metals

Review
Review of the Recent Development in Metallic Glass and
Its Composites
Adit Sharma * and Vladislav Zadorozhnyy

Centre of Composite Materials, National University of Science and Technology «MISiS», Leninsky Prosp. 4,
119049 Moscow, Russia; vuz@misis.ru
* Correspondence: m157218@edu.misis.ru

Abstract: Metallic glasses are known for their mechanical properties but lack plasticity. This could be
prevented by combining them with other materials or by inducing a second phase to form a composite.
These composites have enhanced thermo-physical properties. The review paper aims to outline
a summary of the current research done on metallic glass and its composites. A background in
the history, properties, and their applications is discussed. Recent developments in biocompatible
metallic glass composites, fiber-reinforced metallic glass, ex situ and in situ, are discussed.

Keywords: metallic glass; composite; biocompatible metallic glass composite; in situ; ex situ composite

1. Introduction
Metallic glass is known for its advanced engineering properties. They are amor-
phous. In 1960, Klement et al. from the California Institute of Technology developed the



first metallic glass by using gold silicon alloy [1]. It was detected that 25 percent of the


gold was amorphous when quenched. In 1966, studies were conducted on the effect of
Citation: Sharma, A.; Zadorozhnyy, different cooling rates during rapid quenching of metals from spat cooling. This resulted
V. Review of the Recent Development in the formation of metastable phases, such as in amorphous alloys [2]. Binary Pd–Si glass,
in Metallic Glass and Its Composites.
ternary Pd–Au–Si, and Pd–Cu–Si were prepared at room temperature by quenching at
Metals 2021, 11, 1933. https://
different cooling rates [3]. In 1975, Fe40 Ni40 B20 metallic glass was produced by a melt
doi.org/10.3390/met11121933
spinning technique. Inoue et al. showed the large glass-forming ability of the La–Al–Ni
amorphous alloys [4]. Phase separation of Au55 Pb22.5 Sb22.5 metallic glass was studied
Academic Editor: Tadeusz Kulik
and showed the influence of the surface energy on the metallic glass. It was concluded
that surface energy had a contribution to the decomposition process [5]. Drehman et al.
Received: 22 September 2021
Accepted: 26 November 2021
showed the preparation of Pd40 Ni40 P20 by the undercooling process. During formation,
Published: 29 November 2021
crystallization occurred uniformly, and the activation energy was calculated [6]. The Pd–Ge
and Cu–Zr alloys had higher thermal properties, compared to metallic glass prepared by
Publisher’s Note: MDPI stays neutral
the melt-spinning technique [7]. Zr41.2 Ti13.8 Cu12.5 Ni10.0 metallic glass was alloyed by the in-
with regard to jurisdictional claims in
duction melting process at a cooling rate of less than 10 K/s. It had excellent glass-forming
published maps and institutional affil- ability and the effect of crystallization was studied [8]. Metallic glass is mainly made up
iations. of two types: metal–metalloid and metal–metal combinations. In metal–metalloid [9],
the metalloid constituent comprises 10–20% of the composition. The metal constituent is
more than 80%. Some of the examples of metal–metalloid metallic glass are Pd77 Cu6 Si17 ,
Fe40 Ni40 B20, and Ni49 Fe29 B6 P14 Si2 . In metal–metal, the metal can have any compositional
Copyright: © 2021 by the authors.
ratio. Ni60 Nb40 , La80 Au20, and Fe90 Zr10 are some examples. Some of the commonly used
Licensee MDPI, Basel, Switzerland.
metallic glass are Zr-based [10–13], Fe-based [14–16], Co-based [17,18], Ni-based [19,20],
This article is an open access article
Cu-based [21,22], and Pd-based [23,24] types. Metallic glass is used in biomedical appli-
distributed under the terms and cations [25,26]. Zr-based metallic glass can be used in stents [27]. Fe–B–Nd–Nb metallic
conditions of the Creative Commons glass is used in micro cantilevers [28]. Metallic glass can be used as a micro scanner [29].
Attribution (CC BY) license (https:// They are used in electrical applications [30] and catalysis [31]. Metallic glass is generally
creativecommons.org/licenses/by/ prepared by the rapid cooling of the molten liquid [32], melt-spinning [7,33], powder
4.0/). metallurgy [34], liquid squat quenching [35], magnetron sputtering [36], and pulsed laser

Metals 2021, 11, 1933. https://doi.org/10.3390/met11121933 https://www.mdpi.com/journal/metals

Metals 2021, 11, 1933 2 of 29

quenching [37]. Metallic glass is formed from the continuous cooling of the liquid state.
It is generally non-crystalline in nature. The major criterion for the formation of metallic
glass is its glass-forming ability (GFA). The glass formation ability is dependent on the
critical cooling rate (Rc ). The critical cooling rate (Rc ) is the minimum cooling rate required
to keep the molten amorphous, without any formation of the crystal precipitates during
solidification. The lower the Rc , the higher the glass-forming ability (Table 1). The main
criteria that are used to measure the glass-forming ability are reduced glass transition
temperature (Trg ) and supercooled region (Tsr ). The reduced glass transition temperature
(Trg ) is defined as the proportion of the glass transition temperature (Tg ) to the melting
temperature (Tm ) of the metallic glass. The supercooled region is the region in between
the crystallization temperature (Tx ) and the glass transition temperature (Tg ). Metallic
glass is formed near their eutectic points as compared to the non-eutectic points. The offset
liquidus temperature (Tl ) showed that Tg /Tl have a better correlation criterion to have
a glass-forming ability than Tg /Tm [38]. The GFA is directly proportional to the thickness
of the sample and inversely so to the critical cooling rate (Rc ). Mukherjee et al. showed
that the volume change in the crystallization is correlated with the viscosity at the melting
temperature [39]. The fragility index (m) is related to the glass forming and plasticity of
the metallic glass [40]. The glass forming ability was increased with the addition of Co in
Ce70x Al10 Cu20 Cox . It was due to the increase in the Al-site symmetry and is a characteristic
of the local structure.

Table 1. Different critical cooling rates (Rc ) of metallic glass.

Metallic Glass Rc (K s−1 ) References

Au55 Cu25 Si20 3.4 × 104 [41]
Fe48 Cr15 Mo14 Y2 C15 B6 140–190 [42]
Co75 Si15 B10 3.8 × 108 [43]
Fe79 Si10 B11 3.7 × 108 [43]
Ni75 Si8 B17 2.4 × 108 [43]
Pd77.5 Cu6 Si16.5 1.5 × 108 [43]
Pd40 Ni40 P20 1.4 × 107 [43]
Zr41.2 Ti13.8 Cu12.5 Ni10.0 Be22.5 ≤10 [44]
Al51 Ge35 Ni14 104 [45]
Fe76 Si9 B10 P5 ≤550 [46]
Pd40 Cu30 Ni10 P20 2.08 × 10−5 [47]
Au49 Ag5.5 Pd2.3 Cu26.9 Si16.3 600 [48]
Zr52.5 Ti5 Al10 Ni14.6 Cu17.9 103 –105 [49]
Fe67 Mo4.5 Cr2.3 Al2 Si3 C7 P8.7 B5.5 9.3 × 104 [50]
Al86 Ni6 Y4.5 Co2 La1.5 3.01 × 103 [51]

Metallic glass is known for its mechanical properties [52,53] and has corrosion re-
sistance [54]. The amorphous metals (Figure 1) have a better elastic limit and Young’s
modulus, compared to (the mechanical properties of) the traditional alloys. The defects and
grain boundaries in the crystalline solution make crystalline alloys susceptible to stress cor-
rosion cracking and intergranular corrosion. Peter et al. showed the corrosion resistance of
the metallic glass in an aqueous solution as compared to the crystalline materials [55]. They
have higher wear resistance [56] and elastic behavior [57] compared to crystalline alloys.
Metallic glass exhibits physical–thermal properties in the supercooled region. They
soften in the supercooled region and can be easily transformed into the desired form [58].
Mechanical properties of Zr–10Al–5Ti–17.9Cu–14.6Ni in the supercooled region had ex-
cellent mechanical properties. This was due to the formation of nano-crystallites in the
supercooled region [59]. The Ti46 Zr20 V12 Cu5 Be17 metallic glass matrix composite showed
an increase in the tensile ductility and necking in the supercooled region [60].
Metals 2021, 11, 1933 3 of 29
Metals 2021, 11, 1933 3 of 31

Figure 1.
Figure 1. The
The elastic
elastic limit (MPa) plotted against Young’s modulus (GPa) for different materials. In
total, 1507
total, 1507 metals,
metals,metal–matrix
metal–matrixcomposites,
composites,alloys,
alloys,and
andmetallic
metallicglasses
glasses(at%)
(at%)are
arecompared.
compared.(σ(σ y/E)
y /E)
contour represents
contour representselastic
elasticstrain
strainlimit
limitand
and(σ
(σy22/E)
/E) as
as resilience.
resilience. Reproduced
Reproduced from
from the
the permission
permission of
of
y
ref. [53]. Copyright 2009 Elsevier Ltd.
ref. [53]. Copyright 2009 Elsevier Ltd.

