Design

Rev.
Adv.
strategies
Mater. Sci.
to 40
improve
(2015)the
1-14
plasticity of bulk metallic glasses

DESIGN STRATEGIES TO IMPROVE THE PLASTICITY OF

BULK METALLIC GLASSES
Qiang Zheng1,2
1

School of Materials Science and Engineering, Ningbo University of Technology, Ningbo 315016, P. R. China
2
Ningbo Branch of China Academy of Ordnance Science, Lingyun Road199, Ningbo, 315103, P. R. China

Received: May 19, 2014

Abstract. Bulk metallic glasses (BMGs) have many excellent properties, such as high strength,
high hardness, high specific strength, better corrosion resistance, and excellent soft magnetic
property as well. However, their lack of plasticity due to the shear localization at room temperature
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materials. So far, a great deal of efforts has been devoted to improving the ductility and toughness
of BMGs. In this paper, the-state-of-art eight successful design strategies were summarized in
order to give clues and directions to improve the ductility and toughness of bulk metallic glass.
Both the advantage and disadvantage of each method were briefly analyzed.

1. INTRODUCTION
Recent years, many bulk metallic glasses (BMGs)
systems, such as, Zr-[1,2], Pd-[3,4], Pt-[5], Cu-[6],
Ti-[7], Mg-[8], Fe-[9], La-[10], Au-[11],Y-[12], Ni-[13],
Ca-[14], Hf-[15], Co-[16], Ce-based [17] BMGs, have
been discovered, and the critical size of BMGs can
be centimeter, even at the inch scale. BMGs have
very high strength compared to their crystalline counterparts because of having no dislocations. However, they show very limited plasticity and no work
hardening when the stress exceeds their yielding
one. Actually, the tendency of working softening will
result in localization of plastic flow, therefore formation of shear bands. The fracture of metallic glass
usually happens in one or a few of the primary shear
bands, and the fracture is catastrophic without any
prognostication. Spaepen [18] first proposed free
volume theory to account for deformation in metallic glasses, in which the deformation is localized
and this localization will give rise to the change of
viscosity and finally results in the inhomogeneous
plastic flow. In fact, typical vein patterns are usually
observed on the fracture surface of metallic glasses,

ascribing to the low viscosity in the shear band.

Additionally, the re-solidified droplet can also be
found on the fracture surface, which indicates the
softening or localized melting at the moment of fracturing [19]. This deadly disadvantage of brittleness
of BMGs, especially at room temperature seriously
restricts their application as structural materials.
To solve the brittleness of monolithic BMGs,
many routes have been tried in approaching this
problem. The methods mainly include (1) ex-situ
second phase particles reinforced BMG composites; (2) in-situ formed BMG composites; (3) high
Poisson ratio BMGs; (4) dual phases BMGs with
phase separation; (5) Interpenetrating phases composites; (6) porous BMG; (7) sample size effect and
(8) BMG surface modification. The purpose of all of
the methods is to increase the density of shear
bands in order to dissipate the deformation energy
into much larger volume and to eliminate the stressconcentration, therefore to improve the plasticity as
well which can be found in detail in a recent review
article on shear bands in metallic glass by Greer et
al. [20].

Corresponding author: Q. Zheng, e-mail: qiangzheng616@hotmail.com

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Q. Zheng

2. DESIGN STRATEGIES TO IMPROVE

THE DUCTILITY AND TOUGHNESS
OF BMGS
2.1. Ex situ second phase/BMG matrix
composites
The following factors need to be considered for selecting the second phase: wettability, reaction degree, thermal expansion coefficient and density, etc.
First of all, the second phase should wet well enough
with the matrix, and the density difference between
them should not be large, and this is the premise of
forming homogeneous composites. Secondly, the
reinforcement materials should not react significantly
with the matrix materials because this will induce
the element in the second phase to immigrate into
the matrix materials, and thus change the initial
composition of the matrix materials. It may also
destroy the glass forming ability (GFA) of the melt
of the matrix alloy. Furthermore, the addition of the
second phase should not facilitate the inhomogeneous nucleation of the competing phases. The difference of thermal expansion coefficient between
the second phase and the matrix material determines the internal stress of the composites, and
this will affect the interactions of the second phase
and the shear bands.
Ceramic particle is one of the best reinforce
phases for fabricating composites in crystalline
materials. In 1997, Kato et al. [21] introduced ZrC
particles with a diameter of 3 m into Zr55Al10Ni5Cu30
BMG and in their experiments both the strength and
the plasticity were improved. Fu et al. [22,23] introduced TiB or TiC into Cu47Ti33Zr11Ni6Sn2Si1 amorphous matrix, and different volume faction of TiB or
TiC reinforced amorphous matrix composites was
formed. Johnson group [24,25] added the SiC and
W C particles into different Cu 47 Ti 34 Zr 11 Ni 8 0Zr52.5Ti5Al10Cu17.9Ni14.6 and Zr57Nb5Al10Cu15.4Ni12.6
BMGs and 3~7% plasticity was obtained under
compressive test. For TiB2 particulate reinforced Mgbased bulk metallic composites [26], the plasticity
was improved in a certain degree, and the maximum fracture strength is 1330 MPa and plasticity
strain is 3.2%. These results show that selected
matrix materials should have relatively low melting
temperature so as to control the interface reaction
and keep the original GFA of the matrix materials.
Higher melting point and ductile metal particles
are also another choice to be selected as the reinforcement. Choi-Yim et al. [25,27] added particulate W, Ta, Mo, Nb into V106, and the range of plastic deformation of the material was dramatically

