Journal of Alloys and Compounds 747 (2018) 595e602

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Enhanced strain rate sensitivity of Zr-based bulk metallic glasses

subjected to high pressure torsion
E.V. Boltynjuk a, *, D.V. Gunderov b, c, E.V. Ubyivovk d, M.A. Monclús e, L.W. Yang e,
J.M. Molina-Aldareguia e, A.I. Tyurin f, A.R. Kilmametov g, A.A. Churakova b, c,
A.Yu. Churyumov h, R.Z. Valiev a, b
a
Saint Petersburg State University, 28 Universitetskiy pr., Saint Petersburg 198504, Russia
b
Ufa State Aviation Technical University, 12 K. Marx str., Ufa 450008, Russia
c
Institute of Molecule and Crystal physics RAS. Prospekt Oktyabrya 151, Ufa 450075, Russia
d
ITMO University, 49 Kronverksky pr., Saint Petersburg 197101, Russia
e
IMDEA Materials Institute, Calle Eric Kandel 2, 28906 Getafe, Madrid, Spain
f
Research Institute for Nanotechnologies and Nanomaterials, Derzhavin State University, Tambov 392000, Russia
g
Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
h
National University of Science and Technology “MISiS”, Moscow 119049, Russia

a r t i c l e i n f o a b s t r a c t

Article history: The Zr62Cu22Al10Fe5Dy1 bulk metallic glass (BMG) was subjected to high pressure torsion (HPT) at room
Received 21 October 2016 temperature. The state after HPT processing demonstrates presence of large number of heterogeneities in
Received in revised form amorphous structure e shear bands. Nanoindentation was used to study the effect of HPT processing on
28 February 2018
deformation behavior and strain rate sensitivity (m). It was found that HPT significantly affects me-
Accepted 2 March 2018
chanical behavior of BMG during nanoindentation. Decrease in hardness and Young's modulus was
Available online 3 March 2018
observed after HPT. At the same time HPT processing led to an increase in m from 0.014 for the as-cast
material to 0.036. The lack of serration flow and shear bands around imprints was observed in addition to
Keywords:
Metallic glasses
above mentioned changes. A much less localized deformation mode under nanoindentation along with
High pressure torsion an increase in values of strain rate sensitivity of HPT-processed state in comparison with the initial state
Transmission electron microscopy imply homogeneous deformation behavior after processing. The observed drastic changes in deforma-
Nanoindentation tion behavior and structure can be explained as the formation of a highly-heterogeneous amorphous
Strain rate sensitivity structure resembling nanoglasses in result of HPT processing.
Shear transformation zones © 2018 Elsevier B.V. All rights reserved.

1. Introduction deformation [8,9]. In a similar way, high pressure torsion (HPT) is of

Bulk metallic glasses (BMG) have attracte great interest due to
their excellent mechanical properties, such as high strength, large
elastic elongation limit [1,2]. However, possible applications of
glasses are considerably limited by their brittleness at room tem-
perature [3e5]. The influence of various plastic deformation pro-
cesses on the properties of BMGs has been investigated [6e9] in
order to modify their ductility. Particularly, it has been demon-
strated that accumulative roll bonding (ARB) can lead to increased
ductility of BMGs due to the formation of high density of shear
bands that prevent the propagation of new bands forming during
* Corresponding author.
E-mail address: st024107@spbu.ru (E.V. Boltynjuk).
great interest due to the severe plastic deformation [10,11] induced
into the processed material. In crystalline materials, HPT typically
leads to grain refinement and formation of a nanocrystalline
structure. In amorphous alloys, heavy shear deformation by HPT
generates the formation of a high density of localized SBs, which
modify the local atomic structure of metallic glasses [12e16],
enhance the properties and may lead to increased ductility [16].
Thus, investigation of mechanical properties of amorphous alloys
after HPT processing is of interest from both scientific and tech-
nological points of view. However, HPT-processed samples of
amorphous alloys have small geometrical dimensions, therefore
study of their mechanical properties (values of Young's modulus
and strain rate sensitivity) by means of tensile or compression tests
is quite complicated task.
In recent years nanoindentation has become a widely used

https://doi.org/10.1016/j.jallcom.2018.03.018
0925-8388/© 2018 Elsevier B.V. All rights reserved.
596 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602