Metallicglass
Metallic glasshasexhibits physical–thermal
no crystal defect, and hasproperties
high strength,in the supercooled
hardness, region.
and yield They
strength.
soften
It in the supercooled
has certain shortcomings, region
suchandas acan be easily
brittle naturetransformed into the[61].
and low plasticity desired
Thisformis due [58].
to
Mechanical
the absence of properties of Zr–10Al–5Ti–17.9Cu–14.6Ni
crystal defects and grain boundaries. The in lack
the supercooled
of ductility causesregionahad deteri-ex-
cellent mechanical
oration properties.
in the mechanical This was
properties of theduemetallic
to the formation
glass. The of nano-crystallites
mechanical properties in theof
the metallic glass
supercooled regionin a[59].
non-equilibrium
The Ti46Zr20Vstate 12Cu5are
Be17shifted
metallictoward
glassthe metastable
matrix composite equilibrium.
showed
This physical
an increase inprocess is known
the tensile ductility as and
structural
necking relaxation [62]. This causes
in the supercooled region modification
[60]. in
the physical
Metallicproperties,
glass has such as viscoelastic
no crystal defect, properties,
and has high elasticity,
strength,anelastic,
hardness,magnetic,
and yield and
corrosion,
strength. Itand hasother properties
certain that aresuch
shortcomings, influenced by structural
as a brittle nature and relaxation [63]. There
low plasticity are
[61]. This
two
is duekinds of structural
to the absence ofrelaxations:
crystal defectsα-relaxation
and grain and ß-relaxation.
boundaries. The α-relaxation causescauses
lack of ductility glass
transition phenomena
a deterioration and vitrification
in the mechanical [64]. Itofgenerally
properties the metallic disappears
glass. The below glass transition
mechanical proper-
temperature [64]. The beta-relaxation occurs at high temperatures,
ties of the metallic glass in a non-equilibrium state are shifted toward the metastable equi- affects the mechanical
properties
librium. This of the metallicprocess
physical glass, and influences
is known the plasticity
as structural mechanism
relaxation [62]. [65].
This The
causesbrittleness
modifi-
of the metallic glass can be overcome by the activation of shear zones
cation in the physical properties, such as viscoelastic properties, elasticity, anelastic, mag- [66]. It is defined as
an irreversible shear strain that occurs when stress is applied to a localized
netic, and corrosion, and other properties that are influenced by structural relaxation [63]. deformed non-
crystalline
There are two solid. This,ofinstructural
kinds other words, can be called
relaxations: the formation
α-relaxation of the shearα-relaxation
and ß-relaxation. bands [67].
When stress is induced, plastic deformation occurs by the shearing
causes glass transition phenomena and vitrification [64]. It generally disappears below of the material rela-
tive to its resting part. This causes a change in the shape of the
glass transition temperature [64]. The beta-relaxation occurs at high temperatures, affects material. The localized
cluster is plastically
the mechanical deformed,
properties of thecausing
metallicit toglass,
become andsofter than its
influences theundeformed surround-
plasticity mechanism
ings. This causes more flow of plastic strain into thin bands.
[65]. The brittleness of the metallic glass can be overcome by the activation of shear They can occur by external
zones
and internal factors. Maass et al. showed that the
[66]. It is defined as an irreversible shear strain that occurs when52.2 strength of Zr Ti
stress Cu
5 is17.9 Ni
applied14.6 Alto10a
increases with a decrease in temperature. Shear band activity is
localized deformed non-crystalline solid. This, in other words, can be called the formation increased with an inho-
mogeneous flow through
of the shear bands [67]. Whena single
stressshear band at
is induced, cryogenic
plastic temperatures
deformation occurs[68].by the The shear
shearing
band density, bending strain, and other mechanical properties of Pt57.5 Cu14.7 Ni5.3 P22.5 and
of the material relative to its resting part. This causes a change in the shape of the material.
Zr35 Ti30 Cu8.25 Be26.75 metallic glasses were decreased with an increase in the temperature.
The localized cluster is plastically deformed, causing it to become softer than its unde-
When the same strain was applied, the shear band at lower temperature produced multiple
formed surroundings. This causes more flow of plastic strain into thin bands. They can
bands with smaller lengths, leading to increased properties [69].
occur by external and internal factors. Maass et al. showed that the strength of
Due to the catastrophic failure and brittle nature of metallic glass, researchers have
Zr52.2Ti5Cu17.9Ni14.6Al10 increases with a decrease in temperature. Shear band activity is in-
developed composites with excellent thermo-physical properties.
creased with an inhomogeneous flow through a single shear band at cryogenic tempera-
The aim of the present work is to provide a brief overview of the recent development
tures [68]. The shear band density, bending strain, and other mechanical properties of
in metallic glass with a stress on the progress in the last 10 years. Please note that bulk metallic
Pt57.5Cu14.7Ni5.3P22.5 and Zr35Ti30Cu8.25Be26.75 metallic glasses were decreased with an increase
glass is considered and written as metallic glass in this review.
in the temperature. When the same strain was applied, the shear band at lower tempera-
ture produced multiple bands with smaller lengths, leading to increased properties [69].
Due to the catastrophic failure and brittle nature of metallic glass, researchers have
developed composites with excellent thermo-physical properties.
 The aim of the present work is to provide a brief overview of the recent development
in metallic glass with a stress on the progress in the last 10 years. Please note that bulk me-
tallic glass is considered and written as metallic glass in this review.
Metals 2021, 11, 1933 4 of 29
2. Biocompatible Metallic Glass and Their Composites
Metallic glasses are new in the field of biomedical applications with superior tough-
ness, strength, and
2. Biocompatible ductility,
Metallic compared
Glass to crystalline
and Their Composites alloys. Earlier, metallic glasses were
usedMetallic
for structural
glassesengineering,
are new in theduefield
to their high mechanical
of biomedical properties.
applications Metallic tough-
with superior glasses
are nowadays used as biomaterial implants.
ness, strength, and ductility, compared to crystalline alloys. Earlier, metallic glasses were
Metallic
used for crystalline
structural materials,
engineering, duesuch as titanium
to their alloys, Zr
high mechanical alloys, and
properties. stainless
Metallic steel,
glasses
are used in cardiovascular stents,
are nowadays used as biomaterial implants. hip joints, and bone implants (orthopedic joints) [70].
These crystalline
Metallic crystallinemetals have low
materials, suchstrength, low alloys,
as titanium wear, and corrosion
Zr alloys, andresistance. Com-
stainless steel,
plex
are implants
used can be madestents,
in cardiovascular from hip
metallic glass
joints, andbecause of their(orthopedic
bone implants atomic structure,
joints) promis-
[70].
ing chemistry, and surface configurations. These properties can construct
These crystalline metals have low strength, low wear, and corrosion resistance. Com- a biological re-
sponse (Figure 2) with excellent properties over the present metallic biomaterials.
plex implants can be made from metallic glass because of their atomic structure, promising Figure
2 also explains
chemistry, that the
and surface combination These
configurations. of amorphous
properties structures with ametallic
can construct biologicalconstituents
response
produces bio-metallic glasses. Biomedical metallic glasses have a
(Figure 2) with excellent properties over the present metallic biomaterials. Figurehigh elastic modulus
2 alsoat
2%, compared
explains that theto human bone
combination (1%) and under
of amorphous stress,with
structures theymetallic
have aconstituents
unique ability to flex
produces
with the natural
bio-metallic glasses.bending bone. metallic
Biomedical This concludes
glasses that
havestress
a highwill be uniformly
elastic modulus at distributed,
2%, com-
reducing
pared the stress
to human shielding
bone (1%) and effect,
underand the healing
stress, rate awill
they have be achieved
unique faster
ability to flex [71].
with the
Metallic glass is used in medical–surgical equipment [72], cardiovascular
natural bending bone. This concludes that stress will be uniformly distributed, reducing stents [73]
and orthopedic implants [74].
the stress shielding effect, and the healing rate will be achieved faster [71].

Figure2.2.The
Figure Thebio-metallic
bio-metallic glass
glass is
is formed
formed by
by bioglass
bioglass and
and crystalline
crystalline bio-metallic
bio-metallic alloys.
alloys. This
Thisalso
also
shows the relationship between bioglass, bio-metallic alloys, and bio-metallic glass. Reproduced
shows the relationship between bioglass, bio-metallic alloys, and bio-metallic glass. Reproduced
with permission from ref. [71]. Copyright 2016 Elsevier Ltd.
with permission from ref. [71]. Copyright 2016 Elsevier Ltd.

2.1. Ti-Based
Metallic Biomaterial Metallic
glass is used Glass
in medical–surgical equipment [72], cardiovascular stents [73]
Titanium-based
and orthopedic implantsmetallic
[74]. glass is used in implant applications and has better corro-
sion properties, higher fracture strength, and a lower Young’s modulus than crystalline
2.1. Ti-Based Ti
materials. Biomaterial
45Zr10Cu31PdMetallic
10Sn4 Glass
[75] was prepared by gas atomization and porous
Ti45Zr 10Cu31Pd10Sn4 by
Titanium-based Spark Plasma
metallic glass issintering
used in(SPS). Porous
implant metallic glass
applications and has better
betterfunc-
cor-
rosion properties, higher fracture strength, and a lower Young’s modulus
tionality than the commercially used Ti and Ti–6Al–4V implantable biomaterials. The de- than crys-
talline
creasematerials. Ti45 Zrin
in the porosity 10 Cu Pd10 Sn4glasses
the31metallic [75] was prepared
causes by gas in
an increase atomization and porous
Young’s modulus and
Ti 45 Zr
the 10 Cu31 Pd10 Sn
compressive 4 by Spark
strength and aPlasma
decrease sintering (SPS). Porous
in the corrosion metallic
resistance. glass has
It showed better
better bio-
functionality
compatibilitythan thanthe commercially
the commercial used Ti and Ti–6Al–4V
implantable biomedical implantable
materials. biomaterials.
Similar work The
was
decrease
done by Xie in the porosity
et al. [76] in in the metallic
which Ti45Zr10Cuglasses causes
31Pd10Sn an increase
4 metallic glass wasinmade
Young’s modulus
by the combi-
and the of
nation compressive strength
gas atomization andand a decrease
NaCl in the
powder and corrosion
SPS. resistance.
NaCl powder wasItused
showed better
to keep the
biocompatibility than the commercial implantable biomedical materials. Similar work
was done by Xie et al. [76] in which Ti45 Zr10 Cu31 Pd10 Sn4 metallic glass was made by the
combination of gas atomization and NaCl powder and SPS. NaCl powder was used to
keep the porosity under control. The composite exhibited three times higher yield strength
than human bone and could be used for surgical implants. Ti51 Zr5 Cu41 Sn3 [77] showed
better wear resistance and tribological properties than the pure Ti in the SBF (simulated
 porosity under control. The composite exhibited three times higher yield strength than
human bone and could be used for surgical implants. Ti51Zr5Cu41Sn3 [77] showed better
Metals 2021, 11, 1933 5 of 29
wear resistance and tribological properties than the pure Ti in the SBF (simulated body
fluid). It also showed good biocompatibility in vitro than theTi45Zr5Cu41Ni9 and
Ti45Zr5Cu41Ni6Sn3. A thin-film metallic glass [78] of different ratios, Ti–Cu–Pd–Zr and Ti–
Cu–Pd–Zr:
body B were Itfabricated
fluid). by pulsed
also showed laser depositionin(PLD).
good biocompatibility Boron-added
vitro than theTi45 Zrmetallic
5 Cu41 Ni9 and
glass (Ti–Cu–Pd–Zr:
Ti45 Zr5 Cu41 Ni6B)Snshowed good biocompatibility
3. A thin-film andofcorrosion
metallic glass [78] differentresistance. The glass and
ratios, Ti–Cu–Pd–Zr
transition temperature
Ti–Cu–Pd–Zr: was increased
B were fabricatedwith an increase
by pulsed laserin the boron(PLD).
deposition percentage. There was
Boron-added metallic
non-agglomeration of the RBC
glass (Ti–Cu–Pd–Zr: (red blood
B) showed goodcell) in TFMGs after
biocompatibility 30corrosion
and minutes. resistance.
The morphol-The glass
ogy oftransition
the TiB-2 temperature
cell (Figure 3) shows
was the disturbed
increased nature with
with an increase the
in the addition
boron of EDTA
percentage. to was
There
the cell.
non-agglomeration of the RBC (red blood cell) in TFMGs after 30 minutes. The morphology
of the TiB-2 cell (Figure 3) shows the disturbed nature with the addition of EDTA to the cell.

