Journal of Non-Crystalline Solids 481 (2018) 321–328

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

On the fracture toughness of bulk metallic glasses under Berkovich T

nanoindentation
⁎
H. Guoa,b, C.B. Jianga, B.J. Yanga, J.Q. Wanga,
a
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

A R T I C L E I N F O A B S T R A C T

Keywords: Measurements of fracture toughness from the crack tip opening displacement (CTOD) testing methods are
Bulk metallic glasses complex and paramount important for a range of bulk metallic glasses (BMGs). In this work, we attempted to
Fracture toughness propose an indentation protocol to evaluate indentation fracture toughness based on two key considerations:
Nanoindentation First, the plastic deformation induced damage to the characteristic fracture initiation point calculated from
Continuum damage mechanics
integrating the indentation load-displacement curves is obtained and used to estimate indentation fracture
toughness. Second, the continuum damage mechanics theory has been adopted to identify the characteristic
fracture initiation point. To verify the applicability of the suggested approach, fracture toughness values of BMGs
were estimated and compared with those from CTOD tests in the literature. The estimated fracture toughness
values KC obtained from the indentation tests agreed well with those KQ from the CTOD tests within an ap-
proximately relative difference of 10%. We also found that KQ linearly correlates with KC (KQ = 1.1KC − 3.7).
The value of KQ in Al-based BMG is predicted to be ~35 MPa √ m.

1. Introduction
Fracture toughness, which indicates the resistance to crack propa-
gation, is very important in assessment of structural integrity. In me-
tallic glass (MG) community, initially, the measurement of fracture
toughness has mainly been focused upon the tensile testing of the
edged- or center-notched ribbon specimens [1–4]. With the advent of
bulk metallic glasses (BMGs) with large specimens, there appear more
crack tip opening displacement (CTOD) testing methods to characterize
the fracture toughness of BMGs, such as single-edge notched bend for
three-point bending and compact-tension for tensile loading. Only few
compositions (mainly concentrated on Zr- [5] and Pd-based [6]) are
tough enough to obtain the fatigue pre-cracked toughness KIC. For many
other BMGs, including Fe- [7], Cu- [8], Ni- [9], Zr- [10–12] and Ce-
based [13], the fracture toughness, KQ, ranging from 10 to 100 MPa √ m,
has been assessed without the pre-fatigue procedure. Note that these
testing methods were much sensitive to the specific specimen geometry
and size (specimen depth, specimen thickness and crack size). Thus,
some non-destructive and convenient methods are worthy of at-
tempting to evaluate fracture toughness of the BMGs.
The Vickers indentation test and the nanoindentation test have been
used to characterize fracture behavior of brittle materials, including
glasses, ceramics, films and coatings. Provided the materials exhibit
brittle fracture with minimal crack tip plasticity, this crack pattern can
be used to establish fracture toughness values. The fracture toughness
can be evaluated by either crack-length-based method [14–16] or
crack-energy-based method [17–19]. Such indentation test can be re-
latively quick and easy to perform, require little specialized equipment,
compared to CTOD test required to assess the opening mode toughness.
As recalled by Quinn et al. [20], the indentation fracture toughness is
more related to crack arrest due to the residual stress fields than to
crack propagation, which is the definition of fracture toughness from
the CTOD test. Nevertheless, it gives very useful partially quantitative
information. However, this current indentation test can be applied only
to brittle materials with low fracture toughness (< 10 MPa √ m)
[14–20].
Comparable low toughness values have been reported either by
indentation tests [21] (3.5 MPa √ m) or by COTD tests [22]
(1.5 MPa √ m) on a similar alloy Fe48Cr15Mo14Er2C15B6. A question
therefore arises: is it available for us to assess the fracture toughness
typically around 10–100 MPa √ m for BMGs by indentation tests? Nor-
mally, during loading process, the BMG beneath the indenter experi-
ences the localized plastic deformation [23–25]. The plastic deforma-
tion surrounding the indenter contact area introduces damage
accumulation and leads to ultimate fracture. It is difficult to evaluate
the damage critical level and predict the ultimate damage values at

⁎
Corresponding author.
E-mail address: jqwang@imr.ac.cn (J.Q. Wang).