method to investigate mechanical properties of wide range of following principle. As was mentioned above, the m-value can be
amorphous alloys [17e19]. Nanoindentation in most studies was determined during several uniaxial tensile or compression exper-
used to determine the Young's modulus and hardness and to iments under different strain rates or by using strain rate jump tests
investigate the serrated flow of load-displacement curves of during a single macroscopic test. Generally, in these tests flow
amorphous alloys [20e22]. In several works nanoindentation was stress s and applied strain rate Ɛ_ are linked by the relationship:
also used to study the strain rate sensitivity of amorphous alloys
[23,24]. Strain rate sensitivity (m) provides important information s ¼ Bεm (1)
about the rate limiting processes during plastic flow, such as the
activation volume and energy [23,24]. For crystalline materials, a where B is the temperature-dependent material constant, and m is
low value of m (0.01) indicates the dislocation glide as the con- the strain rate sensitivity parameter. From equation (1), it can be
trolling deformation mechanism. Increased contribution of grain seen that the parameter m can be obtained from the slope of the
boundary sliding and diffusion processes is usually observed at _
plot ln (s) e ln (Ɛ):
higher values of m, leading to superplasticity effects for m values of

0.4 [25]. As a result, the tendency for strain localization is larger
dðln sÞ
for low m values, while high m values are typically associated with m¼ (2)
dðln ε_ Þ
more homogeneous and uniform deformation of the material by
diffusional creep. One can assume the same dependency for It is well known that due to the self-similarity of the pyramidal
amorphous materials, namely that high values of m will contribute indenter and in the absence of indentation size effects, hardness H
to more homogeneous deformation [24], while low values of m will is proportional to flow stress [29] and that the indentation strain
increase the tendency for strain localization processes in amor- rate ε_ ind can be defined as:
phous alloy, dominated by the formation of SBs.
However, to our knowledge, no research on the effect of HPT on
h_
the strain rate sensitivity of BMG's is currently available in litera- ε_ ind ¼ (3)
ture. Thus, investigation of the mechanical properties of amor- h
phous alloys processed by HPT by means of nanoindentation is of where h and h_ are the penetration and rate of penetration of the
interest from both scientific and technological points of view. indenter, respectively. Therefore, it is possible to establish an
Studies have shown that the strain rate sensitivity of amorphous analogy between uniaxial testing and indentation to determine
alloys depends strongly on their structural parameters (free vol- strain rate sensitivity m from:
ume, topological order) [24]. It should be noted that it is extremely
difficult to record changes in these structural parameters of
dðlnHÞ
amorphous alloys by methods of structural investigations, while m¼ (4)
nanoindentation enables recording rather easily changes in Young's dðln_εind Þ
modulus, hardness and strain rate sensitivity, and on the basis of
by performing indentations at varying ε_ ind , as has been shown in
these data one can make conclusions about the direction of changes
previous studies [25].
in the amorphous structure under some treatment. It is evident
Considering that in pyramidal indentation the indentation load
that structural changes during HPT processing should affect strain
P is:
rate sensitivity of the material. The main aim of this work is to study
the effect of HPT processing at various temperatures on mechanical
behavior of the Zr62Cu22Al10Fe5Dy1 BMG by means of P ¼ Ch2 (5)
nanoindentation.
where C is the constant. In order to maintain the constant inden-
2. Experimental tation strain rate with penetration, the loading rate should vary
according to:
2.1. Strain rate sensitivity measurements
P_ h_
To measure strain rate sensitivity by nanoindentation, three ¼ 2 ¼ 2_εind (6)
P h
methods have been widely used: (i) the constant loading rate
method (CRL) proposed by Mayo and Nix [26], in which a steady Therefore, in this study, CSR nanoindentation [27] tests were
loading rate is used until the tip displacement rate becomes nearly conducted with proportional loading rates of 0.005, 0.02 and 0.1
constant; (ii) the constant strain rate method (CSR), proposed by s1, corresponding to indentation strain rates of 0.0025, 0.01 and
Lucas and Oliver [27], which uses an exponential load-time func- 0.05 s1, respectively. In the absence of a continuous measurement
tion to induce a constant strain rate; and (iii) strain rate jump tests of contact stiffness, which would allow determining the contact