Figure 3. Hemocompatibility tests for different TFMGs (Ti-based thin film metallic glasses). (a) Con-
Figure trol
3. Hemocompatibility tests
uncoated TFMGs, (b) for(without
TiB-0 differentBoron),
TFMGs(c) (Ti-based
TiB-1 (4%thin
B), film metallic
(d) TiB-2 glasses).
(8% B) and (e)(a)
TiB-3(14% B).
ControlReproduced
uncoated TFMGs, (b) TiB-0 (without
with permission from ref. Boron), (c)TiB-1 2021
[78]. Copyright (4% B), (d)TiB-2
Elsevier B.V.(8% B) and (e) TiB-
3(14% B). Reproduced with permission from ref. [78]. Copyright 2021 Elsevier B.V.
Ti-based metallic glasses Ti45Zr40Si15 (Cu-free), Ti45Zr40Si10Cu5 (low-Cu), and Ti45Zr20Cu35
Ti-based
(high-Cu)metallic
[79] wereglasses
prepared Tiby
45Zrdifferent
40Si15 (Cu-free),
Cu proportions.Ti45Zr40SiIt10showed
Cu5 (low-Cu),
that metallicand glass
Ti45Zr20with
Cu35 low(high-Cu)
content [79]ofwere
Cu had prepared
good by different Cu proportions.
biocompatibility It showed that
and low cytotoxicity, me-
compared to
tallic glass
pure with
Ti. Ti low content
Zr
45 20 Cu 35 of Cu
(high had
Cu) good
showed biocompatibility
poor in vitro and low
viability, cytotoxicity,
due to the com-
higher con-
pared tent
to pureof theTi. Cu.
Ti45Zr 20Cu
This 35 (high Cu)
suggests that showed
the Ti45 Zr poor40 Siin
15 vitro viability,
(Cu-free), can bedue to the
used higher
in biomaterials.
content of the Cu. This suggests that the Ti Zr Si (Cu-free), can be
Ti47 Cu38−x Zr7.5 Fe2.5 Sn2 Si1 Ag2 Tax (x = 1–4) [80] were prepared by copper mold casting.
45 40 15 used in biomaterials.
Ti47CuThe
38−xZr 7.5Fe2.5Sn2Si1Ag
supercooled 2Tax (x
region of=the
1–4) [80] were
metallic glass prepared
decreased by copper
with anmold casting.
increase in Ta Thecontent.
supercooled region showed
The material of the metallic glass decreased
good bio-corrosion with anmechanical
resistance, increase inproperties,
Ta content.and The a large,
material showed good
supercooled bio-corrosion
region. Laser surface resistance,
remelting mechanical
was used from properties, andbonded
an in situ a large,coating
super- of the
cooledTiregion.
47 Cu38 Zr Laser
7.5 Fesurface
2.5 Sn2 Si1remelting
Nb2 metallicwasglassused[81].from Theanadditional
in situ bonded coating
Nb formed anof the layer,
oxide
Ti47Cuwhich
38Zr7.5Fe prevented
2.5Sn2Si1Nb corrosion.
2 metallic There
glasswas[81].anThe
increase in the hardness
additional Nb formed andan a decrease
oxide layer,in the elas-
whichtic modulus.corrosion.
prevented The non-toxicTherenature,
was anlow elasticin
increase modulus,
the hardnessand corrosion resistance
and a decrease (Table 2)
in the
elastic modulus. The non-toxic nature, low elastic modulus, and corrosion resistance (Ta-Ti–Cu–
can ensure the using of metallic glass as a biocorrosion biomaterial. Nb was added to
Zr–Fe–Sn–Si–Ag
ble 2) can ensure the using [82] of
metallic
metallicglass,
glassand as aTibiocorrosion
47 Cu38−x Zr7.5biomaterial.
Fe2.5 Sn2 Si1 Ag Nb2 Nb
wasx (x = 0, 1, 2; at
added
%) was prepared. The[82]
to Ti–Cu–Zr–Fe–Sn–Si–Ag addition of Nb
metallic showed
glass, and aTidecrease
47Cu38−xZr in7.5the glass
Fe2.5 Sn2Sitransition
1Ag2Nbx temperature,
(x = 0,
superior
1,2; at%) bio-corrosion
was prepared. resistance,
The addition of Nbgood in vitro
showed compatibility,
a decrease and excellent
in the glass transitionmechanical
tem-
properties. Ti Zr
perature, superior bio-corrosion
40 10 Cu Pd [83]
36 resistance,
14 metallic glass was compared with
good in vitro compatibility, and excellent me- conventional Ti–6Al–
4V and could be used in dental implantology. It showed
chanical properties. Ti40Zr10Cu36Pd14 [83] metallic glass was compared with conventional high thermal stability, cytocompati-
bility,and
Ti–6Al–4V resistance
could tobesterilization,
used in dental andimplantology.
good corrosionItresistance.showed high These properties
thermal ensure that
stability,
the material can be considered biomaterial. A
cytocompatibility, resistance to sterilization, and good corrosion resistance. glassy matrix Ti Zr
75 10 15 Si with
These prop-embedded
Ti60 Zr10that
erties ensure Nb15theSi15material
[84] wascan prepared by meltbiomaterial.
be considered spinning with the formation
A glassy matrix Ti of75single
Zr10Si15ß-type
with embedded Ti60Zr10Nb15Si15 [84] was prepared by melt spinning with the formation of of the
nanocrystals. Stable surface passivity was due to the homogeneous distribution
constituents. Nb improved the glass-forming ability, mechanical properties, and resistance
toward the pitting corrosion. Hydroxyapatite was formed in the metallic glass in SBF
(simulated body fluid). Ti60 Zr10 Nb15 Si15 showed wear and bio-corrosion resistance. The
oxide layer was formed in Ti41.5 Zr2.5 Hf5 Cu37.5 Ni7.5 Si1 Sn5 [85] and showed good corrosion
resistance, and hardness. Pitting corrosion was higher in the artificial saliva solution than
in SBF (simulated body fluid). Ti41.5 Zr2.5 Hf5 Cu37.5 Ni7.5 Si1 Sn5 has lower cell viability L929
Metals 2021, 11, 1933 6 of 29

and NIH3T3 cells. This shows that metallic glass can be used in bone tissue and has
excellent osseointegration. Ti-based nano glass composite with sub-micro-nanometer-sized
hierarchical glassy structure was prepared by magnetron sputtering. Enhancement in cell
proliferation, better biocompatibility, and bioactivity was attained by the formation of
button-like clumps [86].
Table 2. Mechanical and corrosion properties of the Ti-based metallic glass and composite.

Young’s Compressive Corrosion Values

Chemical Composition Preparation Method Reference
Modulus (GPa) strength (MPa) Ecorr (V)/Icorr (A m−2 )
Ti45 Zr10 Cu31 Pd10 Sn4 Gas atomization 100 ± 3.2 2060 ± 85 Ecorr = −0.206 [75]
Ti45 Zr10 Cu31 Pd10 Sn4 Spark Plasma sintering 10–30 2060 – [76]
Ti51 Zr5 Cu41 Sn3 Laser Cladding – – Icorr = 10−5 [77]
Ti45 Zr5 Cu41 Ni6 Sn3 Pulsed laser deposition – – Icorr = 1.33 [78]
Ti45 Zr20 Cu35 (high-Cu) Ti45 Zr20 Cu35 (high-Cu) 77 – Ecorr = –0.259 ± 0.041 [79]
Ti47 Cu38−x Zr7.5 Fe2.5 Sn2 Si1 Ag2 Tax
Copper mold casting 100 2028 ± 32 – [80]
(x = 1–4)
Ti47 Cu38 Zr7.5 Fe2.5 Sn2 Si1 Nb2 Laser surface remelting 153.6 – Icorr = 12 × 10−6 [81]
Ti47 Cu38−x Zr7.5 Fe2.5 Sn2 Si1 Ag2 Nbx
Melt spinning Process 100.4 ± 0.1 2010 ± 66 Icorr = 0.1 Am−2 [82]
(x = 0, 1,2; at%)
Ti40 Zr10 Cu36 Pd14 Tilt copper mold-casting 96 1930 Icorr = 6 × 10−9 [83]
Ti60 Zr10 Nb15 Si15 Melt spinning – – Ecorr = −0.195 ± 0.025 [84]
Ti41.5 Zr2.5 Hf5 Cu37.5 Ni7.5 Si1 Sn5 Induction heating 150.4 ± 4.7 2000 ± 78 Icorr = 10−5 [85]

2.2. Zr-Based Biomaterial Metallic Glass

Zr-based metallic glass has anticipated properties in orthopedic applications [87]. It
is used in arthroplasty, bone screws, and intramedullary nails. The main problem with
Zr-based metallic glass is that it does not allow adhesion and tissue growth at the host
site. Metallic glass Zr44 Ti11 Cu10 Ni11 Be25 [88] was converted into ceramic films. Ceramic
conversion treatment (CCT) in an oxidizing medium was used in the supercooled region of
the metallic glass to convert its surface. Thermal oxidation was performed at 350 ◦ C for 40 h
and at 380 ◦ C for 4.5 h to alter the surface properties. There was an increase in the surface
hardness and Young’s modulus (Table 3), and the coefficient of friction was reduced. SAOS-
2 human osteoblast-like cells increased surface coverage for the untreated surface. This
shows that metallic glass increased its biocompatibility and tribological properties. The
surface quality of the Zr-based metallic glass (Zr67 Cu10.6 Ni9.8 Ti8.8 Be3.8 ) [89] was improved
by bioactive hydroxyapatite suspended powder in dielectric fluid from electro-discharge
machining (EDM). The surface hardness was increased and a crack-free HA-EDMed sur-
face, with nanopores, was achieved. Tribocorosion was studied for Zr65 Cu18 Ni7 Al10 , and
Zr55 Cu30 Ni5 Al10 found that Zr65 Cu18 Ni7 Al10 [90] has better plasticity and can be used as a
potential load-bearing implant. Abrasive wear was experienced in both metallic glasses.
The passive nature of the Zr65 Cu18 Ni7 Al10 showed a negative effect on tribological corro-
sion. Zr48 Cu36 Al8 Ag8 [91] thin film (at.%) was prepared by a 316L stainless steel substrate
by applying magnetron sputtering. The membrane should have good scratch resistance,
mechanical properties, and lower Young’s modulus. TFMG-coated steels showed good
corrosion resistance in SBF (simulated body fluid) and a non-cytotoxic nature in L929 cells.
Low energy ion implantation [92] was done on the (Zr0.55 Al0.10 Ni0.05 Cu0.30 )99 Y1 to improve
the biocompatibility and activity of the metallic glass. Ca-ion showed an increase in cell
adhesion and changed the cell behavior. A higher cell proliferation was observed in Ni-free
Zr60 + x Ti2.5 Al10 Fe12.5 − x Cu10 Ag5 (at. %, x = 0, 2.5, 5) [93]. Zr55 Cu30 Ni5 Al10 based metallic
glass shows the highest wear rates in the different electrolyte systems (NaCl, phosphate
solution with and without protein) as compared to the crystalline structure. The formation
of the nanocrystalline (Zr2 Cu) leads to the formation of a passive layer, leading to corrosion
 glass. Ca-ion showed an increase in cell adhesion and changed the cell behavior. A h
cell proliferation was observed in Ni-free Zr60 + xTi2.5Al10Fe12.5−xCu10Ag5 (at.%, x = 0,
[93]. Zr55Cu30Ni5Al10 based metallic glass shows the highest wear rates in the differen
trolyte systems (NaCl, phosphate solution with and without protein) as compared
Metals 2021, 11, 1933 crystalline structure. The formation of the nanocrystalline (Zr2Cu) leads to the form
7 of 29
of a passive layer, leading to corrosion resistance (Figure 4). The author conclude
the Zr-based metallic glass should be mixed with the (Zr2Cu) nanocrystalline parti
improve the passivation [94].
resistance (Figure 4). The author concluded that the Zr-based metallic glass should be
mixed with
Table the (Zr2 Cu)
3. Mechanical andnanocrystalline particles
corrosion properties of thetoZr-based
improve the passivation
metallic [94].
glass and composite.
Table 3. Mechanical and corrosion properties of the Zr-based metallic glass and composite.
Preparation Young’s Modu- Compressive Corrosion Values
Chemical Composition Refe
Method lus (GPa)
Compressive Corrosion Valuescorr(V)/Icorr (A·m )
Strength (MPa) E −2
Chemical Composition Preparation Method Young’s Modulus (GPa) Reference
Ceramic conversion Strength (MPa) Ecorr (V)/Icorr (A m−2 )
Zr44Ti11CuCeramic
10Ni11Be2
conversion
145.70 ± 3.13 – Ecorr = −0.02 V [
Zr44 Ti11 Cu10 Ni11 Be2 treatments
145.70 ± 3.13 – Ecorr = −0.02 V [88]
treatments
Magnetron sputter-
Zr48Cu36Al8Ag
Magnetron
8 113.92 – Icorr = 7.24 × 10−6 [
Zr48 Cu36 Al8 Ag8 ing 113.92 – Icorr = 7.24 × 10−6 [91]
sputtering
Zr60 + xTi2.5Al10Fe12.5− xCu10Ag5 Copper mold cast-
Zr60 + x Ti2.5 Al10 Fe12.5− x Cu10 Ag5
Copper mold casting 70–78240–255 ± 3 240–255
Icorr±=30.86–1.23 Icorr = 0.86–1.23 [
(at.%, x = 0, 2.5, 5)(at.%, x = 0, 2.5, 5) ing 70–78 [93]

Figure 4. SEM images

Figure of tribocorrosion
4. SEM wear of (a) c-BMG,
images of tribocorrosion (b)(a)a-BMG,
wear of c-BMG,and
(b)(c) Zr andand
a-BMG, alumina
(c) Zrcounterparts,
and alumina(d) c-BMG
(e) a-BMG, and (f) Zr. Reproduced with permission from ref. [94]. Copyright © 2021 Elsevier B.V.
counterparts, (d) c-BMG, (e) a-BMG, and (f) Zr. Reproduced with permission from ref. [94]. Copyright
© 2021 Elsevier B.V.
Ni-free Zr65Ti2.5Al10Fe7.5Cu10Ag showed good mechanical properties and in vitr
Ni-free Zrcompatibility
65 Ti2.5 Al10 Fe7.5 Cu10
[95]. ZrAg
55Alshowed
10Cu30Nigood
5 was mechanical
alloyed withproperties and in
1 at.% yttrium forvitro
surface roug
biocompatibility
and[95].
cellZr 55 Al10 CuThe
behavior. 30 Ni5addition
was alloyed with yttrium
of 1 at.% 1 at.% yttrium
did notforhave
surface
any rough-
substantial eff
ness and cell behavior. The and
proliferation addition of 1 at.% yttrium
cell adhesion, did notinhave
but a decrease any phosphatase
alkaline substantial effect
(ALP) activit
on proliferation and cell
seen [96]. adhesion, but a decrease in alkaline phosphatase (ALP) activity
was seen [96].