Fig. 1. The compressive stress-strain for tungsten/

Zr41.25Ti13.75Cu12.5Ni10Be22.5 composites with different
volume fraction of tungsten. Reprinted with permission from R. D. Conner, R. B. Dandliker and W. L.
Johnson // Acta Mater. 46
(00/ - /0 p (00/
Elsevier.

improved under compression due to the formation

of multiple shear bands in the presence of particles.
Conner et al. [28] selected the tungsten and steel
fibers as the reinforcement phase for the classic
Zr41.25Ti13.75Cu12.5Ni10Be22.5 BMG (Vitreloy 1). This kind
of materials shows excellent properties, and the
compressive yielding strength is above 2100 MPa
and plastic strain is above 15% when the volume of
tungsten fibers exceeds 60%. The compressive
stress-strain for tungsten/ Zr41.25Ti13.75Cu12.5Ni10Be22.5
composites with different volume fractions of tungsten is shown in Fig. 1. Other metal particles, such
as Nb [29], Fe [30], porous Mo [31] and Ti [32] reinforced Mg-based BMGs have fracture strength of
900~1100 MPa and compressive plastic strain in
the range of 10~40%.
The ex situ second phase reinforced BMG composites can be divided into two categories: one is
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be stress concentration at the interface of the soft
reinforcement phase and the matrix with the increasing of deformation degree. When the stress concentration reaches a critical value, the formation of
the first shear band will be triggered. Then, the stress
around the particle will decrease after shear band
formation. Meanwhile, shear bands will form around
other particles where the stress concentration
reaches the critical value. Therefore, multiple shear
bands form and propagate in the composite material. The shear band will expand to the directions of

Design strategies to improve the plasticity of bulk metallic glasses

harder particles, then the higher loading is needed

to be applied. Therefore, usually BMG composites
have higher strength and less plasticity when they
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2.2. In situ second phase/BMG

composites

Fig. 2. SEM backscattered electron image of in situ

composite microstructure (magnification = 200x).
(Inset:
X-ray diffraction
pattern
for
(Zr75Ti18.34Nb6.66)75X25, in situ composite. X represents
the moiety Be9Cu5Ni4). Reprinted with permission
from C. C. Hays, C. P. Kim and W. L. Johnson //
Phys. Rev. Lett. 84
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the neighboring particles because the effect of residual stress in the matrix material. This will make
it impossible that the shear bands propagate in the
composites without being blocked/pinned or absorbed. The final result will be that these shear
bands are blocked by the nearby particles or they
bypassed/got through and then be blocked again,
and so on. Shear band branching will happen when
the propagation of the shear bands is blocked by
the particles. And, shear bands will stop propagation/expanding because of the decreasing of stress
at the tip of shear bands when they come into the
particles. The results of these interactions will lead
to the homogeneous distribution of multiple shear
bands, and finally the plasticity will be strengthened.
For the latter, the matrix material will deform first
and the shear band will initiate within matrix materials. After that, the stress concentration will happed
at the interface of these two different phases, which
will lead to the formation of multiple shear bands.
When the extending of the shear bands meets the
second harder phase, they will deflect and change
their initial directions. In both cases, the effects of
interactions between the second softer/harder phase
and the matrix material are to facilitate the formation and to impede the extending of the multiple
shear bands. If shear bands would get through the

The formation of the in situ BMG matrix composites is to utilize the preferred precipitation of a certain primary phase during the solidification process
of the melt, but this would not give rise to the crystallization of the remained melt. After that, the remained melt will be cooled continuously, and
changed into amorphous phase and thus the BMG
matrix material reinforced by the in situ second
phase formed. Compared to ex situ method, the interface between the second phase and the matrix
material combines closely, and the second phase
is distributed homogeneously as well if in situ
method was applied. On the technology side, this
kind of materials can be finished in one step and
has the advantage of concise and short flow diagram.