[28,29], in which the loading rate is suddenly changed during an area and the hardness continuously during each indentation test,
indentation experiment to compute the change of hardness with strain rate sensitivity was obtained from the change in apparent
strain rate. This method is capable of deriving the strain rate hardness Hap with indentation strain rate at the end of the loading
sensitivity from a single indentation experiment, while the first segment, using the form:
two methods require multiple indents at varying loading/inden-
tation strain rates to derive the change of hardness with different P
Hap ¼ (7)
strain rates. In the present study, the constant strain rate method AðhÞ
was used due to the following reasons: unlike CRL, the CSR tech-
nique maintains the constant strain rate during the entire experi- where the apparent contact area A(h) was obtained from the known
ment; unlike strain rate jump tests, the CSR method measures diamond area function of the indenter, i.e., the apparent hardness
hardness from not-deformed structure, as different strain rates are neglects any elastic contribution to the penetration depth. Previous
applied on fresh locations on the sample surface. studies have already shown the validity of this approach to deter-
Strain rate sensitivity measurements were carried out using the mine the strain rate sensitivity [28].
 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602
2.2. Materials and methods
The BMG with a nominal composition of Zr62Cu22Al10Fe5Dy1
was used in this study. Cylindrical rods of 5 mm in diameter and
50 mm in length were fabricated by the copper mold casting of
pure elements. The cast rod was cut into discs with a thickness of
2 mm for HPT processing. The sample was placed upon the HPT
anvils with 10 mm in diameter and compressed to a disc with a
diameter 10 mm. During the HPT process, the discs were deformed
at a rotation speed of 1 rpm under an applied pressure of 6 GPa for 5
revolutions at room temperature (RT). Using such an HPT tech-
nique, solid samples with a thickness of 0.2e0.3 mm and a diam-
eter of 10 mm were produced. Three different structural states of
this Zr-based BMG were investigated: as-cast, HPT-processed at
room temperature and as-cast annealed at 500  C for 10 min.
Amorphous or crystalline structure was revealed by X-ray
diffraction (XRD) under Cu radiation employing a Bruker Phaser D2.
Calorimetric measurements (DSC) were performed using a Netzsch
DSC 204 F1 Phoenix calorimeter with a typical heating rate of 20  C/
min. Density measurements were made according to the procedure
described in Ref. [30]. The structure of the samples was investigated
by Zeiss Libra 200FE transmission electron microscope (TEM) at an
accelerating voltage of 200 kV. Samples for TEM study were pre-
pared in cross-section, i.e. in direction perpendicular to the spec-
imen plane by Focused Ion Beam (FIB) using a Zeiss Auriga cross
beam. Detailed lamella sample preparation described in Ref. [31].
Prior to nanoindentation experiments, all specimens were me-
chanically polished with a series of diamond suspensions followed
by 0.05 mm colloidal silica. The indentation tests were performed
using a Micro Materials Nanotest platform 3 with a standard Ber-
kovich diamond indenter tip with load and displacement resolu-
tions of 0.1 mN and 0.1 nm, respectively. The machine compliance
and indenter geometry calibrations were performed using a refer-
ence fused silica sample. Experiments were conducted at RT in
load-control mode with a peak load of 200 mN for three propor-
tional loading rates 0.005, 0.02 and 0.1 s1, corresponding to 0.0025
s1, 0.01 s1 and 0.05 s1 equivalent strain rates, respectively.
Nanoindentation measurements were performed at distances of
half the disc radius from the center of the disc surface. The
indentation tests include three segments: a constant strain rate
loading up to maximum load, holding at the maximum load for 5 s,
and complete unloading in 5 s. At least ten indentation tests were
conducted for each strain rate. Scanning probe microscope (SPM)
images of indents were obtained by Hysitron Triboindenter TI950.
3. Results
X-ray diffraction analysis was carried out to study the structure
of the HPT-processed sample as well as the initial Zr-based BMG rod
and the specimen after annealing (Fig. 1). According to the XRD-
patterns, the structure of as-cast BMG rods is amorphous. HPT-
processed state retained its amorphous structure. XRD demon-
strates shift of first peak position to lower 2q: from 37.11 in initial
state to 36.85 for state processed by HPT. Shift of first peak position
to lower 2q means increase in value of first coordination sphere
radius (R1). Radius of first coordination sphere could be determined