2.3. Magnesium-Based Biomedical Metallic Glass

Magnesium alloys degrade over time and do not need surgery to remove them. They
have a density similar to bone (1.8–2.1 g/cm3 ) and can be used as an allograft [97]. In vivo
studies of Mg66 Zn30 Ca4 and PCL composite [97] were examined and it was found that
the composite was biocompatible. The composite properties can withstand 100% elonga-
tion when stress is applied and have thermal properties. Scaffolds of PCL/Mg metallic
glass and PCL/nHA/Mg metallic glass [98], when immersed in SBF (simulated body
fluid), showed their bioactivity. The mechanical properties were affected faster in the
early stages of the hydrolysis but were slower later regarding in vitro loss. The composite
scaffolds also controlled magnesium release. The scaffolds have better mechanical proper-
ties, hemocompatibility and can be used in orthopedic implants. The bio-corrosion and
cytotoxicity of two relaxed and crystallized Mg70 Zn26 Ca4 ribbons [99] in MTT (tetrazolium-
based colorimetric assay) showed that the relaxed metallic glass had better biocorrosion
Metals 2021, 11, 1933 8 of 29

resistance and biocompatibility. MTT (tetrazolium-based colorimetric assay) assay used

with Schwann cells concluded its application in nerve tissue regeneration. Tribological
studies of Mg65 Zn30 Ca5 [100] in phosphate-buffered saline (PBS) applied on ball-on-disk
reciprocating sliding showed that the metallic glass had the highest wear resistance with a
comparison with AZ31B alloy and pure Mg. The corrosion potential decreases the tribolog-
ical contact and increases the corrosion current densities of the Mg-based alloys. The wear
resistance suggests that magnesium-based metallic glass can be used in future orthopedic
implants. A new composition of metallic glass Mg(85 − x) Ca(8 + x) Au7 (with x = 0, 2, 4) [101]
and Mg(81 − x) Ca10 Au7 Yb(2 + x) (with x = 0, 8) showed resistance to the crystallization and
has the potential to be used in sterilization procedure in biomedical applications. The
absence of non-toxic elements in the metallic also plays a major role in its biomedical usage.
In vitro studies of Mg66 Zn30 Ca4 − x Srx [102] (x = 0, 1 and 1.5 at.%) metallic glass was stud-
ied for the bone-forming MC3T3-E1 pre-osteoblast and for the viability in the orthopedic
implant. The results showed that metallic glass had more cell adhesion compared to AZ31B
alloy, caused the proliferation of pre-osteoblasts, and no cytotoxicity occurred. These
properties suggest that metallic glass is biocompatible and has the potential for biomedical
applications. Mg66 Zn30 − x Ca4 Agx [103] (x = 0, 1 and 3 at.%) showed that the addition
of Ag improved corrosion and suppressed hydrogen evolution. Properties like corrosion
resistance, and Ag alloy’s anti-bacterial and cytotoxicity properties make it biocompatible.
The Mg-based metallic glass can be used as a biomaterial material. Comparison studies
(Figure 5) were performed between Mg66 Zn30 Ca4x Srx [104] (x = 0, 0.5, 1 and 1.5 at.%) and
MgZnCaSr. It showed that Mg66 Zn30 Ca4x Srx has the better glass-forming ability, increased
Metals 2021, 11, 1933 9 of 31
corrosion resistance, good mechanical properties, and cytocompatibility. These properties
show future potential in biomedical applications.

Figure 5. AAcomparison
Figure comparisonofofcorrosion rates
corrosion of the
rates Mg-Zn-Ca-Sr
of the (BMGs),
Mg-Zn-Ca-Sr biodegradable
(BMGs), BMGs,
biodegradable and
BMGs,
crystalline
and Mg alloys
crystalline in physiological
Mg alloys solution.
in physiological Reproduced
solution. with permission
Reproduced from ref.
with permission from[104].
ref.Copy-
[104].
right 2014 2014
Copyright Elsevier Ltd. Ltd.
Elsevier

The alloying
The alloying ofof2%2%toto4% 4%ofofYb YbtotoMgMg Zn
6666 Zn3030Ca
Ca44 [105] increased
increased the the ductility
ductility of of the
the
composite. This
composite. This is
is due
dueto tothethepresence
presenceofofextensive
extensiveshear shearbandsbandsininMg Mg66 Zn
66 Zn
30 Ca
30 Ca
2 Yb
2 Yb and
and
(Yb22) Mg
(Yb Mg66 66Zn3030Yb
Yb44(Yb
(Yb4).
4 ).Further,
Further,ininvitro
vitrostudies
studies showed
showed that that the
the addition of 4% Yb de- de-
creasescytotoxicity.
creases cytotoxicity.ItItwaswasconcluded
concludedthat thatthe
theMg Mg Zn
6666 Zn3030Yb
Yb44 amorphous
amorphous compositecompositecan canbebe
used
usedin infuture
futurebiomaterial
biomaterialimplants.
implants. Alloying
Alloying Mn Mn to to
MgMg x Zn
69 −69−x 27Ca4
Zn27 4Mnxx (x = 0, 0.5 and and 11
at.%)
at.%) showed
showed aa decrease
decrease in in the
the mechanical
mechanical strength
strength and and glass-forming
glass-forming ability ability ofof the
the com-
com-
posite.
posite. There
There waswas anan increase
increase in in the
the bio-corrosion
bio-corrosion resistance
resistance (Table(Table4) 4)and
andcell cellviability
viabilityof of
osteoblasts.
osteoblasts. The The strength
strength of of the
the composite
composite is is similar
similar to to bone
boneimplants
implants and andcan canbe beused
usedas as
biomaterials.
biomaterials. Metallic
Metallic glasses
glasses withwithdifferent
differentthicknesses
thicknesses[106], [106],Mg Mg Zn
6767 Zn2727Ca
Ca44 at
at different
different
cooling rates (30 m/s (M1) and 10 m/s (M2)) were
cooling rates (30 m/s (M1) and 10 m/s (M2)) were prepared by Mg prepared by Mg Zn
6767Zn28 Ca
28Ca55 metallic glass.
glass.
ItIt showed
showed that
that metallic
metallic glass
glass with
with aa lower
lower cooling
cooling raterate hadhad aalesser
lessercorrosion
corrosion rate ratein inthe
the
saline
saline solution
solutionand andwaswassusceptible
susceptibleto topitting
pittingcorrosion.
corrosion.

Table 4. Mechanical and corrosion properties of the Mg-based metallic glass and composite.

Compressive Corrosion Rates Ecorr

Chemical Composition Preparation Method Reference
Strength (MPa) (V)/Rcorr(w/sqt)
Metals 2021, 11, 1933 9 of 29

Table 4. Mechanical and corrosion properties of the Mg-based metallic glass and composite.

Compressive Corrosion Rates Ecorr

Chemical Composition Preparation Method Reference
Strength (MPa) (V)/Rcorr (w/sqt)
Relaxed Mg70 Zn26 Ca4 ribbon/Crystallized Ecorr = (−1.21 ± 0.065)/
Melt spinning – [99]
Mg70 Zn26 Ca4 ribbon (−1.38 ± 0.087)
Melt pinning/
Mg65 Zn30 Ca5 ball-on-disk 715–854 Ecorr = −1.23 [100]
reciprocating sliding
Mg66 Zn30 Ca4x Srx (x = 0, 0.5, 1, and 1.5 at.%) Induction-melting 787 ± 22–847 ± 24 Rcorr = 8.76 × 104 [104]
Mg67 Zn27 Ca4 Induction-melting 545–364 −1.116 [106]

2.4. Fe- and Sr-Based Metallic Glass Biomedical Metallic Glass

Fe-based biomaterials are known for their load-bearing implants and are used in hip
prostheses, dental implants, and bone fixators in the hip and knee. A thin layer of metallic
glass (Fe37 Cr15 Mo2 B26 C7 Nb3 Si3 Al6 Mn1 (%at)) was [107] formed with a 316L stainless
steel substrate by using the ESD method. The layer was biocompatible, uniform, dense,
and showed high adhesion. J-quenching and flux treatment were used to prepared a
Fe80 − x − y Crx Moy P13 C7 (x = 10, y = 10; x = 20, y = 5; x = 20, y = 10, all in at.%) [108]. This
metallic glass has higher corrosion resistance than the 316L stainless steel and TC4 and is
biocompatible. Micrographs also showed that the Fe-based metallic glass was filled with
NIH 3T3 cells, shown on the left side of Figure 6. This shows the biocompatibility of Fe-
based metallic glass. Fe73.5 Nb3 Cu1 Si13.5 B9 [109] was ball milled for 48 h and three kinds of
magnetic fluid, Fe73.5 Nb3 Cu1 Si13.5 B9 MR fluid, CoFe2 O4 FF, and Fe3 O4 FF (ferrofluid), were
prepared. The metallic glass showed the potential for use in hyperthermia in tumor therapy.
The addition of Nb in Fe55 − x Cr18 Mo7 B16 C4 Nbx (x = 0, 3, and 4 at.%) [110] improved the
Metals 2021, 11, 1933 corrosion resistance in the ringer solution and can be used as a biomaterial. Sr60 Mg10 18 Zn 31-
of 22
based metallic glass has a low glass transition temperature and has homogenous flow in
the supercooled region. The chemical and physical properties of Sr60 Mg18 Zn22 suggest
that it can be used as a biomaterial [111].
glass. Fe73.5Nb3Cu1Si13.5B9 [109] was ball milled for 48 h and three kinds of magnetic fluid,
Fe Nb3Cu1Si13.5B9MR fluid, CoFe2O4 FF, and Fe3O4 FF (ferrofluid), were prepared. The
2.5.73.5Summary
metallic glass showed
Bio-metallic glassthe potential
materials andforcomposites
use in hyperthermia
are knowninfortumor
theirtherapy. The addi-
high mechanical
tion of Nb in Fe55−xCr18Mo7B16C4Nbx (x = 0, 3, and 4 at.%) [110] improved the corrosion
properties and corrosion resistance. Zr-based metallic glasses have adhesion and host
resistance in the Mg-based
site limitations. ringer solution andglasses
metallic can be used
causeashydrogen
a biomaterial.
gas toSrrelease
60Mg18Zn22-based me-
and can cause
tallic glass has a low glass transition temperature and has homogenous
degradation of the material. This can be prevented by adding ceramic coatings flow in themetallic
and super-
cooled
materials region. The
to the chemical
metallic andmatrix.
glass physicalItproperties
was shown of Sr 60Mg18Zn22 suggest that it can be
that metallic glasses show better
used as a biomaterial [111].
properties than traditional alloys.

Figure 6. Cont.
Metals 2021, 11, 1933 10 of 29

Figure 6.
Figure 6. Morphologies
Morphologies ofof NIH
NIH 3T3
3T3 cells
cells (Swiss
(Swiss mouse
mouse embryo
embryo fibroblasts
fibroblasts 3-day
3-day transfer,
transfer,inoculum
inoculum33×× 105 cells) cultured
105 cells) cultured
on (a) 316L SS, (b) TC4, (c) Cr10Mo10, (d) Cr20Mo5 and (e) Cr20Mo5 for 2 days. On the right side are enlarged micrographs of
on (a) 316L SS, (b) TC4, (c) Cr10 Mo10 , (d) Cr20 Mo5 and (e) Cr20 Mo5 for 2 days. On the right side are enlarged micrographs
the counterparts. Reproduced with permission from ref. [108]. Copyright 2015 Elsevier B.V.
of the counterparts. Reproduced with permission from ref. [108]. Copyright 2015 Elsevier B.V.

