168 V. Schroeder, C.J. Gilbert, R.O. Ritchie, Scripta Mater. 40 Japan Institute of Metals, Sendai, 1982, pp. 1427–1430.
(1999) 1057–1061. 202 A. Inoue, T. Shimizu, S. Yamaura, Y. Fujita, S. Takagi, H.M.
169 A. Schroeder, R.O. Ritchie, Acta Mater. 54 (2006) 1785–1794. Kimura, Mater. Trans. 46 (2005) 1706–1710.
170 C.J. Gilbert, V. Schroeder, R.O. Ritchie, Metall. Mater. Trans. 203 M. Sistiaga, A.R. Pierna, J. Non-Cryst. Solids 329 (2003) 184–
A30 (1999) 1739–1753. 187.
171 K.M. Flores, W.L. Johnson, R.H. Dauskardt, Scripta Mater. 49 204 C.H. Smith: Rapidly Solidified Alloys: Processes, Structures,
(2003) 1181–1187. Properties, Applications, Marcel Dekker, New York 1993, pp.
172 G.Y. Wang, P.K. Liaw, A. Peker, M. Freels, W.H. Peter, R.A. 617–663.
Buchanan, C.R. Brooks, Intermetallics 14 (2006) 1091–1097. 205 R. Hasegawa, J. Non-Cryst. Solids 287 (2001) 405–412.
173 M.E. Launey, D.C. Hoffmann, W.L. Johnson, R.O. Ritchie, 206 R. Hasegawa, Mater. Sci. Eng. A 375-377 (2004) 90–97.
Proc. Natl. Acad. Sci. 106 (2009) 4986–4991. 207 N. Nishiyama, K. Amiya, A. Inoue: ‘‘Amorphous and Nano-
174 R. Raghavan, R. Ayer, H.W. Jin, C.N. Marzinsky, U. Rama- crystalline Metals’’, in R. Busch, T.C. Hufnagel, J. Eckert, A.
murty, Scripta Mater. 59 (2008) 167–170. Inoue, W.L. Johnson, A.R. Yavari. (eds.): Proc. Materials
175 G.Y. Wang, P.K. Liaw, Y. Yokoyama, A. Peker, W.H. Peter, B. Research Society, Vol. 806, Warrendale, PA, 2004, pp. 387–
Yang, M. Freels, Z.Y. Zhang, V. Keppens, R. Hermann, R.A. 392.
Buchanan, C.T. Liu, C.R. Brooks, Intermetallics 15 (2007) 208 S. Yoshida, T. Mizushima, T. Hatanai, A. Inoue, IEEE Trans.
663–667. Magnetics 36 (2000) 3424–3429.
176 P.E. Donovan, Acta Metall. 37 (1989) 445–456. 209 J. Schroers, B. Lohwongwatana, W.L. Johnson, A. Peker,
177 R.D. Conner, R.B. Dandliker, W.L. Johnson, Acta Mater. 46 Mater. Sci. Eng. A 449–451 (2007) 235–238.
(1998) 6089–6102. 210 S.L. Zhu, X.M. Wang, G.Q. Xie, F.X. Qin, M. Yoshimura, A.
178 C.C. Hays, C.P. Kim, W.L. Johnson, Phys. Rev. Lett. 84 (2000) Inoue, Scripta Mater. 58 (2008) 287–290.
2901–2904.