https://doi.org/10.1016/j.jnoncrysol.2017.11.008
Received 19 September 2017; Received in revised form 31 October 2017; Accepted 8 November 2017
Available online 15 November 2017
0022-3093/ © 2017 Elsevier B.V. All rights reserved.
H. Guo et al. Journal of Non-Crystalline Solids 481 (2018) 321–328

failure point. To overcome this challenge, it has been suggested that the
indentation deformation energy per unit area absorbed to a critical
indentation depth can be correlated with the fracture energy for frac-
ture initiation [26–28]. Thus, we could consider evaluating the in-
dentation fracture toughness on the basis of deformation energy ab-
sorbed to a critical indentation depth at failure point. A continuum
damage mechanics (CDM) has been a useful method to predict failure
behavior for a wide range of materials (metals [29], composites [30],
etc.). Based on the CDM theory, it can represent the amount of re-
sistance to crack growth or the amount of energy required for a pre-
existing flaw to propagate and attain a critical limit [31]. The CDM
theory was used to determine the characteristic fracture initiation point
by Lee et al. [28] who successfully assessed the indentation fracture
toughness in ductile materials using nanoindentation. Thus, it is rea-
sonable to evaluate the indentation fracture toughness in BMGs.
In current work, the indentation tests were examined for six well
studied and representative BMGs, Fe65Mo14C15B6 [7], Cu49Hf42Al9 [8],
Ni40Cu5Zr28.5Ti16.5Al10 [9], Zr55Al10Ni5Cu30 [10], Ce60Al20Ni10Cu10
[13] and Al86Ni6Y4.5Co2La1.5 [32]. To verify the applicability of the
suggested approach, fracture toughness values of BMGs were estimated
and compared with those from CTOD tests in the literature.

2. Theoretical

Under an external load, highly concentrated stress and strain fields

are generated ahead of crack tip and the degree of the stress con-
centration depends on the constraint effect of the crack [33]. Indenta-
tion into a material may also produce a deformation field concentrated
highly by the surrounding material. However, there is a distinct dif-
ference between the indentation deformation and the deformation
ahead of the crack tip, that is, the principal stress components within
the edge of impression are compressive, while those around the crack
tip are tensile. To simplify the analysis of various stress components, the
indentation deformation is assumed to be axisymmetric. Preliminary
computer simulations of an axisymmetric model showed that the degree
of constraint in the deformation was similar to that ahead of crack tip
[28]. Therefore, the indentation deformation energy per unit area ab-
sorbed to a critical indentation depth could be correlated with the Fig. 1. Schematic of various stages in nanoindentation fracture for the specimen. Stage 1:
fracture energy for fracture initiation [26–28]. accumulation of damage; Stage 2: initiation of fracture, the crack is positioned at the
boundary of the plastic zone; Stage 3: crack propagation. a is the length of the contact
The fracture initiation is considered to be the result of the accu-
impression after unloading; b is the length of half-penny crack; c is the plastic zone size.
mulation of plastic damage [34,35]. From a microscopic point of view,
the damage and failure of BMGs occur after the void nucleation, growth
and coalescence. In order to understand the nature of the fracture on the bottom area of the plastic zone in the following analysis. This is
mechanism of BMG in nanoindentation, the schematic in Fig. 1 shows also consistent with MD simulation results of MGs that the crack in-
various stages in nanoindentation fracture. Based on this study, three itiation always occurs near the bottom of the plastic zone [40].
stages in the nanoindentation fracture appear to exist: (1) accumulation
of damage; (2) initiation of fracture; (3) crack propagation. In the first 2.1. Indentation fracture toughness KC
stage, as the indenter load P increases, the hemispherical plastic zone
generated under the contact expands. In the second stage, when the In the indentation test, cracks are produced when brittle BMGs are
indentation load is high enough to reach the critical value P⁎ (corre- indented [16]. While indentation does not induce severe cracking
sponding to the critical indentation depth h⁎), a median crack initiates in comparatively ductile BMGs with high fracture toughness
beneath the plastic deformation zone and propagates downward. If (> 10 MPa √ m), estimating fracture toughness using indentation based
P > P⁎, the fracture morphology follows the evolution from median to on cracking cannot be used. Therefore, it is necessary to find other
half-penny crack, as shown in the third stage. It is well known that most approach that does not require crack length measurement to identify
relevant crack systems include median, radial and half-penny cracks fracture.
[36]. The median crack is established through the indentation model by Load-displacement (P-h) studies in the nanoindentation have been
Chiang et al. [37,38] under plane-strain condition. The essence of conducted on films and coatings to develop crack-energy-based models
Chiang's model is that the plastic zone size is determined by plastic [17,41–43]. Calculation of the energy released during cracking is a
work of indentation. It is assumed that the crack initiates at the bottom measure of the fracture toughness.
of the elastic/plastic boundary, which is also an assumption of the crack
U
initiation mechanisms proposed by others [36,39]. As reported by Pharr KC = GC E = E
A (1)
et al. [36], the indentation-induced residual stress field leads to driving
force on the median-radial crack and then to half-penny crack. Fur- where GC is the critical strain energy release rate, U is the fracture
thermore, Lawn and Evans [39] suggested that the crack initiation energy, E is the Young's modulus, A is the fracture area. The fracture
process is controlled by the elastic/plastic indentation field, then be- energy, U, is suggested to be the plastic deformation energy during
comes a median and eventually a half-penny crack. Therefore, we focus fracture. For mechanically thick films exhibiting half-penny cracks,