2.2.1. In situ precipitated second

phase during solidification
The primary crystalline phase precipitates preferentially from the melt by adjusting the alloy composition and controlling the cooling rate. The composition of the remained melt deviates from the initial
nominal one, however still keeps a better GFA, and
transforms into glass phase during the further cooling process. In this way, the in situ second phase/
BMG composite forms. The primary crystalline
phase can be micro scale dendrite, or nano scale
particle depending on different systems. The first
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and preparing a Zr-based BMG composite with excellent properties. They first selected the alloys on
the line connected the classic BMG formerZr41.2Ti13.8Cu12.5Ni10Be22.5 and tough Zr-based solid
solution phase ( -phase). Upon cooling from high
temperature, the melt undergoes partial crystallization by nucleation and subsequent dendrite growth
of the phase in the remaining liquid. The remaining liquid subsequently freezes to the glassy state
producing a two phase microstructure containing
-phase dendrites in a glassy matrix. SEM image

Q. Zheng

Fig. 3. Enhanced room-temperature tensile ductility of DH1, DH2, and DH3. Backscattered SEM micrographs showing the microstructure of DH1 (a) and DH3 (b) where the dark contrast is from the glassmatrix
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DH2, and DH3 in room-temperature tension tests. (d) Optical micrograph of necking in DH3. (e) Optical
micrographs showing an initially undeformed tensile specimen contrasted with DH2 and DH3 specimens
after tension testing. (f) SEM micrograph of the tensile surface in DH3 with higher magnification shown in
the inset. SEM micrographs of necking in DH2 (g) and DH3 (h). (i) Brittle fracture representative of all
monolithic BMGs. Reprinted with permission from D. C. Hofmann, J. Y. Suh, A. Wiest, G. Duan, M. L. Lind,
M. D. Demetriou and W. L. Johnson // Nature 451
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of in situ composite microstructure is given in Fig.

2. And, it is reported that Zr-based BMG composites have excellent mechanical properties with compressive plasticity of 6% and tensile ductility of 5%,
and fracture strength of 1.7 GPa at room temperature. It is worthy noting that the average Charpy
impact toughness for this Zr-based BMG composite is 200 kJ/m2, and 250% higher than that of monolithic Zr-based BMG. Qiao et al. [35,36] and Zhang
et al. [37] also got better tensile strength and a large
tensile plastic strain of 15.5% at room temperature
for Ti-based BMG composite using the Bridgman
solidification method. Additionally, Mg-based BMG
composites reinforced by homogeneously dispersed
-Mg with 14H [38] and 6H [39] long period stacking (LPS) structure have fracture strength of ~1.2
GPa and the compressive plastic strain can reach
~18%.

2.2.2. Coarsening the second

precipitated phase using
semi-solid processing
Because of the uncontrolled condition during the
normal solidification process, the precipitated crystalline phases have different size at different parts.
In order to fabricate homogeneously distributed dendrites in BMG composites, the semi-solid processing technology was applied, and it can produce a
more uniform microstructure which varies minimally
with cooling rate. Johnson et al. [40] increased Ti
content to reduce density and eliminated Ni to enhance fracture toughness of the glass on the basis
of Vitreloy 1 and synthesized in situ Zr-based BMG
composite with reinforced bcc structure dendrite
Zr40Ti45Nb14Cu1 homogeneously distributed in a
glassy matrix. This composite has tensile plastic-

Design strategies to improve the plasticity of bulk metallic glasses

this kind of method. But, most of the BMG matrixes

have the tendency of brittleness [43-45], because
the structural relaxation resulted from the heating
process as well as the precipitated brittle intermetallic phases will both deteriorate the mechanical
properties. Therefore, the non-satisfying results restrict the widely application of this method.

2.2.4. Phase transformation mediated

ductility of bulk metallic glass
Fig. 4. Engineering tensile stress-strain curves of
the BMG composites. Dashed lines indicate the
unloading process. Top inset shows the outer appearance of the tensile samples pre-strained at the
different stages and the lower inset shows the true
tensile stress-strain curves, indicating a significant
strain-hardening behavior. Reprinted with permission
from Y. Wu, Y. H. Xiao, G. L. Chen, C. T. Liu and Z.
P. Lu // Adv. Mater. 22
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VCH Verlag GmbH & Co. KGaA, Weinheim.
ity of 9.6~13.1% at room temperature, apparent
necking happens and reduction in fracture area is
about 40~50%. Enhanced room-temperature tensile ductility of semi-solid processing in situ Zr-based
BMG composites is shown in Fig. 3. And, this is
another milestone for synthesizing metallic glass
composites. After that, many groups are following
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composites by semi-solid processing method. Thus,
many papers investigation on tensile properties of
BMG composites are emerging after 2008.