from Ehrenfest equation 2R1sinq ¼ 1.23l, where l e is the wave-
length of radiation [32]. Values of radii of first coordination spheres
for as-cast and HPT-processed states are summarized in Table 1.
Increase in value of first coordination sphere means increase in free
volume content [33]. HPT processing leads to increase in value of
full width at half maximum (FWHM) by 50% in comparison with
the initial state (Table 1). Increase in FWHM [6] due to the defor-
mation was attributed to increase in free volume content. Such
increase of average interatomic distances or formation of shear
597
bands may cause increase of free volume in amorphous matrix after
HPT processing. Annealing at 500  C induces crystallization of the
BMG, as shown in the XRD-patterns in Fig. 1.
DSC study confirmed the amorphous nature of as-cast and HPT-
processed states. Temperature of glass transition and crystallization
onset are 395 and 474.5  C for as-cast state (Table 1). HPT leads to a
slightly decrease in temperatures of glass transition and crystalli-
zation onset by a few degrees (Fig. 2).
Density measurements were made in the as-cast and HPT-
processed samples of the Zr62Cu22Al10Fe5Dy1 BMG according to
the unique procedure [30]. The most widely used method for the
density measurements of metallic samples, including BMGs, is the
method of hydrostatic weighing [34]. However, density measure-
ment of HPT-processed samples by hydrostatic weighing is
extremely complicated and not accurate due to the small sizes,
complex shape and small thickness of the samples after HPT. In this
connection, the existing literature lacks data about the direct
measurements of the effect of HPT on the density of amorphous
alloys. The possibility of measuring the density of samples of
amorphous alloys subjected to HPT emerged when a new unique
method was developed [30] that enabled measuring the density of
samples with very small sizes and a complex shape. The density
variation demonstrates that the initial Zr62Cu22Al10Fe5Dy1 BMG has
the density r equal to 6.98 g/cm3 (Table 1), which correlates with a
rather good accuracy with the measurement data for bulk samples
of the Zr62Cu22Al10Fe5Dy1 BMG obtained by hydrostatic weighing
[34]. HPT processing leads to a decrease in the density values by
2.15% as compared to the initial state. Such decrease in the density
values of the sample indicates the formation of many regions with
increased free volume, shear bands, as a result of HPT. The decrease
in the density values can also be attributed to the emergence of
pores and cracks in the HPT-processed sample, but studies by op-
tical metallography and scanning electron microscopy SEM with
different magnifications of the HPT-processed samples reveal the
absence of any pores and cracks in the HPT-processed state of the
Zr62Cu22Al10Fe5Dy1 BMG.
TEM images of the initial and HPT-processed state are shown in
Fig. 3. General view of lamella sample for as-cast state is shown in
Fig. 3a. Homogeneous amorphous structure with few tiny crystals
with a size of 40e100 nm is observed. However, the volume frac-
tion of these crystals is very low, and undetectable by the XRD
Fig. 1. X-ray diffraction patterns of: as-cast Zr62Cu22Al10Fe5Dy1 BMG, as-cast
Zr62Cu22Al10Fe5Dy1 BMG subjected to HPT at room temperature and as-cast
Zr62Cu22Al10Fe5Dy1 annealed at temperature of 500  C for 10 m.
598 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602
Table 1
Structural parameters of as-cast and HPT-processed Zr62Cu22Al10Fe5Dy1 BMG: temperatures of structural transformations occurring during heating; values of FWHM for the
first amorphous halo, radius of the coordination sphere (R1); values of density (r).
Material Glass transition,  C
as-cast BMG 395
HPT at room temperature 390
Fig. 2. DSC curves of as-cast and HPT-processed Zr62Cu22Al10Fe5Dy1 BMG.
measurements, thus as-cast state can be considered as predomi-
nantly amorphous. High resolution TEM (HR TEM) image of as-cast
state revealed homogeneous amorphous structure, which is
confirmed by selected area electron diffraction (SAED) on inset
(Fig. 3b). In contrast to the as-cast state, state after HPT processing
demonstrates presence of large number of heterogeneities in
amorphous structure e shear bands (Fig. 3c). SAED from state
processed by HPT revealed the amorphous halo, as well as a few
faint crystalline reflections from nanocrystals. Nanocrystals with
sizes of few nanometers form directly in the shear bands as a result
of HPT-induced nanocrystallization.
Typical indentation load-penetration (P-h) curves obtained
from nanoindentation on three different samples at equivalent
strain rates of 0.0025 s1, 0.01 s1 and 0.05 s1 are shown in Fig. 4.
HPT leads to a decrease in the values of elastic modulus and