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H. Guo et al. Journal of Non-Crystalline Solids 481 (2018) 321–328

A = πb2/2, where b is the length of the crack. However, these can be

applied only to brittle materials with low fracture toughness
(< 10 MPa √ m).
For brittle materials, the released energy is totally dissipated in
creating new surfaces of the crack. For ductile materials, a plastic zone
is developed in the crack tip, and the released energy is dissipated both
in the plastic deformation of the plastic zone and in creating new sur-
faces [44]. The plastic work is usually around 1000 times the surface
energy. It is thus reasonable to conclude that the plastic work dom-
inates the fracture toughness [45,46].
For ductile materials, a new energy model is suggested in terms of
indentation energy to fracture (GIEF), which is proposed on the concept
that the indentation deformation energy per unit area to a critical in-
dentation depth is related to the plastic energy portion of the fracture
energy per unit area [26–28,47].

hp∗ hp∗ P (hp ) Wp

KC = G IEF E = E ∫0 Pm (h p ) dhp = E ∫0 A
dhp = E
A
(2)
where Pm is the mean indentation contact pressure, hp is the plastic
indentation depth, and hp∗ is the critical plastic indentation depth at the
fracture point. Wp is the plastic deformation energy, A is the contact
area of indentation tip due to the unrecoverable plastic deformation.
For a spherical indenter, the fracture area is given by: A = πd2/4,
Fig. 2. (a) A schematic illustration of a typical load versus indenter displacement (P-h)
where d is the chordal diameter of the indentation [28]. curve showing quantities used in the analysis [60]. The quantities shown are h: the in-
It is noted that Eqs. (1) and (2) are nearly identical to the in- denter displacement at peak load; hf: the final depth of the contact impression after un-
dentation fracture toughness in terms of plastic work per unit fracture loading; hc: the contact depth; Wp: the plastic energy; We: the elastic energy and Wt: the
area. Thus, the indentation fracture toughness could be given: total energy. (b) A schematic representation of a section through an indentation test, a is
the length of the contact impression after unloading; b is the length of half-penny crack; c
Wp is the plastic zone size; α is the axis-to-face angle of the pyramidal indenter.
KC = GC E = E
A (3)

When indentation load is high enough, the median crack nucleates
and grows just underneath the plastic zone during loading and extends
to the surface of the sample with a final semicircular shape. The BMG
experiences a considerable amount of plasticity prior to fracture. Here,
the BMG will initiate a crack at fracture initiation point. Trying to
measure the fracture point, the indentation technique will be a new
attempt to evaluate the indentation fracture toughness at shallow in-
dentation.
The plastic deformation energy, Wp, can be obtained from the in-
dentation P-h curve. Fig. 2(a) schematically shows the typical P-h re-
sponse for an indentation experiment. The total energy, Wt, is obtained
by integrating the loading curve from zero depth to the critical in-
dentation depth at the fracture point, h⁎:
h h k (h∗)n + 1
Wt = lim∗
h→h
∫0 P dh = lim∗
h→h
∫0 khn dh =
n+1
The loading portion is generally described by the power-law rela-
tion: P = khn, where k is the loading curve constant and n is the loading
Indentation into the BMGs produces a deformation field where there
exists fracture releasing stored energy, the fracture area can be simply
assumed by the plastic zone region, as indicated in Fig. 2(b).
π
A = lim ⎛ b2 − ah f ⎞
b→c ⎝ 2 ⎠ (6)
where a is the length of the contact impression after unloading, b is the
length of half-penny crack, c is the plastic zone size, hf is the final depth
of the contact impression after unloading. As shown in Fig. 2(b), the
relationship between c, a and h, hf is given by: tanα ≈ c/h ≈ a/hf,
where α is the axis-to-face angle of the pyramidal indenter. For the case
of Berkovich indentation, α = 65.27°. The linear relationship between
hf/h and H/Er for each indenter angle can be expressed as: hf/
h = 1 − λH/Er [49]. A median crack is initiated near the bottom of the
plastic zone at a characteristic fracture initiation point h⁎. Thus the
(4) fracture area is given by
2
π H⎞
A = lim∗ h2 ⎡ 2 ⎛ ⎤
⎢ 2 (tan α ) − 1 − λ Er tan α⎥
⎜ ⎟