2.2.3. Nano particles reinforced

amorphous matrix composite
(Crystallization from amorphous
solids)
Amorphous alloy is a kind of metastable materials,
and it has the tendency to crystallize during heating process. This kind of properties can be applied
to synthesize in situ composites containing precipitated phases with the length of tens nanometer
which are distributed in amorphous matrix when a
proper annealing process, mainly annealing temperature and time is selected. This kind of composites would have certain plasticity due to the interactions between nano phases and shear bands and
good interface properties which are facilitated to the
formation of multiple shear bands. Since the 1990s,
widely researches have been done to improve the
ductility of Zr- and Cu-based BMGs [41,42] using

Many in situ BMG matrix composites were synthesized successfully; however, most of them show
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the stress-strain curve or the maximum stress is
usually defined as failure. To circumvent this problem, it is necessary that in situ precipitated phase
should have work-hardening properties to impede
the propagation of shear bands of monolithic metallic glasses. Recently, people pay more attention to
the phase transformation formed second phase/BMG
composites. Zhang, Lu, Zheng, Eckert group [46,47,)RX
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Fig. 4. It can be seen that BMG composite exhibits
a distinct tensile behavior with yielding stress of 1280
MPa, maximum tensile strength of 1650 MPa and
7% plastic strain. Additionally, this kind of composite exhibits a martensitic transformation from B2 to
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pronounced work hardening of this kind of BMG
composites. This transformation during deformation
process not only enhances the plasticity of BMG
composites but also leads to overall work hardening of the composite on compressive loading just
like that in crystalline materials.

2.3. Monolithic BMG with high

Poisson ratio
Currently, it is not clear about the intrinsic factors
that affect the macro-plasticity of monolithic BMG.
Some researches indicate that there is a certain
correlation between the Poisson ratio and plasticity of BMG [53]. As a rule of thumb, BMGs have a
higher Poisson ratio may have a better plasticity
[53-57].

Q. Zheng
petition between plastic flow and cleavage propagation that controls the fracture process in MG. A higher
decreases the potential energy of the shear transformation zone (STZ), thereby increasing the tendency of plastic deformation in mitigating fracture
stress concentration [60]. However, so far there is
no other monolithic BMG except Pt-based BMG with
higher Poisson ratio and a larger plasticity was successfully designed.

2.4. BMGs with phase separation

Fig. 5. Stress-strain curve of amorphous monolithic

Pt57.5Cu14.7Ni5.3P22.5 BMG. Reprinted with permission
from J. Schroers and W. L. Johnson // Phys. Rev.
Lett. 93
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Chen et al. [54] first suggested that the higher
of MGs, as indicative of the ease of atomic
regroupings, is responsible for the ductile plastic
deformation. Recently, Schroers et al. [55] found
that a Pt-based BMG with a high value of 0.42
exhibits large compressive plasticity with compressive strength of 1400 MPa, plastic strain of 20%
and high fracture toughness (KQ= 80 MPa.m1/2) at
room temperature. In Fig. 5, stress-strain curve of
amorphous monolithic Pt57.5Cu14.7Ni5.3P22.5 BMG is
shown.
Independently, Lewandowski et al. [53] proposed
a critical value of /B %
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such transition is exhibited in Fe-based BMGs
[58,59]. Wang group [56] systematically studied the
correlation between the ductility and composition
in Zr-Ti-Ni-Al system. BMGs with different elastic
properties were obtained by adjusting the alloy compositions. Their results indicated that the plasticity
of BMGs is sensitive to the composition change.
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smaller than 1 at.%, will have a dramatic effect on
the ductility of BMGs. The apparent compressive
plasticity of monolithic Zr64.13Cu15.75Ni10.12Al10 BMG can
reach 160%, while for another Zr65Cu15Ni10Al10 BMG
(within 1 at.%) has nearly no plastic strain. These
obvious and different experimental results are ascribed to the different Poisson ratio of 0.377 and
0.355 for Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10
BMG, respectively. Correlation of toughness/ductility with (or /B) for MG is explained in terms of
competition between shear and dilatation or com-

Recently, it indicated [56,61,62] that if there is some

inhomogeneous structure in BMGs, for example,
dual amorphous structure, then, better plasticity may
be obtained. The earliest work to obtain the dual
amorphous structure is to add two kinds of alloy
elements which have positive mixing enthalpy. In a
certain composition range, GFA and plasticity can
be improved together [63]. But the challenging question is how to locate the optimal BMG composition
having the phase separation? Du et al. [64] determined the best Zr63.8Cu16.2Ni15Al5 BMG composition
with the dual amorphous structure using the thermodynamic calculation method. The experimental
results indicated that there are two kinds of Cu rich
and Ni rich amorphous phases existed and the
macro-compressive plasticity strain can reach 30%.
In Fig. 6, room temperature stress-strain curve for
as-cast 2 mm diameter cylinders of two-glassyphase Zr-based BMG. It can be seen that two-