2.5. Summary
3. Fiber-Reinforced Metallic Glasses Composites
Bio-metallic glass
Fiber-reinforced metalmaterials
matrix and composites
composites are for
are used known
their for their high
mechanical mechanical
properties and
properties
industrial applications, due to their low-cost production and performance. They arehost
and corrosion resistance. Zr-based metallic glasses have adhesion and usedsite
in
limitations.
the aerospace Mg-based metallicindustries.
and automobile glasses cause hydrogen of
The formation gas
thetooxide
release and canlayer
or carbide causeondeg-
the
radation
fiber can of the material.
degrade This properties
its physical can be prevented by adding
[112]. Metallic ceramic
glass coatings
is known for itsand metallic
mechanical
materials
propertiestobutthelacks
metallic glass matrix.
plasticity; It was shown
a combination that metallicmetallic
of fiber-reinforced glasses show better
glass can prop-
produce
erties than traditional
a composite with goodalloys.
mechanical properties. In recent research, the vacuum pressure in-
filtration processing method was used to produce a carbon fiber/Ti37.3 Zr22.7 Be25.5 Fe5.5 Cu9
(at.%) composite [113]. Microstructure control, good bonding, and strain percentage were
increased, due to the interaction between carbon fiber and shear bands in the metallic glass.
Mechanical strength (Table 5) of the tungsten fiber/Zr41.2 Ti13.8 Cu10 Ni12.5 Be22.5 [114] was
increased. This can be attributed to an increase in fiber volume fraction (Vf ). Similar studies
of tungsten fiber/(Zr40.08 Ti13.30 Cu11.84 Ni10.07 Be24.71 )99 Nb1 [115] increased the mechanical
properties of the composite. Nb was added to increase the properties and interference
of the composite. The yield stress of the composite gradually decreased with the shear
softening. TiNi fibers [116] in metallic glass matrix generated the propagation of multiple
shear bands and induced the TRIP effect, resulting in superior mechanical properties. The
more the fiber volume fraction (Vf ), the better the mechanical properties of the composite.
Tungsten fiber [117] of various dimensions was reinforced in Zr-based metallic glass. The
mechanical properties of the composites increase with a decrease in the size of the tungsten
fiber. Inhibition of shear bands and different fracture modes caused the superior compres-
sive properties. The maximum compressive strength for the composite was 3079 MPa. A
composite was produced by a different volume fraction of the tungsten strings/Zr-based
metallic glass [118]. The 68% volume fraction tungsten composite showed the highest
mechanical properties among the different composites. The enhanced mechanical proper-
ties are attributed to the spatial geometry, which modifies the stress pattern, resulting in
the formation of multiple shear bands in the composite. A laminate structure of carbon
Metals 2021, 11, 1933 11 of 29

fiber-reinforced epoxy and Zr44 Ti11 Ni10 Cu10 Be25 showed an increase in the adhesion of
the composite [119]. A composite [120] based on volume fraction tungsten fiber reinforced
with metallic glass at different temperatures showed that the higher the volume fraction
of the tungsten, the better the mechanical properties. Both the quasistatic strength and
the dynamic strength decrease with an increase in the temperature. Mg-based metallic
glass reinforced with carbon fiber has engineering applications [121]. Al matrix composites
reinforced with Fe74 Mo4 P10 C7.5B2.5 Si2 (at.%) [122] metallic glass fibers were prepared by
ball milling and hot pressing. The plastic deformation and strength were increased due
to the presence of shear slip planes and the axial orientation of the fiber. The addition of
the Nb in the W/Zr-based metallic glass composite can increase the interaction between
the composite [123]. Chen et al. showed that for W/Zr-based composite, splitting of the
composite and the critical energy dissipations for the shear banding are obtained as a
function of the strain rate and tungsten volume fiber fraction [124]. It was found that the
transition mode in the failure in the W/Zr composite is controlled by the shear to normal
strength ratio [125]. B. Zhang et al. studied the effect of tungsten fiber orientation in a
tungsten/Zr-based metallic glass composite. It was concluded that with the increase in
orientation angle θf , the tensile strength decreased and no plasticity was present [126].
Deformation in W/Zr-based metallic glass occurs in two phases. In uniaxial compression,
the metallic glass matrix deforms homogenously, but buckling of the tungsten fiber occurs
first. After further deformation, shear band propagation occurs in the composite, and the
splitting of tungsten fiber with shear bands takes place in the fracture of the composite [127].
A comparison between different composite W/Zr and W/Cu metallic glass showed that
the W/Cu-based composite has higher cohesion strength and compression stress and
strain. The fracture mechanism of the composites was related to the distinct glass-forming
ability of the monolithic metallic glasses [128]. Shear bands in the 61.4 vol% (Figure 7)
tungsten wires/ Zr-based metallic glass cause good mechanical properties and cohesion
in the composite [129]. Wang et al. [130] showed that at a strain rate below 3000 s−1 ,
the compressive strength of the composite Wf /Zr based metallic glass (60%) increased.
A ballistic test on the W/Zr-based metallic glass composite showed that the penetration
depth of the composite is 50% more than the tungsten heavy alloy rods (95W rod) [131].
The mechanical properties of the Wf /Zr-based metallic glass composite are increased with
an increase in the Nb content. Nb increases the interfacial strength in between the tungsten
fiber and metallic glass [132]. Stainless steel capillaries reinforced in Zr-based metallic glass
showed an increase in plastic strain by 14% [133].

Summary
Fiberglass and metallic glass composites are low-cost in production. Tungsten b
fiberglass reinforced with metallic glass produces high yield strength and plastic strain. The
addition of Nb increases the interfacial strength between the metallic glass and fiber. The
free volume also determines the properties of the fiber glass and metallic glass composites.

Table 5. Mechanical properties of fiber-reinforced metallic glass composite.

Yield Strength Fracture Plastic Strain

Chemical Composition Preparation Method Reference
(MPa) Strength (MPa) (%)
Vacuum pressure
Carbon fiber/Ti37.3 Zr22.7 Be25.5 Fe5.5 Cu9 1880 ± 80 – 4.8 ± 1.0% [113]
infiltration processing
Forward melt
Tungsten fiber/Zr41.2 Ti13.8 Cu10 Ni12.5 Be22.5 – 1600 11.7% [114]
infiltrating method
Tungsten Quasi-static
2200–2500 – 26% [115]
fiber/(Zr40.08 Ti13.30 Cu11.84 Ni10.07 Be24.71 )99 Nb1 compression
Pressure infiltration
TiNi fiber/Zr47 Ti13 Cu11 Ni10 -Be16 Nb3 2100 – 14% [116]
casting
Infiltration and rapid
Tungsten fiber/Zr41.2 Ti13.8 Ni10.0 Cu12.5 Be22.5 – – 37% [117]
solidification
Metals 2021, 11, 1933 12 of 29

Table 5. Cont.

Yield Strength Fracture Plastic Strain

Chemical Composition Preparation Method Reference
(MPa) Strength (MPa) (%)
Tungsten Infiltration and rapid
1680 2505 27.1% [118]
strings/(Zr40.08 Ti13.30 Ni11.84 Cu10.07Be24.71 )99 Nb solidification method
Resistive furnace
Tungsten fiber/Zr41.2 Ti13.8 Cu12.5 Ni10.0 Be22.5 2100 – 20% [120]
and quenching
Al matrix
Ball milling/
composites/Fe74 Mo4 P10 C7.5B2.5 Si2 (at.%) 115 ± 8 4200 40% [122]
Hot pressing
metallic glass fibers
Infiltration and
Tungsten fiber/Zr41.2 Ti13.8 Cu12.5 Ni10 Be22.5 – – 23% [124]
rapid solidification
Infiltration and rapid
Tungsten fiber/Zr41.2 Ti13.8 Ni12.5 Cu10 Be22.5 433 – 12.6% [127]
solidification method
Continuous infiltration
Tungsten fiber/Zr41.25 Ti13.75 Cu12.5 Ni10 Be22.5 1230 – 0.75% [128]
process
Wf (60% vol)/Zr41.25 Ti13.75 Cu12.5 Ni10 Be22.5 Melt infiltration casting 2300 – 24% [130]
Metals 2021,Ti11, 1933
Wf/(Zr 13 of 31
41.2 13.8 Cu12.5 Ni10 Be22.5 )100-x Nbx
Melt infiltration casting 2450 – 20% [132]
composites with x = 1, 3, 5 and 7.

Figure 7. A representation of the (a) new continuous infiltration process, (b) a bunch of BMG MC
Figure 7. A representation of the (a) new continuous infiltration process, (b) a bunch of BMG MC
(bulkmetallic
(bulk metallic glass
glass matrix
matrix composites),
composites), (c,d) SEM(c,d) SEM
images images
of the of the of
cross section cross
BMGsection
MC bunchof BMG MC bunch
having
having 61.4 vol%
61.4 tungsten
vol% wires and
tungsten wires(e) and
TEM (e)
image
TEMof the interaction
image of thebetween the tungsten
interaction betweenandthe tungsten and
the Zr41.25Ti13.75Cu12.5Ni10Be22.5 (Vit 1, at%) shown in the inset of (d). Reproduced with permission
the Zr Ti Cu12.5 Ni10 Be22.5 (Vit 1, at%) shown in the inset of (d). Reproduced with permission
from ref.41.25
[129].13.75
Copyright 2012 Elsevier B.V.
from ref. [129]. Copyright 2012 Elsevier B.V.
Summary
4. Metallic Glass/Polymer Composites
Fiberglass and metallic glass composites are low-cost in production. Tungsten b fi-
A reinforced
berglass high magnetoelectric voltage
with metallic glass producescoefficient
high yieldshowed that
strength and the P(VDF-TrFE)
plastic strain. The polymer
film laminated
addition on metallic
of Nb increases glass (Fe
the interfacial Co
strength
67 B Si
between
18 14 1 ) with
the an epoxy
metallic glass resin
and adhesive
fiber. The composite
free
canvolume
be usedalsofor
determines the properties
magnetoelectric of the harvesting
energy fiber glass and metallic
[134]. glass composites.
Mg-based metallic glass/PCL
composite shows biodegradable properties and can be used in biomedical applications [97].
4. Metallic Glass/Polymer Composites
Al-based metallic glass/PET composite was prepared by ball milling and subsequent spark
A high magnetoelectric voltage coefficient showed that the P(VDF-TrFE) polymer
plasma sintering. The author concluded that a change in the chemical composition took
film laminated on metallic glass (Fe67Co18B14Si1) with an epoxy resin adhesive composite
place due to the partial crystallization of the composite [135]. Similar work was done
can be used for magnetoelectric energy harvesting [134]. Mg-based metallic glass/PCL
composite shows abiodegradable
by producing metallic glass/polymer composite
properties and can bybiomedical
be used in mechanical alloying and sparks
applications
[97]. Al-based metallic glass/PET composite was prepared by ball milling and subsequent
spark plasma sintering. The author concluded that a change in the chemical composition
took place due to the partial crystallization of the composite [135]. Similar work was done
by producing a metallic glass/polymer composite by mechanical alloying and sparks
plasma sintering. The composite showed that it can be used as an antifriction material and
Metals 2021, 11, 1933 13 of 29

plasma sintering. The composite showed that it can be used as an antifriction material
and in tribology [136]. M.Y. Zadorozhnyy et al. found that the adhesion of the metallic
glass/polymer composite can be increased by adding 10 mass% of triethoxyvinylsilane.
The composite (HDPE/Mg67,5 Ca5 Zn27,5 ) also showed high thermal conductivity and elastic
modulus [137]. A composite based on Zr65 Cu17.5 Ni10Al7.5 and PTFE polymer showed the
formation of Zr2 Cu and Zr2 Ni intermetallic, and the addition of metallic glass increased
the thermal conductivity in the composite [138]. A silicone polymer was used as a binder
to form a metallic glass–polymer nanocrystalline structure (Fe-based composite). It was
also concluded that the composite showed improvement in soft magnetic properties [139].
Zr-based metallic glass/polyacrylonitrile (PAN) composite can be used to produce nitrogen
selective applications [140]. Metallic glass–polyisoprene nanolaminate causes an increase
in the plastic flow and can be used in structural and nanodevices. The composite also
shows corrosion and wear resistance [141]. A similar study was conducted by producing
Fe64 Co17 Si7 B12 metallic glass and polyvinylidene fluoride (PVDF) using an epoxy resin,
which has a piezoelectric response and can be used in miniature electronic devices and
ultra-low power applications [142].