h→h ⎝ ⎠
exponent. ⎣ ⎦
2
The ratio of plastic deformation energy to total energy for a com- π H⎞
= (h∗)2 ⎡ 2 ⎛ ⎤
⎢ 2 (tan α ) − 1 − λ Er tan α⎥
⎜ ⎟

plete loading-unloading cycle can be written as: Wp/ ⎝ ⎠ (7)

⎣ ⎦
Wt = 1 − λ(1 + γ)H / Er [48,49]. Where γ = 0.27 and
λ = 1.5tanθ + 0.327 for 60° ≤ θ ≤ 80° are the curve-fitting para- Finally, under the plane stress condition, the indentation fracture
meters from a number of FEM simulations, which are close to the values toughness KC can be calculated by combining Eqs. (3), (5) and (7)
reported from experiments [50]. For the case of Berkovich indentation, H
θ = 70.3°. H is the nanoindentation hardness, Er is the reduced Young's 1 − λ (1 + γ ) E k (h∗)n − 1
r
KC = E
modulus, 1/Er = (1 − ν2)/E + (1 − νi2)/Ei, where E and Ei are the H 2 n+1
Young's modulus of the specimen and the indenter, respectively, while ν
π
2 (
(tan α )2 − 1 − )
λ E tan α
r (8)
and νi are the Poisson's ratio of the specimen and the indenter. Note that In the case of Berkovich indentation λ = 4.52, γ = 0.27,
for diamond, Ei = 1141 GPa and νi = 0.07. Hence, the plastic de- tanα= 2.17. k and n can be derived from the power-law relation be-
formation energy can be determined: tween the load and the displacement: P = khn. H, Er and E are easily
H k (h∗)n + 1 obtained from the nanoindentation tests. Overall, based on the P-h
Wp = ⎡1 − λ (1 + γ ) ⎤ curve, the calculation of indentation fracture toughness is convenient
⎢
⎣ E r⎥
⎦ n+1 (5)
when the critical indentation depth h⁎ is known.