hardness. Annealing at temperatures of 500  C leads to an increase
of both parameters. A similar behavior was observed for the all
indentation rates (Fig. 4b and c). The state after annealing at a
temperature of 500  C demonstrates the highest value of elastic
modulus (111 GPa).
There were visible serrations on the load-penetration curve for
the as-cast BMG, indented at the lowest indentation strain rate
(Fig. 5a). Higher indentation strain rates, however, led to the sup-
pression of serrations (Fig. 4b and c), and the load-penetration
curves became smoother. It should be noted that the presence of
visible serrations on the load-penetration curves for the amor-
phous alloys indented at the lowest indentation strain rate and the
suppression of serrations at higher indentation strain rates have
been observed in many works, in particular, in Refs. [22,35,36].
Serrated flow is a signature of the formation of shear bands in BMGs
[35]. Interestingly, the BMG after HPT did not exhibit serration flow
at any indentation strain rate (Figs. 4 and 5a). SPM images of in-
dents in the as-cast and HPT-processed states after nano-
indentation at equivalent strain rate 0.05 s1 are shown in Fig. 5b
Crystallization onset,  C FWHM, degree R1, Å r, g/cm3
474 4.00 2.98 6.98
467 6.20 3.00 6.83
and c, respectively. Many shear bands are observed around imprint
in the as-cast BMG (Fig. 5b). No shear bands are observed after HPT
processing (Fig. 5c). So, HPT processing reduces or completely
eliminates strain localizations in large shear bands (which are
observed in form of serrations in load-penetration curve or arcs
around the imprint), that leads to a more homogeneous deforma-
tion under nanoindentation [16]. It should be noted that the
nanoglasses with cluster-type structure did not exhibit serration
flow on the load-penetration curves and shear bands around im-
prints, however, visible serrations and shear bands were observed
for the corresponding homogeneous amorphous specimen [36].
The BMG after annealing at 500  C did not exhibit serration flow.
The latter is expected at annealing at 500  C led to crystallization as
shown by the XRD above. Deformation mechanism was changed
from shear banding to dislocation flow due to the crystallization
and serration flow disappears.
Values of strain rate sensitivity, Young's modulus are summa-
rized in Table 2. The strain rate sensitivity of the as-cast BMG was
0.014. HPT processing led to an increase in m values by a factor of
2.57 with respect to the as-cast state. m decrease significantly to
0.001 after annealing at 500  C. It should be noted that there is an
inverse relationship between the values of Young's modulus and
the values of strain rate sensitivity (Table 2).
4. Discussion
The results of the present study are compared with a summary
of literature data on the SRS of different BMGs in Table 3. While
negative strain rate sensitivities have been often reported for many
BMGs tested by compression, positive values of strain rate sensi-
tivity are reported in the case of nanoindentation experiments. The
difference in SRS obtained by compression and nanoindentation
can be mainly attributed to the different stress states imposed by
the different methods [37,38]. As a matter of fact, during nano-
indentation, the constraint introduced by the surrounding unde-
formed volume induces a large stress triaxiality, more similar to
compression under high hydrostatic stresses rather than uniaxial
compression [37,38]. Additionally, the small size of the deformed
volume during nanoindentation suppresses crack formation. This
typically leads to a more homogeneous deformation of BMGs in
nanoindentation than macroscopic compression tests [39], result-
ing in positive values of strain rate sensitivity [24]. The results
obtained in the current study with positive values of strain rate
sensitivity agree well with those obtained for similar BMGs by
nanoindentation studies [24]. Therefore, the current results sup-
port the conclusion that HPT processing leads to an increase in SRS.
The decrease in the elastic modulus observed after HPT pro-
cessing can be attributed to softening due to the introduction of a
large amount of free volume during HPT processing [16]. Density
measurements and shift of amorphous halo to lower 2q confirm
this. It has been found that BMG after HPT does not exhibit serrated
flow even at the lowest indentation strain rate. It is known that
each serration on the load-penetration curve is a signature of the
formation of a “large noticeable” shear band that accommodates
deformation. The lack of serrations on the load-penetration curve
for BMG subjected to HPT can be explained by the following factor.
 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602 599