Fig. 6. Room-temperature stress-strain curves for

as-cast 2 mm diameter cylinders of two-glassyphase Zr-based BMG with conventional Zr-based
BMG as a reference. The inset shows the deformed
sample. Reprinted with permission from X. H. Du,
J. C. Huang, K. C. Hsieh, H. M. Chen, J. S. C. Jang
and P. K. Liaw // Appl. Phys. Lett. 91 (2007) 131901,
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Design strategies to improve the plasticity of bulk metallic glasses

glassy-phase Zr-based BMG has a larger true strain
than that of conventional Zr-based BMG. Another
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a Zr-based BMG containing Cu and Co, because
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ratio between Zr45Cu50Al5 and Zr55Co25Al20 BMGs,
new Zr-based bulk metallic glasses (BMGs) with
improved plasticity were developed. When the concentration ratio is 1:1, compressive plasticity of 12%
was achieved which was attributed to atomic-scale
chemical/structural fluctuations achieved through
liquid-phase separation.
Phase separation will result in some regions with
different chemical compositions, different cooperation numbers and different nearest atomic numbers.
Finally, there will be inhomogeneous distribution of
hardness (modulus). The formed two amorphous
phases have different critical shear stress (CSS) to
facilitate the shear bands. When yielding, the relatively soft phase will have more free volume, and will
deform and shear preferentially, which will become
the center of nucleation. Additionally, more interfaces between the soft and hard phases which having higher CSS will impede the extension of shear
bands, facilitate the initiation of shear bands, and
result in macro plasticity. But, the dual amorphous
phase is not the sufficient condition. For instance,
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the dual amorphous phases are very brittle, while
the monolithic BMG (x=2.5) has a good ductility.

2.5. Interpenetrating BMG/ductile

metal composites
In contrast to most BMG composites, in which the
reinforcement phase are discrete, interpenetrating
phase composites (IPCs) [67,68] have emerged
which contain no isolated phases and each individual solid phase within the fully dense composite
formed a completely homogeneously interconnected
network. This kind of structure creates the opportunity to introduce large-volume of ductile phase into
the metallic glass and leads to a totally uniformed
phase distribution. In this interpenetrating phase
composites, both the matrix and the reinforced
phase form their own network in the three dimensional space which endows this composite some
properties that are better than those of traditional
composites having discrete reinforced phases. This
interpenetrating structure is facilitate to the formation of shear bands, and can improve the load bearing ability and impact resistance because the ap-

plied loading stress at the point/on the surface can

be dissipated and transmitted quickly in three dimensional space. Researcher have systematically
studied the SiC[68], W metal [69-71], Ti metal
[68,72] and Fe [73] metal/amorphous bi-continuous
phases composites which showed excellent plastic deformation ability. Especially for the W/Ti-based
BMG composite prepared by pressure infiltration,
the fracture strength increases from 1852 MPa for
the as-cast composite to 2112 MPa for the extruded
composite. Typical true stress-true strain curves for
the pure metallic glass, pure tungsten, the as-cast
composite, and the as-extruded composite was
shown in Fig. 7. The improved mechanical properties of the as-extruded composite are proposed to
contribute to the stable interface between the metallic glass phase and tungsten phase and the high
dislocation density of the tungsten phase [71].

2.6. Porous BMG (BMG foam)

Although Apfel and Qiu [74] proposed a potential
BMG-foaming process as early as 1996, it was not
until 2003 that Schroers et al. [75] successfully
foamed the Pd43Ni10Cu27P20 BMG by releasing water vapor during decomposition of a hydrated B2O3
flux. Later, Wada et al. [76] foamed the same alloy
by water quenching a mixture of the Pd-Cu-Ni-P alloy liquid and solid salt (NaCl) in a silica tube, followed by dissolution of the NaCl. Brothers et al.
[77] prepared the first Zr-based BMG foam by melt
infiltration (MI) Zr57Nb5Cu15.4Ni12.6Al10 into a bed of
hollow carbon microspheres.
After that, people tried many different methods
to prepare different BMG foam materials [78-84].
Demetriou et al. [81] utilized Zirconium hydride as
a foaming agent to fabricate amorphous Fe-based
metal foam taking advantage of the low hydrogen
solubility of the glass-forming alloy. The porosities
up to 65% were produced, and the BMG foam has
homogeneous cellular morphologies which exhibit
cell-size uniformity, but no data about the mechanical properties were reported. They [83] also used a
powder metallurgy route to consolidate metallic
glass blended with blowing agent particulates
(MgCO3) to produce expandable precursors, and the
yielded porosity can be as high as 86%. Xie et al.
[82] also investigated the porous Zr55Cu30Al10Ni5 bulk
metallic glass fabricated by spark plasma sintering
(SPS) process. Their results show that the porous
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in the sintered porous BMG samples which generate multiple shear bands. Pd42.5Cu30Ni7.5P20 BMG was