Summary
Metallic glasses have high strength but lack plasticity. The polymer has low strength
and high plasticity. The combination of both can produce a composite with good thermo-
physical properties. The lack of interaction between the polymer and metallic glass is a
major drawback and can be avoided by using binders. M.Y. Zadorozhnyy [137] showed
that silane can be used as a binder between metallic glass and polymer.

5. Ex Situ Metallic Glass Composites

Ex situ [143] metallic glass composites are generally formed by mechanical alloying or
atomization of the powder. These composites have a glassy phase and reinforcement of
second phase particles. The variation in particle size varies from micrometer to nanometer.
It can also be formed by introducing a second phase as reinforcement in the glassy matrix.
Metallic glass matrix/fiber reinforcement composite are some of its examples. A Ti-based
metallic glass composite showed that with an increase in the Zr content, the mechanical
properties improved. The solid solution strengthening of ex situ Ti layers hinders the
propagation of shear bands and improves the mechanical properties [144]. The addition of
Nb in Ti-based metallic glass increases the bond interference and mechanical properties
(Table 6) of the composite. The formation of the α-Ti gradient layer helps in restraining
the shears bands, which leads to the formation of multiple shear bands and increases
the plasticity of the composite [145]. The electroless copper plating forms a stable and
protective layer between SiC particles and Mg-based metallic glass. The SiC particles
increase the plastic zone size, and the Cu coating helps in the prevention of shear bands,
improving the plasticity [146]. The ex situ Mg-based metallic glass composite showed
that shear band stability can hinder the motion of shear bands [147]. A work hardening
behavior was seen in the composite because of the porous NiTi particle in Mg-based
metallic glass. The hindrance of the movement of the single shear bands leads to the
increase in the plasticity of the composite [148]. Zr-based metallic glass drill bits can be
used in orthopedic drills in medical applications [149]. Ex situ Ta (0–6 vol%) particles
were reinforced by pulse laser technique on Zr-based metallic glass, and no harmful
crystalline particles were present. There was the formation of sub-zero and nano-size
Ta particles in the weld fusion zone. Ta also affected the glass transition temperature
and glass-forming ability of the composite [150]. An interfacial reaction occurred when
an ex situ composite was welded. There was the formation of an interfacial layer in
the reinforced phase (Ta) in PM, WFZ, and HAZ zones. A more stable ZrCu layer was
formed in WFZ [151]. The La-based composite showed good mechanical properties but can
cause plastic strain, due to the formation of oxide defects [152]. Ti particles in Mg-based
composite increase the plasticity of the composite due to the multiple shear bands. The
Metals 2021, 11, 1933 14 of 29

plasticity of the composite depends on Ti particle size and interparticle spacing [153]. In
similar studies, J.B. Li et al. showed that shear band propagation (Figure 8) was restricted
by the semi-uniform confinement zones of Ta particles. The plasticity was dependent on
the interparticle size and confinement zone [154].
Metals 2021, 11, 1933 15 of 31

Table 6. Mechanical properties of ex situ metallic glass composite.

Table 6. Mechanical properties

Yieldof ex situ metallic glass
Strength composite. Plastic Strain
Fracture
Chemical Composition Preparation Method Reference
(MPa) Strength (MPa) (%)
Yield Strength Fracture Plastic
Chemical Composition Preparation Method
Melt spinning/ Reference
Ti63 − x Zrx Ni5.3 Cu9 Be22.7 (at.%, x = 52) 1552 ± 20 (MPa)1956 ±Strength
20 (MPa)
8.4 ±Strain
0.2% (%) [144]
Ex situ method
Melt spinning/Ex situ
Ti63-xZrxNi5.3Cu9 Be22.7 (at.%, Melt
x = 52)
spinning/ method 1552 ± 20 1956 ± 20 8.4 ± 0.2% [144]
(Ti0.328 Zr0.302 Ni0.053 Cu0.09 Be0.227 )100 − x Nbx 1078 ± 10 1112 ± 5 5.10 ± 0 [145]
Quenching
Melt spinning/Quench-
20%TiNi/Mg59.5 Cu (Ti0.328Gd
Zr0.30Ag
2Ni0.053Cu0.09Be0.227)100−xEx
Nbsitu
x)
– 1078 ± 101173 1112 ± 5 12.1% 5.10 ± 0. [145]
[148]
22.9 11 6.6 ing
20%TiNi/Mg59.5Cu22.9Gd 11Ag
Melt spinning/Injection
6.6 Ex situ – 1173 12.1% [148]
La55 Al25 Cu10 Ni10 /35 mesh Ta particles 720 – 40% [152]
cast melting
Melt spinning/Injection
La55Al25Cu10Ni10/35 mesh Ta particles 720 – 40% [152]
Mg58 Cu28.5 Gd11 Ag2.5 /Ti particles Injection casting cast melting 800 – 25% [153]
Mg58Cu28.5Gd11Ag2.5/Ti particles Injection casting 800 – 25% [153]
Two-step arc melting
Zr47.3 Cu32 Ag8 Al8 Ta4 Si0.7 /ex situ Ta particles process Two-step arc melting
and 1770–1800 1800 44% [154]
Zr47.3Cu32Ag8Al8Ta4Si0.7/ex situ Ta par-
process and suction
suction casting 1770–1800 1800 44% [154]
ticles
(Zr48 Cu36 Al8 Ag8 )99.25 Si0.75 /Ta particles Suction casting casting 1800 1850 22% [155]
Zr48Cu36Al8Ag8)99.25Si0.75/Ta particles Suction casting 1800 1850 22% [155]

Figure 8. SEM images of fracture area of (a) monolithic Zr47.3Cu36Ag8Al8Si0.7 BMG, (b) Zr47.3Cu32Ag8Al8Ta4Si0.7 BMGC, (c)
Figure 8. SEM images of fracture area of (a) monolithic Zr47.3 Cu
Zr47.3Cu32Ag8Al8Ta4Si0.7BMGC with ex situ added, 3 vol.% Ta, and (d) Zr47.3Cu32Ag8Al8Ta4Si0.7 BMGC 36 Ag
with 8 Aladded,
ex situ 8 Si0.7 9BMG,
vol.% Ta.(b) Zr47.3 Cuwith
Reproduced 32 Ag Al Ta Si
permission
8 8 4 0.7fromBMGC,
ref. (c)
[154]. Zr Cu
Copyright
47.3 2012
32 Ag Al Ta
Elsevier Si
B.V.
8 8 4 0.7 BMGC with ex situ added, 3 vol.%
Ta, and (d) Zr47.3 Cu32 Ag8 Al8 Ta4 Si0.7 BMGC with ex situ added, 9 vol.% Ta. Reproduced with
permission from ref.Ex situ Ta particles in the Zr-based composite showed an increase in plasticity due to
[154]. Copyright 2012 Elsevier B.V.
shorter interplanar spacing. The interfacial area was also increased due to the bigger vol-
ume fraction particles [155].
Ex situ Ta particles in the Zr-based composite showed an increase in plasticity due
to shorter interplanar spacing.
6. In Situ Metallic TheComposites
Glass interfacial area was also increased due to the bigger
volume fraction particles [155].
The plasticity of the metallic glass composite can be increased by introducing a sec-
ond phase, which can block the propagation of shear bands. The formation of multiple
6. In Situ Metallic Glasscan
shear bands Composites
increase the plasticity of the metallic glass composite. The crystalline
The plasticity of the metallic glass composite can be increased by introducing a second
phase, which can block the propagation of shear bands. The formation of multiple shear
bands can increase the plasticity of the metallic glass composite. The crystalline phases
Metals 2021, 11, 1933 15 of 29

occur during the solidification of the melts, which increases the plasticity. These composites
are in the form of crystalline phases, nanocrystalline phases, and dendritic phases [156].
Ex situ metallic composites are generally prepared by techniques such as ball milling and
the melt infiltration process [142]. Different particles of size ranging from micrometer
to nanometer are induced. In situ composites are produced by thermal treatment, high-
pressure torsion, and hot extrusion processes. Secondary particles, such as crystalline,
semicrystalline, and quasi-crystalline, are formed. By controlling the kinetics and thermo-
dynamics of the metallic glass in the supercooled region, the crystallization process can be
avoided. The heat treatment process is generally done to control the crystallization process.

6.1. Crystalline/Nanocrystalline Metallic Glass Composites

A dual crystalline phase, α- and β-phase reinforced in Ti-based metallic glass com-
posite showed good mechanical properties. This could be attributed to the hindrance of
shear bands by crystalline phases and α-phase toughening in the β-phase [157]. The high
torsion method was used to prepare a nanocrystalline composite and a Cu-rich nanocrystal
increased the yield and ultimate strength of the metallic glass. The strain hardening and
elongation were increased by the increase in the free volume [158]. Nanoporous metallic
glass (Fe–Ni–Co) composite can be used in clean energy applications [159]. Martensitic
transformation of nanocrystalline Ti50 Ni47 Fe3 composite can provide near-ideal strain and
strength in a composite [160]. FeCrMoCB metallic glass can be used in joint replacement
implants [161]. Uniformity in the eutectic phase and Fe2 B nanocrystalline structure plays
an important role in the properties of a material. The nanocrystalline structure of Fe-
based metallic glass enhances the mechanical properties (Table 7) of the composite [162].
The enhancements in the absorption kinetics of Mg-based metallic glass occur due to the
formation of nanocrystals by the control agents present in the ball milling process. The
dehydrogenation in the Mg60 Ce10 Ni20 Cu10 metallic glass was controlled by the formation
of nanocrystal hydrides [163]. Nanocrystals in the Fe-based metallic glass that occurred
during partial annealing led to an increase in the ferromagnetic properties of the composite.
Crystalline particles present in the composite increased the volume fraction, which resulted
in increasing the hardness of the composite [164]. Q. Zhou et al. showed that the addition
of Sn to Ti-based metallic glass has wear resistance and can produce the formation of a
continuous tribolayer. This tribolayer during sliding shows improved the tribological prop-
erties [165]. A. Yao et al. showed that the nanocrystalline metallic glass (Al82 Ni6 Co3 Y6 Cu3 )
can be used as an easy precursor in manufacturing non-porous electrodes [166]. Crys-
talline Fex N in FeSiCrB metallic ribbon provided high electric resistance, magnetic moment,
works as a binder, and boosts magnetic properties in the FeSiCrB metallic ribbon. The
stacking factor of the magnetic material is near 100% and the composite can be used as
a soft magnetic material in electrical and electronics machines [167]. The composite of
Zr/nanocrystalline Fe metallic glass has better compressive strength and hardness than
the Zr metallic glass [168], but 40% above the volume fraction of Fe-based metallic glass
causes cracks and pores formation. X. Ji et al. discussed that microstructure evolution is
related to the solidification of the cooling rate, impact-induced temperature rise, plastic
flow, oxidation, and interdiffusion of the metal elements [169]. Non-planar thin film (CuO-
Cu2 O)/ZnO: Al heterojunctions have applications in solar and electronic devices [170]. W.
R. Jian et al. studied that the volume fraction of the Cu64 Zr36 crystal particles can achieve
a balance between hardness, hardness, and ductility [171]. Partial nano-crystallization
of Zr-based composite has anticipated vibration and electric transport properties [172].
Microstructure analysis (Figure 9) of the Ti-based composite showed that the crystallization
occurred in the amorphous phase in two phases, and the formation of nanocrystals (B2)
and precipitation of the γ-TiCu phase occurred afterward [173].
Metals 2021, 11, 1933 16 of 29
Metals 2021, 11, 1933 17 of 31

Figure 9.
Figure 9. XRD
XRD pattern
pattern of
of (a)
(a) DSC
DSC curve,
curve, (b)
(b) SEM-BSE
SEM-BSE (backscattered electron) image,
(backscattered electron) image, (c)
(c) and
and TEM
TEM BF
BF image,
image, (d)
(d) of
of as-cast
as-cast
alloy, together with SAED patterns obtained from an amorphous matrix, (e,f) B2 particle. Reproduced with permission
alloy, together with SAED patterns obtained from an amorphous matrix, (e,f) B2 particle. Reproduced with permission
from ref. [173]. Copyright 2016 Elsevier B.V.
from ref. [173]. Copyright 2016 Elsevier B.V.