Fig. 3. (a) STEM-BF image of the as-cast Zr62Cu22Al10Fe5Dy1 BMG; (b) HRTEM image of Zr62Cu22Al10Fe5Dy1 BMG with SAED on inset. (c) STEM-BF image of as-cast
Zr62Cu22Al10Fe5Dy1 BMG subjected to HPT at room temperature. (d) HRTEM image of Zr62Cu22Al10Fe5Dy1 BMG subjected to HPT at room temperature with SAED on inset.

Fig. 4. Typical load-penetration curves for the as-cast BMG, as-cast BMG subjected to HPT room temperature and as-cast BMG annealed at 500  C tested at equivalent strain rates (a)
0.0025 s1, (b) 0.01 s1 and (c) 0.05 s1.
600 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602

Fig. 5. (a) Enlarged region of the load-penetration curves for the as-cast BMG and BMG subjected to HPT at 20  C tested at equivalent strain rate 0.05 s1. Serrations are observed in
the as-cast state and not observed in HPT-processed. SPM images of indents in the as-cast (b) and HPT-processed (c) states after nanoindentation at equivalent strain rate 0.05 s1.

Table 2
Values of reduced Young's modulus, hardness and m of the Zr-based BMG for three different states measured at a strain rate of 0.0025 s1.

Material Reduced Young's modulus, GPa Hardness, GPa m

as-cast BMG 90 5.18 0.014

HPT at room temperature 85 4.60 0.036
BMG annealed at 500  C for 10 min 111 6.81 0.001

HPT leads to the formation of a high density of shear bands in
accordance with the TEM data (Fig. 2b). Shear bands formed during
HPT are heterogeneities in the amorphous structure [8,16]. These
shear bands, on the one hand, prevent the propagation of “large”
“noticeable” shear bands during subsequent nanoindentation, and
on the other hand, play the role of the sources for the formation of
multiple “fine” shear bands. Multiple propagations of these “fine”
shear bands are not registered on the load-penetration curve,
therefore the load-penetration curve for the HPT-processed sample
looks so smooth even at the lowest indentation strain rate. It should
be noted that the nanoglasses with cluster-type structure did not
exhibit serration flow on the load-penetration curves, however,
visible serrations were observed for the corresponding homoge-
neous amorphous specimen [34]. The absence of visible serrations
on the load-penetration curves was explained by the uniform
nanoglass deformation by the formation of numerous shear bands
being activated simultaneously at cluster boundaries [34]. More-
over, this nanoglass exhibit unique ductility under both compres-
sive and tensile loading.
An increase in the value of strain rate sensitivity leads to
decrease in the volume of shear transformation zone (STZ) and
therefore to decrease in size of shear bands. STZ volumes were
found to be 4.22 and 1.79 nm3 for as-cast and HPT-processed states,
respectively (according to the equations described in Ref. [24]). It is
proposed a correlation between volumes of STZ and ductility of
BMG, i.e. larger volumes of STZ correspond to more ductile BMG.
However, such correlation was established only for homogeneous
BMG [24]. Our results demonstrate decrease in STZ volume after
HPT processing along with formation of heterogeneities (shear
bands) in amorphous structure (Fig. 3d) and more homogeneous
deformation during nanoindentation (Fig. 5). Thus, for heteroge-
neous amorphous structures there may be an opposite correlation
 E.V. Boltynjuk et al. / Journal of Alloys and Compounds 747 (2018) 595e602 601

Table 3
Strain rate sensitivity of various BMGs.

Material Test condition m

Zr52.5Ti5Cu17.9Ni14.6Al10 (Vitreloy 105) and its Rate jump tests in compression with ε_ between 0.0001 ± 0.0005
composites reinforced with 6%graphite [40] 3.3  103 and 3.7  104 s1
Vitreloy 105 [41] Compression at various T (196 e 77  C) and ε_ Positive between 196 and 73  C, 0.002
3.33  105 e 0.2 s1 above 73  C
Vitreloy 105 [42] Compression with ε_ 2.34  103 e 1.87  101 s1 0.0026
Pd40Ni40P20 [43] Compression with ε_ 3.3  105 e 2x103 s1 Negative
Pd-20 at.%Si [44] Compression with ε_ 104 e 102 s1 Fracture strength decreases with ε_ , yield
strength remains nearly invariant
Zr57Ti5Cu20Ni8Al10 [45] Compression with ε_ 104 e 103 s1 Failure stress increases with ε_
Zr/Hf-based BMGs [46] Dynamic compression Fracture strength decreases with increasing ε_
Zr38Ti17Cu10.5Co12Be22.5 [47] Quasistatic and dynamic compression with ε_ 105 Fracture strength decreases with increasing ε_