Q. Zheng

Fig. 7. Typical true stress-true strain curves for the pure metallic glass, pure tungsten, the as-cast composite, and the as-extruded composite. Reprinted with permission from Y. F. Xue, H. N. Cai, L. Wang, F. C.
Wang and H. F. Zhang // Appl. Phys. Lett. 90
) . /(0 ( p) .7 Wd
[
US ?ef
[
f
gf
WaXFZk
e[
Ue%

isothermally held at 853K for 3~12 hours under hydrogen pressure of 1~4 MPa, after that Pd-based
BMG was quenched by oil or water [80]. The obtained BMG has a volume ratio of 1.7~3.7% spherical porosity which is homogeneously distributed with
diameter of 20~30 mm and distance of 80~110 m.
Compared with monolithic BMG, the porous BMG
has a plastic strain of 4.5 ~18%, and the yielding
strength is 1520 MPa which is slightly lower than
that of monolithic BMG having a fracture strength of
1630 MPa. Tensile and compressive stress-strain
curves of Pd42.5Cu30Ni7.5P20 BMG rods with different
porosities were shown in Fig. 8. The disadvantage
of the porous BMG is that when the porosity is
higher, the strength was dramatically decreased
even though the plasticity was improved.
Sometimes a few methods can be combined
together to improve the plasticity of BMG. A classic
example need to be mentioned: first Ni-based BMG
composite by mixing metallic glass powder with
fugitive second phase (brass) was prepared by powder extrusion [84], then followed by dissolution the
fugitive brass in an aqueous HNO3 solution [79]. The
porous metallic glass has a specific surface area of
23.5 m2/g [85]. Another example is to first produce
phase separated Y20Ti36Al24Co24 BMG consisting of
two phase amorphous alloy: Ti43.3Y3.7Al15.3Co37.7 and
Y38.8Ti12.8Al37.1Co11.3 amorphous phases. Then the
nanometer-sized porous Ti-based metallic glass was
obtained by selectively dissolving the Y-rich phase
by both chemical and electrochemical treatments
in 0.1 M HNO3 solution. However, the mechanical
properties of BMG foam are not good enough which
indicates that BMG foam is not an ideal way to improve the ductility of BMGs. BMG foam may be a
good candidate for catalytic applications, for instance

[86] the nanoporous metallic glass Pd, fabricated

by de-alloying Pd30Ni50P20 exhibited a remarkable
catalytic activity for the Suzuki-coupling reaction and
is reusable and sustainable without a significant loss
of catalytic activity.
Usually, the porous BMGs prepared by the abovementioned methods have a disordered pore structure and size. To obtain a uniform pore structure
and size, Chen et al. [87] prepared Zr-based BMG
with unidirectional pores by electrochemical etching of tungsten wires of the W/BMG composites.
The result indicates that yield strength decreases
from 2000 to 820 MPa for monolithic and porous Zrbased BMG and the plastic strain before fracture
increases from 0.3% to 0.62%, respectively.

Fig. 8. Tensile and compressive stress-strain curves

of Pd42.5Cu30Ni7.5P20 BMG rods with different porosities. Reprinted with permission from T. Wada, A.
Inoue and A. L. Greer // Appl. Phys. Lett. 86 (2005)
),(0 . p) ,7 Wd
[
US ?ef
[
f
gf
WaXFZk
e[
Ue%

Design strategies to improve the plasticity of bulk metallic glasses

Fig. 9. Sample I at various stages of tensile elongation during the in situ TEM experiment. The average
ef
d
S[d
Sf
WiSeSTagf,w( -4 s-1. The straight gauge section is marked with dashed white lines. (a-e) This
series of video frames demonstrates that the virgin sample before testing (a) was uniformly elongated to a
strain of 15% (b), where non-uniform deformation began; one major shear was initiated, and the shear offset
grew with further straining together with significant elongation in the necked region indicated by the white
arrow (c-e). The tensile strain for e reached 45%. Reprinted with permission from H. Guo, P. F. Yan, Y. B.
Wang, J. Tan, Z. F. Zhang, M. L. Sui and E. Ma // Nature Mater. 6
) . . , p) .DSf
gd
WFgT[
eZ[Y
Group.