Cu-based metal–intermetallic nanostructured

Cu-based metal–intermetallic nanostructuredcomposites compositeshave havehighhighthermal
thermal stabil-
stability,
ity, high ductility, and superior strength because of their distinctive
high ductility, and superior strength because of their distinctive microstructure and irregu- microstructure and
irregular deformation mechanism. This composite can have
lar deformation mechanism. This composite can have applications in construction, military, applications in construction,
military,
automobile, automobile,
and aerospaceand aerospace
[174]. [174].
The
The formation
formationof ofprecipitation
precipitationofof thethenano-sized
nano-sized Ni2NiSnTi phase occurs during anneal-
2 SnTi phase occurs during an-
ing in the
nealing inmetallic
the metallicglassglass
(Ti45Cu
(Ti4145Ni
Cu6Zr5Ni
41
Sn ),
3Zr
6 5
and
Sn 3
an
), increase
and an in
increasethe wear
in theresistance, micro-
wear resistance,
hardness, and wear resistance is induced by the nanocrystals
microhardness, and wear resistance is induced by the nanocrystals [175]. J.-K. Lee et al. [175]. J.-K. Lee et al. showed
that
showedthe that
deformation of W/Ni-based
the deformation metallic metallic
of W/Ni-based glass composites
glass compositesdependsdepends
on the layered
on the
structure of the nanograined
layered structure tungsten matrix
of the nanograined tungsten and its reinforcement
matrix [176]. The addition
and its reinforcement [176]. The of
boron
addition in the Mo–Ni–Si–B
of boron metallic glass
in the Mo–Ni–Si–B can increase
metallic glass can theincrease
glass-forming ability of theability
the glass-forming com-
posite. Mo–Ni–Si–B
of the composite. metallic glass
Mo–Ni–Si–B can be
metallic usedcan
glass to beform useda metallic
to form glass–nitride nanocom-
a metallic glass–nitride
posite coating layer
nanocomposite and has
coating layeranand
application in wear resistance
has an application in wear coatings [177].
resistance The porosity
coatings [177].
structure
The porosity of Zr 70Cu24Al4Nb
structure 2 metallic
of Zr 70 Cu A glass
24 l4 Nb 2can be
metallic influenced
glass can by be the SPS
influencedprocedure.
by the The
SPS
higher
procedure.sintering temperatures
The higher sintering lead to the formation
temperatures lead to ofthe
nanocrystals
formation in of the composite.inThis
nanocrystals the
composite. has
composite This an composite has an
application inapplication
functional inmaterials
functional[178]. materialsThe [178]. The coerciv-
coercivity of the
ity72of
Co the
B19.2 SiCo
4.8Cr724Bmetallic
19.2 Si4.8 Cr 4 metallic
glass is changedglassbyisthe changed by the intermediate
intermediate nanocrystalline nanocrystalline
phase, result-
phase,
ing in anresulting
amorphous in ansoft
amorphous
state to asoft state to a monocrotaline
monocrotaline hard magnetichard statemagnetic
[179]. Q.state
Xing[179].
et al.
Q. Xing et
showed thatal.pre-compression
showed that pre-compression
treatment for treatment
RE65Co25Alfor RE65 Co25
10 metallic Al10can
glass metallic
induce glass can
the for-
induce the formation of the nanocrystalline composite. The
mation of the nanocrystalline composite. The pre-compression treatment is good for ther- pre-compression treatment is
good for thermal and mechanical properties [180]. The decrease
mal and mechanical properties [180]. The decrease in the plasticity of Ti-based metallic in the plasticity of Ti-based
metallic
glass glasstois the
is due duedecimation
to the decimation
of theof thevolume
free free volume and and microcracks,
microcracks, andand precipitation
precipitation of
of nanocrystals
nanocrystals leads
leads to to brittle
brittle fracture
fracture [181].
[181]. R. R. Babilas
Babilas et al.
et al. showed
showed that
that in Mg
in Mg 60 Cu
60Cu 30,Y
30Y10 10 ,
the
the homogenous
homogenous metallic
metallic glassglass
has morehas more corrosion
corrosion resistanceresistance
than the than the nanocrystalline
nanocrystalline parti-
particles in the composite [182]. The nanocrystalline Mg
cles in the composite [182]. The nanocrystalline Mg rod obstructs the propagation of shear rod obstructs the propagation
of shear
bands in bands
thin-film in thin-film metallic
metallic glass. Theglass.
moreThe the more
Mg content the Mgincontentthe thininfilm,
the thin film, the
the better the
better the ductile behavior. The author concluded that the composite can be used in micro-
Metals 2021, 11, 1933 17 of 29

electronic–mechanical biomedical devices [183]. The increase in the fraction ß-type phase
leads to the degradation and decrease in the mechanical properties in Ti60 Zr10 Nb15 Si15 as
compared to Ti75 Zr10 Si15 . This leads to a high H/ER ratio and proposes an application in
high wear resistance [184]. Ag in Zr56 Co22 Al16 Ag6 , in the local structure of the Zr–Co–Al,
is influenced by the positive mixing of Ag and Co in Zr56 Co22 Al16 Ag6 . The nucleation rate
and growth rate at a maximum temperature are credited to ultrafine nanocrystals [185].
L.M. Zou et al. showed that the addition in the content of Fe in TiNbZrTa increased the
glass-forming ability and enthalpy of crystallization and transformed the structure from a
nanocrystalline structure in the nanocomposite matrix with nanocrystals in an amorphous
matrix [186]. A sintered and porous structure Ti-based metallic glassy/nanocrystalline
composite has application in structural and functional applications [187]. The increase
in the Cu–Ni content in Ti–Zr–Cu–Ni–Co amorphous alloys showed an increase in the
compressive strength and plasticity in the composite [188,189]. Dynamic martensitic trans-
formation and heterophase structure increased the strength and plasticity of the composite
in the Ni–Cu–Ti–Zr composite [190]. The addition of Fe in the Ti–Cu amorphous alloy
led to the formation of CuTi2 intermetallic compounds, which degraded the mechanical
properties of the composite [191]. I.S Golovin et al. studied the change in the internal
friction values; the structural changes occurred due to the martensitic transformation in
the Ni40 Cu10 Ti33 Zr17 composite [192]. The addition of Y, Nb, and Al in (Ti–Ni–Cu–Zr)
metallic glass induced transformational plasticity and an increase in yield strength [193].
Structural relaxation occurred in the Zr–Cu–Ni–Al metallic glass, storage modulus and
internal friction changed due to the amorphous alloy crystallization [194]. The formation
of the NiTi2 phase in the (Ti–Ni)–(Cu–Zr) phase caused degradation in the mechanical
properties of the composite [195].

Table 7. Mechanical properties of crystalline/nanocrystalline metallic glass composites.

Preparation Yield Strength

Chemical Composition Ultimate Tensile Plastic Strain Reference
Method (MPa)
Melt Spinning/
Ti31.2 Zr28.7 Ni5 Cu8.5 Be21.6 Mo5 1410 1625 3.6% [157]
quenching
High-Pressure
Zr52.5 Cu17.9 Al10 Ni14.6 Ti5 1793 2023 0.4% [158]
Torsion
Arc melting/
Ti50 Ni47 Fe3 1700 2250 5.5% [160]
annealing
Zr48 Cu36 Al8 Ag8 /Fe65.4 C7.1 Si3.3 B5.5 P8.7 Cr8 Al2 hot-pressing
– – 3.4 ± 0.1 [168]
(nanocrystalline) method
Cu85 Zr10 Al5 arc melter 1800 2160 1.3 [174]
Milling/spark
W/Ni59 Zr20 Ti16 Si2 Sn3 1730 2409 2.6 [176]
plasma sintering
Arc melting/
Ti44 Zr20 Nb12 Cu5 Be19 1438 – 8.6 [181]
annealing
Mgx Zrx Cux Sputtering 1700 – 52% [183]
Copper mold
Ti-40Nb (Ti74.4 Nb25.6 ) casting/melt 544 ± 66 – 28 ± 7 [184]
spinning method

6.2. Dendritic and Quasicrystal Metallic Glass Composite

G.H. Duan et al. showed that the shear bands can be terminated in two ways for
dendritic phases. The first is the change in the position of the direction of the shear bands
beside the boundaries of dendrites and glass matrix. The second one is the dendrites
blocked the shear bands in the glass matrix [196]. Distinct microstructure in FeCrMoBC
alloy with different cooling rates can be achieved by laser-directed energy deposition.
The varying cooling rates generate the microstructure of soft crystalline dendrites with
an amorphous matrix and lead to an intrinsic toughening mechanism [197]. J.I. Lee et al.
prepared a metallic glass and alumina composite with the dendritic structure and showed
Metals 2021, 11, 1933 18 of 29

Metals 2021, 11, 1933 19 of 31

that the composite at 800 ◦ C showed the highest compressive strength of 2490 ± 65 MPa
between
in in situthe samplesIn[198].
dendrites. A new deformation
this method, dendrites aremethod
insertedthat
and pulls apart
then torn wasin
apart discovered
the tough-
in in situ dendrites. In this method, dendrites are inserted and
ened amorphous matrix during the plastic flow [199]. Dendritic ß-Ti phase and marten- then torn apart in the
toughened amorphous matrix during the plastic flow [199]. Dendritic
sitic transformation increased the strain hardening of the composite. The author also stud- ß-Ti phase and
martensitic
ied the different volume fraction of ß-Ti dendrites and their impact on the compositealso
transformation increased the strain hardening of the composite. The author and
studied the different volume fraction of ß-Ti dendrites and their
concluded that the combination of ß-Ti and 38% volume fraction demonstrates high duc-impact on the composite
and
tilityconcluded
and strengththat [200].
the combination
The in situofβ-Tiß-Tidendrite
and 38%phasevolume in fraction demonstrates
Ti-MG stabilizes high
the plastic
ductility and strength [200]. The in situ β-Ti dendrite phase in Ti-MG
flow, and the generation of nucleation sites of the multiple shear bands leads to enhanced stabilizes the plastic
flow, and the
plasticity andgeneration of nucleation
strength (Table 8) of thesites of the multiple
composite [201]. S.shear
Yangbands leads to enhanced
et al. concluded that the
plasticity and strength (Table 8) of the composite [201]. S. Yang et al. concluded that
intermediate glassy phase at the nanoscale that is deformed homogenously could be re-
the intermediate glassy phase at the nanoscale that is deformed homogenously could
lated to the mechanical behavior of the Ti68Cu13.2Pd5.6Sn1.2Nb12 alloy [202]. The defor-
be related to the mechanical behavior of the Ti68 Cu13.2 Pd5.6 Sn1.2 Nb12 alloy [202]. The
mation-induced martensitic transformation in the B2–ZrCo dendrite in Zr–Co–Al (Z1) dis-
deformation-induced martensitic transformation in the B2–ZrCo dendrite in Zr–Co–Al
played high strength and plasticity. High strength and low plasticity were also found in
(Z1) displayed high strength and plasticity. High strength and low plasticity were also
Zr–Co–Al (Z5), due to the presence of a large eutectic inter-dendritic phase in the crystal-
found in Zr–Co–Al (Z5), due to the presence of a large eutectic inter-dendritic phase in the
line phases [203]. N. Hua et al. showed that high-strength ultrafine eutectic–dendrite com-
crystalline phases [203]. N. Hua et al. showed that high-strength ultrafine eutectic–dendrite
posites with a high range of ductility and strength can be attained without rapid solidifi-
composites with a high range of ductility and strength can be attained without rapid
cation and an injection mold casting procedure [204]. The Ti16.6Nb6Co5.1Cu6.5Al alloy has
solidification and an injection mold casting procedure [204]. The Ti16.6 Nb6 Co5.1 Cu6.5 Al
better potential than commercial Ti alloys in biomedical applications [205]. The mechani-
alloy has better potential than commercial Ti alloys in biomedical applications [205]. The
cal properties in Ti–Zr–Nb–Cu–Be were increased and showed structural stability after
mechanical properties in Ti–Zr–Nb–Cu–Be were increased and showed structural stability
annealing,
after due due
annealing, to slight β-thermal
to slight relaxation
β-thermal [206].
relaxation The The
[206]. addition of Nb
addition of in
Nbthein Ti–Zr–Cu–
the Ti–Zr–
Pd–Sn metallic
Cu–Pd–Sn metallicglass and
glass andformation
formation ofofthe
theβ-Ti
β-Tiphase
phaseincreased
increased the plasticity (Figure
the plasticity (Figure10)10)
and work- hardening feature [207]. The figure shows the increase
and work- hardening feature [207]. The figure shows the increase in plasticity with the in plasticity with the
additionof
addition ofNb.
Nb.