e103 s1
Zr65Cu20Fe5Al10 [48] Compression with ε_ 5  106 e 5x103 s1 Does not exhibit strain rate sensitivity
Zr65Cu20Fe5Al10 [48] Compression with ε_ 5  103 e 5x102 s1 0.0026
Pd40Ni40P20 [24] Rate-jump nanoindentation with r_ 13.2e264 mn/s 0.0067
Pt57.5Cu14.7Ni5.3P22.5 [24] 0.0089
Cu60Hf25Ti15 [24] 0.011
Zr55Cu25Ni10Al10 [24] 0.013
Ni53Nb20Ti10Zr8Co6Cu3 [24] 0.012
Zr44Cu44Al6Ag6 [24] 0.021
Zr62Cu22Al10Fe5Dy1 (present study) Constant strain rate nanoindentation with ε_ 0.014
Zr62Cu22Al10Fe5Dy1 subjected to HPT at 2.5  103, 102 and 5  102 s1 0.036
room temperature (present study)
Zr62Cu22Al10Fe5Dy1 annealed at 500  C 0.001
for 10 m (present study)

between STZ volumes and ductility, as was previously observed for
ductile heterogeneous amorphous structures, formed by pre-
liminary plastic deformation [6e9]. Increased values of strain rate
sensitivity (decreased STZ volume) for the HPT-processed state
correspond to lower activation barrier and more active formation of
shear bands under loading due to a more heterogeneous structure
in comparison with the initial state. Also, as was mentioned above,
shear bands formed due to the HPT processing could play role of
heterogeneities. It should be noted that HPT deformation of an
amorphous TiNiCu alloy leads to the formation of a heterogeneous
cluster-type amorphous structure with a modified free volume
[31,49,50]. Crystallization annealing at 500  C results in an even
higher elastic modulus increase, but a significant reduction of strain
rate sensitivity down to 0.001, typical for crystalline metals.
5. Conclusions
Effect of high pressure torsion processing on the strain rate
sensitivity of bulk metallic glasses was studied for the first time in
present paper. According to the XRD and TEM data, the structure of
as-cast BMG rods and HPT-processed state is amorphous. HPT leads
to the formation of numerous shear bands in amorphous matrix.
Nanoindentation demonstrates changes in the mechanical behav-
iour e values of Young's modulus, hardness and strain rate sensi-
tivity BMG. HPT processing leads to a decrease in the elastic
modulus, hardness and an increase in strain rate sensitivity with
respect to the as-cast condition. It was found that BMG after HPT
does not exhibit serration flow at any indentation strain rate which
is not typical for BMGs. The observed lack of serration flow and
increase in values of strain rate sensitivity for BMG subjected to HPT
can be explained as the formation of high-heterogeneous (where
numerous shear bands play the role of heterogeneities) amorphous
structure in results of HPT processing. More studies are required to
elucidate this.
Acknowledgements
The authors acknowledge Saint Petersburg State University for a
research grant 6.65.43.2017 (XRD study, TEM study and FIB sample
preparation, DSC study). Research has also been supported by the
RFBR grant No.17-08-00974 (HPT processing). Authors at IMDEA
acknowledge funding from the Spanish Ministry of Economy and
Competitiveness through project MAT2012-31889 and the Madrid
regional government through project S2013/MIT-2775, DIMMAT, to
conduct this work (nanoindentation). LWY acknowledges the China
Research Council for his PhD scholarship (nanoindentation). The
work was partially supported in the framework of the Competi-
tiveness Increase Program of NUST «MISiS» (K2-2014-013, K2-
2017-089) (alloys preparation). A.K. would like to thank the DFG/
SPP 1594 program for funding the project under HA1344/30-1
(density measurements). The scientific investigations were per-
formed at the Research Centre for X-ray Diffraction Studies, Inter-
disciplinary Resource Centre for Nanotechnology, Centre of
Thermal Analysis and Calorimetry of the Research Park of St.
Petersburg State University.
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