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H. Guo et al.
2.2. Determination of critical indentation depth h⁎
In order to determine the fracture toughness, the critical indentation
depth h⁎ is still needed. h⁎ cannot be measured by direct methods be-
cause there is no distinguishable mark to identify fracture during in-
dentation. It is well known that a continuous increase in indentation
depth results in the damage accumulation which greatly contributes to
the non-linear decreasing of stiffness and hardness beneath the in-
denter. These physical changes are often used as indicators to predict
the onset of fracture [51]. Thus, to determine h⁎ indirectly, we adopted
the concepts of CDM, which has been widely used to predict failure in
structures loaded statically and dynamically. According to the CDM
theory, the damage variable D was introduced by Kachanov [52] to
characterize the deterioration of the mechanical properties due to
material damage. D can be also represented by hardness-based damage
quantification [51,53]:
HD
D=1−
H0
where HD is the measured hardness and H0 is the indentation hardness
which would exist without any damage. The hardness HD at various
indentation depth can be calculated at each unloading, HD = Pmax/
Ac = Pmax/(24.5hc2 + 2400hc), where Pmax is the peak load, Ac is the
projected contact area and hc is the contact depth. The measured
hardness-displacement (HD-h) relationship can conveniently be written
as: HD = ghm, where g is the curvature depending on the geometry of
the indenter tip and material properties and m is the exponent. The HD
decreases with the increase of indentation displacement h. It is note-
worthy that due to the indentation size effect [54], H0 could be ob-
tained from the average H, rather than the highest hardness obtained
from the first point in HD-h curve. If a critical hardness HD∗ which is the
damaged material hardness at fracture initiation, can be determined,
one can obtain h⁎.
The critical hardness HD∗ can be obtained from the critical damage
value D⁎ through Eq. (9). The material beneath the indenter experiences
localized shear stresses due to compressive indentation force in the
loading axis. If the shear stresses induce void nucleation, the void vo-
lume fraction f may increase with increasing indentation load. By as-
suming that voids are uniformly distributed with nearest-neighbor
spacing l, f and D can be calculated using the void radius r. For a cross-
sectional area, D can be described as πr2/l2, while f can be given as
(4πr3/3)/l3. Thus, D can be represented in terms of f as [28]:
π BMGs under different maximum loads increased from 2 mN to 24 mN
D= f 2/3
(4π /3)2/3
Thus, the critical damage value D⁎ can be achieved if we know the
critical void volume fraction f⁎, which means the value of f at the
fracture initiation point. Previous studies show f⁎ = 0.25 at the initia-
tion of stable crack growth in ductile materials [28,55,56]. Recently, it
has been found that the cavitation process can be used to account for
the fracture toughness of BMGs [57–59]. The fracture is governed by a
cavitation mechanism via multiple nanoscale void nucleation and
coalescence in the front of the crack tip. However, f⁎ has not been ex-
tensively studied in BMGs. Thus, f⁎ = 0.25 is assumed here as an
Table 1
The nanoindentation hardness (H), Poisson's ratio (ν), Young's modulus (E) and reduced Young's modulus (Er) for Fe65Mo14C15B6, Cu49Hf42Al9, Ni40Cu5Zr28.5Ti16.5Al10, Zr55Al10Ni5Cu30,
Ce60Al20Ni10Cu10 and Al86Ni6Y4.5Co2La1.5 BMGs. Data for ν from Refs [7–10,13,32].
Metallic glasses H (GPa)
Fe65Mo14C15B6 14.5 ± 0.5
Cu49Hf42Al9 7.3 ± 0.2
Ni40Cu5Zr28.5Ti16.5Al10 7.1 ± 0.2
Zr55Al10Ni5Cu30 5.3 ± 0.2
Ce60Al20Ni10Cu10 2.3 ± 0.1
Al86Ni6Y4.5Co2La1.5 4.9 ± 0.2
Journal of Non-Crystalline Solids 481 (2018) 321–328
approximation to determine critical damage value D⁎ of BMG. Then,
critical hardness HD∗ can be calculated from Eq. (9). Consequently, h⁎
can be ascertained by extrapolation from the plot of HD-h. The in-
dentation fracture toughness KC can be finally obtained through Eq. (8).
3. Experimental procedure
In order to validate the theoretical analysis, the instrumented
indentation tests were carried out on different kinds of
BMG-forming systems [7–10,13,32]: Fe65Mo14C15B6, Cu49Hf42Al9,
Ni40Cu5Zr28.5Ti16.5Al10, Zr55Al10Ni5Cu30, Ce60Al20Ni10Cu10 and
Al86Ni6Y4.5Co2La1.5. Master alloy ingots were prepared by arc-melting
the mixtures of the constituent elements with a purity of better than
99.99% under a Ti-gettered argon atmosphere. In order to ensure
compositional homogeneity, the alloy ingots were melted four times.
The cylindrical BMG rods of 1 mm diameter were produced by copper
mold casting method.
The instrumented indentation tests were carried out using MTS
(9)
Nanoindenter XP with a Berkovich diamond indenter with a tip radius
of ~ 20 nm. Prior to the nanoindentation tests, the specimens mounted
in epoxy resin were wet ground up to 5000 SiC abrasive papers, and
then polished with 1.5 μm diamond paste to a mirror finish, followed by
supersonic cleaning in ethanol and distilled water. The final surface
roughness values of all samples were determined to be about 20 nm
using a LEXT OLS 4000 laser scanning confocal microscope. All the tests
were conducted in a load-controlled mode with peak loads ranging
from 2 to 24 mN, in 2 mN increments. The indents were performed at a
loading rate of 0.05 mN/s and a data collection frequency of 20 Hz. A
minimum of 12 indents at each load was performed for each specimen,
and the average value was obtained in analyzing the fracture toughness.
For each BMG, at least four samples taken from independent as-cast
rods were used for measurement to ensure that the result is statistically
meaningful. In addition, after indentation testing, the indentation mi-
crograph was examined using Supra 55 scanning electron microscopy
(SEM). The material properties of the six BMGs are listed in Table 1.
4. Results and discussion
4.1. Identification of KC
The P-h curves of Fe65Mo14C15B6, Cu49Hf42Al9, Ni40Cu5Zr28.5
Ti16.5Al10, Zr55Al10Ni5Cu30, Ce60Al20Ni10Cu10 and Al86Ni6Y4.5Co2La1.5
with the interval of 2 mN at a loading rate 0.05 mN/s are shown in
(10)
Fig. 3. For comparison, the P-h curves of the six BMGs exhibited in the
insets of Fig. 3 are presented in Fig. 4(a). The nanoindentation hardness
(H) and Young's modulus (E) values of each BMG are derived using
Oliver-Pharr method [60], and the results are listed in Table 1. The Fe-
based BMG shows the highest hardness and Young's modulus of
14.5 ± 0.5 GPa and 200.5 ± 0.9 GPa, respectively, while the Ce-
based BMG shows the lowest hardness and Young's modulus of
2.3 ± 0.1 GPa and 31.2 ± 0.8 GPa, respectively. From Figs. 3 and
4(a), the indentation load and the indentation displacement display
good power-law relationship, the correlation factor R of the fitting lines
ν E (GPa) Er (GPa) Ref.
0.331 200.5 ± 0.9 188.2 ± 0.9 [7]
0.351 120.3 ± 0.8 122.5 ± 0.8 [8]
0.363 110.2 ± 0.5 114.3 ± 0.5 [9]
0.369 88.2 ± 0.1 93.8 ± 0.8 [10]
0.313 31.2 ± 0.8 33.6 ± 0.8 [13]
0.347 80.3 ± 0.7 84.6 ± 0.7 [32]
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H. Guo et al. Journal of Non-Crystalline Solids 481 (2018) 321–328