Figure10.
Figure 10.Compressive
Compressive engineering
engineering stress–strain
stress–strain (σ
(σ −−ε)ε)curves
curvesofofthe
thebase
baseand
andNb-added
Nb-addedalloys,
alloys,
Reproduced with permission from ref. [207]. Copyright 2016 Elsevier
Reproduced with permission from ref. [207]. Copyright 2016 Elsevier B.V. B.V.

A2%
A 2% addition of the the Si
Sito
toTi
Timetallic
metallicglass
glassproduced
produced a dendritic,
a dendritic, which
whichenhances
enhances the
mechanical
the mechanical properties
propertiesof the composite
of the [208].
composite J. Cui
[208]. J. et
Cuial.etshowed that the
al. showed thatplasticity of the
the plasticity
Tithe
of 50ZrTi
20Nb 12Cu
50 Zr 5Be
20 Nb is 5enhanced
13Cu
12 by the emergence
Be13 is enhanced of the plastic
by the emergence of thedimple
plasticfracture
dimple and mul-
fracture
tiplemultiple
and shear bandsshear[209].
bands The solidThe
[209]. solution
solid strengthening effect is caused
solution strengthening bycaused
effect is the impurities
by the
impurities that are in
that are immersed immersed in thephase
the ß titanium ß titanium
in the phase
Ti48Zr20inNb the Ti548
12Cu BeZr Nb12
. The
1520 Cu5 Bealso
author 15 . The
con-
author
cludedalso
thatconcluded
the additionthatofthe addition
a high of aof
amount high amount
oxygen of oxygen
caused causedindegradation
degradation the composite in
[210]. During solid solution strengthening, the strength and hardness of the dendrites
Metals 2021, 11, 1933 19 of 29

the composite [210]. During solid solution strengthening, the strength and hardness of the
dendrites were increased in the Ta-based metallic glass, resulting in the generation of mul-
tiple shear bands, which improve the plasticity of the composite [211]. A new approach to
form a high-strength Ti-based composite was proposed by inducing a brittle inter-dendritic
phase (e.g., Co, Cr, or Cu) until the alloy exhibited β-Ti morphology completely [212].
H. S. Arora et al. showed that the friction stir processing procedure can be used for local-
ized microstructural transformation and homogeneous distribution in the composite [213].
The strain rate of the Zr39.6 Ti33.9 Nb7.6 Cu6.4 Be12.5 composite is affected by the dispersion of
the fracture and shear bands [214]. The withdrawal velocity in Zr-based metallic glass can
affect the morphology and mechanical properties. The volume fraction in the crystalline
phases is accountable for the improvement in the plasticity of the composite [215]. The
formation of dendritic B2 CuZr improves the yield strength and ductility of the Zr metallic
glass-based composite [216]. The shear band formation can be reduced by inducing qua-
sicrystals in the amorphous matrix. They also hinder the formation of shear bands and
cause the formation of multiple shear bands, increasing the plasticity [217]. The icosahedral
quasistatic phase in the Mg matrix increases the plasticity (Table 9) and overall strength
of the composite and has a chemical correlation between the quasicrystal phase and the
metallic glass matrix [218]. The formation of the I-phase favored by oxygen impurity in the
(Zr65 Cu15 Al10 Ni10 )90 Nb10 leads to the reducing of the undercooling in the alloy melt, and
during cooling, the long-range order of the icosahedral order is easily trapped [219].
Table 8. Mechanical properties of dendritic of metallic glass composites glass composite.

Yield Strength Ultimate Tensile

Chemical Composition Preparation Method Plasticity Reference
(MPa) Strength
cold crucible levitation
Ti48 Zr20 Nb12 Cu5 Be15 metallic glass 1160 1310 10.7% [199]
melting/copper mold casting
BT80 copper mold casting 1046 ± 17 1326 ± 15 9.1 ± 0.3 [200]
(Ti51 Zr38 Nb11 )71 Cu9 Be20 suction casting method 2053 – 8.06 [201]
Ti68 Cu13.2 Pd5.6 Sn1.2 Nb12 suction casting 1300 – 23.7 [202]
Zr54 Co35 Al11 (Z1) Suction cast/Quenching 1323 ± 10 – 28.7± 0.1 [203]
Zr54 Co35 Al11 (Z5) Suction cast/Quenching 1950 ± 10 – 3.0 ± 0.1 [203]
Ni90 Hf10 arc-melting 1910 – 34.4 [204]
Ti16.6 Nb6 Co5.1 Cu6.5 Al Arc melting/Casting 1230 ± 50 – 11 ± 1% [205]
Ti48 Zr20 Nb12 Cu5 Be15 arc-melting/copper casting 1599 – 34% [206]
Suction casting/
Ti56 Zr6 Cu19.8 Pd8.4 Sn1 .8 Nb8 1690 2680 20 [207]
copper molding
melt-spinning/
(Ti0.425 Cu0.425 Ni0.075 Zr0 .075 )1−x Six 1497 ± 50 – 10.3 ± 0.1 [208]
suction casting
Melt Spinning/Copper-mold
Ti38.8 Zr28.8 Cu6.2 Be16.2 Nb10 (Ta0.5 (VF)) 1517 2610 20.3 [209]
suction casting
Melt spinning/
Ti68.8 Nb13.6 Cr5.1 Co6 Al6 .5 1100 ± 20 1290 ± 50 21 ± 3 [212]
Casting method
Arc melting/the semisolid
Zr60.0 Ti14.7 Nb5.3 Cu5.6− Ni4.4 Be10.0 (at%) treatment plus 1260 2050 16.7 [215]
Bridgman solidification
Arc melter/copper mold
cast Cu47.5 Zr47.5 Al5 (series 130) 1311 1628 13.94 [216]
suction casting

Table 9. Mechanical properties of quasicrystal of metallic glass composites glass composite.

Chemical Composition Preparation Method Yield Strength (MPa) Fracture Strength (MPa) Plastic Strain Reference
Mg66 Zn29 Ca4 Y Semi-solid processing 850 870 0.6% [218]
Metals 2021, 11, 1933 20 of 29

Summary
Metallic glass composites are generally prepared by either ex situ or in situ processes.
In the ex situ process, secondary phases are produced by ball milling or melt infiltration.
In situ processes are generally heat treatment for secondary phases. The formation of
semi-crystalline, nanocrystalline, and quasi-crystalline particles can produce a metallic
glass composite with high properties. Crystalline materials are ductile, and metallic glass
lacks plasticity. The combination of both in a crystalline/metallic glass composite enhances
the mechanical properties.

7. Conclusions and Prospects for the Future

Metallic glass is amorphous and is known for its mechanical properties, such as high
toughness and strength, but lacks plasticity. It can be used in various applications [10–31]
and is prepared by techniques such as melt-spinning, liquid squat quenching, powder
metallurgy, magnetron sputtering, and pulsed laser quenching. The formation of metallic
glass depends on the supercooled region and the critical cooling rate (Rc ). Metallic glass has
excellent mechanical properties as compared to crystalline materials but has low plasticity.
This can be overcome by the introduction of secondary materials to form a metallic glass
composite. The main aim of this review is to provide a brief overview; the background on
metallic glass, its properties, and its application are discussed. Biocompatible composite
and metallic glass based on Ti, Mg, Fe, and Sr are discussed. They have high strength and
can be used in bioimplants and stents. The ex situ composites, fiber-reinforced metallic
glass composites, are a metallic glass polymer and are also discussed. These composites
have increased physical–mechanical properties. Biomaterial composites and metallic
glass based on Ti, Mg, and Fe, are discussed. Metallic glass composite could be used as
degradable bioimplants. Ti–Zr–Cu–Pd–Sn shows better workability than the commercial
Ti and Ti–6Al–4V bioimplants. Biocompatibility and corrosion resistance can be increased
by adding boron to Ti-based metallic glass. In general, Ti-based metallic glass and its
composite show better cytocompatibility, corrosion resistance, and mechanical properties.
Fiber-reinforced metallic glass composites and metallic glass/polymers composites are
also discussed. Zr-based metallic glass is used in the musculoskeletal system. Zr–Ti–Cu–
Ni–Be metallic glasses are used in ceramic films to increase their biocompatibility and
tribological properties. Zr–Cu–Ni–Al composites have better plasticity and are used in
load-bearing implants. The formation of the (Zr2 Cu) nanocrystals leads to passivation,
and an increase in the Y% increases cell activity. The Mg–Zn–Ca/PCL composite shows
biocompatibility. PCL/nHA/Mg (MG) controls the Mg ions release. Mg–Zn–Ca ribbons
have better resistance, biocompatibility, and tribological properties. It was also shown
that the corrosion resistance of Mg–Zn–Ca is better than the commercial AZ31B and Mg.
The addition of the Ag in Mg–Zn–Ca increases the corrosion and controls the hydrogen
evolution. The cooling rate of the Mg–Zn–Ca metallic glass also influences the corrosion
rate in the saline solution. Fe-based composites have potential in hyperthermia and
tumor therapy. The formation of the carbon fiber/Ti–Zr–Be–Fe–Cu and W/(Zr–Ti–Cu–Ni)
increases the mechanical properties, and the addition of Be in the Zr–Ti–Ni–Cu increases the
adhesion of the composite. The addition of the Nb increases the interfacial strength between
the W/MG composite. Recent research was conducted on MG and polymer composites.
Some examples are Mg(MG)/PET, Mg(MG)/HDFE, Zr(MG)/PAN, and Cu(MG)/PTFE.
They are used in structural and industrial applications. Various binders, such as silane, can
be used to improve the interaction between metallic glass and polymer. The addition of the
secondary reinforcement and introduction of the secondary phases increases the mechanical
properties of the metallic glass composites. These composites are generally prepared by
mechanical alloying or heat treatment procedures. The introduction of multiple shear
bands and the formation of nano-crystalline, dendritic, and quasicrystal phases increase
the plasticity of the metallic glass composite.
Metals 2021, 11, 1933 21 of 29

There is a great scope for composites based on metallic glass. Both physical and
chemical properties can be increased by it. In the future, metallic glass composites have
bright prospects in engineering and industrial applications.

Author Contributions: A.S., conceptualization, investigation, writing—original draft preparation;

V.Z., review and editing. All authors have read and agreed to the published version of the manuscript.
Funding: The reported study was funded by RFBR, project number 20-32-90041. V.Z. gratefully
acknowledges the financial support made within the Ministry of Science and Higher Education of
the Russian Federation in the framework of the Increase Competitiveness Program of NUST «MISiS»
(grant number K3-2015-036).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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