2.7. Sample size effect on ductility

exhibited by metallic glasses
For the monolithic glasses, a recent discussion [88]
suggests that the low ductility and the corresponding low process-zone size of BMGs would become
unimportant when the sample dimensions are reduced down to micrometer regime.
It is well known that amorphous ribbon with a
thickness of tens micrometer can be bent even to
0 oi[
f
ZagfX
d
SUf
gd
[Y%MZkTg] Wf
S[
UYSee[
e
brittle? Is there size effect existing in bulk metallic
glass as that in crystalline metals [89]? Sample
size effect was proposed by Ashby et al. [87] who
assumed that if the sample size is much smaller
than the critical process zone size of the material,
there is likely to be plastic flow without fast fracture.
In 2007, Zheng et al. [90] fabricated a Mg-based
BMG micro-pillar with a diameter of 12 m using
dual Focused Ion Beam (FIB) which showed 3.2%
overall plastic strain. The micro-pillar sample shows
an obvious size effect compared with the larger
samples having diameters of 1 mm and 4 mm which
have no or nearly zero plasticity. After that, Guo et
al. [91] in situ tested the FIB fabricated Zr-based
BMG sub-micro samples in a transmission electron microscope (TEM). Large tensile strain about
23%-45%, obvious necking and the area reduction
ratio at fracture as high as 80% were observed in
their experiments (see Fig. 9). Jang and Greer [92]
found that the Zr-Ti-Co-Be metallic glass deformed
homogeneously with the engineering tensile strain
of about 6% before necking and fracture, resulting
from the suppressed shear banding in small-sized
specimen. Under confined testing conditions, tensile ductility can be further enhanced compared with
the free-standing uniaxial tension test. Volkert et

al. [93] also tested an array of uniaxial compression on PdSi metallic glass columns with diameters
range from 140 nm to 8 m. It was found that when
diameter smaller than 400 nm, homogeneous deformation will happen after elastic regime. Otherwise, the columns will exhibits shear band formaf
[
a a SbS WSf
, of
af
ZWaSV[YSj
[
e%
Agl [et
al. [94] even fabricated metallic glass nanopillars
with diameters ranging from 90 to 600 nm to be
tested in situ TEM in order to investigate the intrinsic and extrinsic effect of metallic glass. In order to
rule out any artifact induced by the ion-beam damages, Luo et al. [95] designed one perfect experiment by in situ controlling the W probe to touch
and compress the nonohill producing at the edge of
TEM sample. It is amazing that Al90Fe5Ce5 metallic
glass with a size <20 nm can be extremely elongated to ~200%. Remarkably, even an atomic chain
was formed after sample necking, which was never
observed in metallic glasses. Recently, Wang et al.
[96] in situ observed the deformation experiments
of Pd-based metallic glass submicro-sized wires in
TEM. Compared to bulk counterparts, MG wires
exhibit intrinsic ultrahigh tensile strength of ~2.8
GPa, which is twice as high as that in Pd-based
BMG.
Except for the abovementioned nano/micro pillars fabricated by FIB and nonahills of the TEM
samples produced by the twin-jet method, another
size effect factor is aspect ratio of BMG [97-100].
Bei et al. [98] also found that the fracture surfaces
of the small specimens are smooth without the characteristic vein patterns seen in large specimens.
With increasing the mechanical-testing size of specimen, it is demonstrated that more pronounced action of elastic recoveries of specimen led to a decrease in plasticity because of larger shear strain
was introduced in shear bands. Recently, Sarac et

10

Q. Zheng

Fig. 10. Effects of surface treatment on plasticity in uniaxial compression. (a) Two as-cast samples are
compared with those with treated surfaces: one abraded, and two peened samples. (b,c) Scanning electron
micrographs of areas (shaded in the inset to a) close to the fracture surface show that shear-banding is
sporadic in an as-cast sample (b), but uniformly distributed in a peened sample (c). Reprinted with permission from Y. Zhang, W. H. Wang and A. L. Greer // Nature Mater. 5
) - /,. p) - DSf
gd
WFgT[
eZ[Y
Group.

al. [101] designed metallic glass heterostructure with

second phase at micrometer scale and systematically studied the effect of diameter, spacing and different array mode of second phase on deformation
behavior of artificially designed metallic glass
heterostructures. They pointed out that there exists a maximum peak when d/s=1 in Fig. 4a of Ref.
[101] which gives the relationship between the ratio
of diameter (d) and spacing (s) of second phase
and fracture stress-strain under tensile condition. It
was shown that even the traditional BMG can be
ductile as the casting size and mechanical-testing
size of specimen were concurrently decreased to a
certain extent.

2.8. BMG surface modification

Shot peening treatment is also called shot peening
strengthening, which is an effective method to improve the fatigue life and corrosion resistance of the
conventional alloys. After shot peening, a certain
thickness of the reinforcing layer was formed on the
deformed surface of alloys. This induces compressive stresses only in a thin surface layer and the
tensile stress in the interior is small and relatively
uniform. Zhang et al. [102] controllably induced residual stresses in a bulk metallic glass by shot
peening method, and they improved the mechanical performance, in particular the plasticity. The effects of shot peening are dramatic, with the compressive plasticity increased from the average 6%,

maximum 7%, in as-cast samples to average 11%,

maximum 22%, in peened samples (see Fig. 10).
The other BMG surface modification method was
from Wang et al. [103] by applying surface mechanical attrition treatment (SMAT) which was proposed
by K. Lu and J. Lu in 1999 [104] . It is reported [103]
that SMAT is an effective method to form gradient
amorphous microstructures across the sample
thickness. The results showed that bulk metallic
glasses can exhibit both a high strength of 2 GPa
and an unprecedented tensile elongation of 2-4% at
room temperature. The underlying reason is that the
tensile ductility comes along with a gradient amorphous microstructure, which promotes multiple
shear banding while suppresses shear cracking at
room temperature. Because SMAT can produce
u
eaX
f
W WVv
8C=egd
X
SUWiZ[
U
Zcan offer easy sites
for shear band nucleation as suggested in the previous work [98].
Another BMG surface modification method is
metal coating confinement, such as Cu, Ni, and Cu/
Ni bilayer coating electroplating [105-107], which
have been proved to be effective in toughing Zr-based
BMG. This is similar to shrink-fit metal sleeve confinement [108] in which the highly dense and frequent interacting and arresting events of shear bands
formed that are the origin of the observed large global plasticity. However, it is worth noting that the
plasticity enhancement was found to be closely related to the thickness of metal coating.

Design strategies to improve the plasticity of bulk metallic glasses

3. SUMMARY
Bulk metallic glass is a new kind of material which
has the potential application as structural materials. However, due to its brittleness and no plastic
strain at room temperature, it is not reliable to be
applied as structural materials. In this paper, we
summarized state-of-the-art eight design strategies
to improve the ductility and toughness of monolithic
BMGs. A key point is that usual methods and experiences to improve the crystalline materials can
TWs
Tad
d
aiWVtS Vf
aTWSbb[
WV[f
ZWS ad
bZage
alloy research field.
Design strategies can be divided into two categories: intrinsic compositional manipulation and
extrinsic modification. Monolithic BMG with high
Poisson ratio, BMG with phase separation, in situ
BMG composites can be grouped into intrinsic compositional manipulation and the others are belonging to the extrinsic modification. Among them, the
in-situ BMG composite seems to be the most promising method because of the good interface properties and the blocking of shear band propagation and
facilitating the formation of multiple shear bands
which are induced by the existing of ductile crystalline phase.
The key point to improve the plasticity of BMG
is that both multiple shear bands and stable shear
deformation ability should be the premise of the
considerable tensile plasticity for metallic glasses.
Facilitating shear band initiation and impeding shear
band localization, especially under tensile condition, is a strong deterrent to apply BMG as structural materials. Suggestions and challenges for future efforts are how to obtain metallic glass with
strain hardening and stable reliability, especially for
bulk metallic glass? Because when the specimen
size of metallic glass is larger than the equivalent
critical shear offset, the shear deformation is unstable, usually leading to a brittle fracture [109].
Theoretically, to tough BMGs, understanding shear
bands is the basis and the key to the future application of metallic glasses as a new class of structural materials, as pointed out in Ref. [20]. Technically, to solve the brittleness of BMG, many design
methods can be can combined together, for example, in situ plus ex situ method to obtain BMG
composites with strain hardening properties or BMG
composites strengthened by shot peening method
or SMAT. Sever plastic deformation [110] is an effective method to induce work hardening properties
in order to improve ductility of BMGs. Only after
strain hardening and stable reliability obtained for
BMG, the real and wide application as structural

11

material will be realized. Otherwise, it is only can

be a good candidate for small scale applications,
such as MEMS/NEMS.

ACKNOWLEDGEMENTS
This work was supported by the Start-up Grant from
Ningbo University of Technology, China Postdoctoral
Science Foundation under grant No. 2012M511390
and No. 2013T60608, Natural Science Foundation
of Ningbo City under grant No. 2012A610102 and
the Technology Foundation for Selected Overseas
Chinese Scholar, Ministry of Human Resources and
IaU[
S IWUgd
[
f
kaXf
ZWFWabWv
eHWbgT[
UaX9Z[S%
Also, the author would like to thank Elsevier Ltd.,
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim,
Nature Publishing Group, American Physical Society and AIP Publishing LLC for copyright licenses
and permissions provided by Copyright Clearance
Center (CCC) - www.rightslink.com.

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