Fig. 3. The load versus displacement (P-h) curves for (a) Fe65Mo14C15B6, (b) Cu49Hf42Al9, (c) Ni40Cu5Zr28.5Ti16.5Al10, (d) Zr55Al10Ni5Cu30, (e) Ce60Al20Ni10Cu10 and (f)
Al86Ni6Y4.5Co2La1.5 BMGs under different maximum loads increased from 2 mN to 24 mN with the interval of 2 mN at a loading rate 0.05 mN/s. The indentation load and indentation
displacement display good power-law relationship (P = khn), the correlation factor R of the fitting lines are all > 0.999, shown in the insets of Fig. 3, respectively.

are all > 0.99. The best-fit values of the parameters k and n are ob-
tained and the results are also presented in Table 2. The observed ex-
ponent, n ~ 1.7, lies between those for spherical and conical indenters
(n = 1.5 and 2, respectively). This reinforces the notion that, in the
depth range of interest, the shape of the Berkovich indenter transitions
from spherical to conical and cannot be adequately described by either
geometry alone.
Note that the critical indentation depth h⁎ corresponding to HD∗
cannot be obtained directly from the indentation tests, and it should be
determined by extrapolation of the proper fit of HD-h relations. Fig. 4(b)
shows the relation of HD and h for the six BMGs, whose fitting lines
show good power-law relationship, the correlation factors R of the fit-
ting lines are all > 0.99, as listed in Table 2. From extrapolation of the
HD-h fitting curves, the value of h⁎ corresponding to HD∗ is determined
as shown in Fig. 4(b). It is found that h⁎ is much larger than the max-
imum indentation displacement. Finally, the indentation fracture
toughness KC for the BMGs used in the present study can be estimated
through Eq. (8) using h⁎ values determined as above. The values of KC
are 41 ± 2, 62 ± 3, 42 ± 2, 50 ± 4 and 11 ± 1 MPa √m for
Fe65Mo14C15B6, Cu49Hf42Al9, Ni40Cu5Zr28.5Ti16.5Al10, Zr55Al10Ni5Cu30
and Ce60Al20Ni10Cu10 BMGs, respectively, as listed in Table 2.
4.2. Verification
To show the predicative capability of Eq. (8) for estimating in-
dentation fracture toughness of BMGs, fractue toughness values esti-
mated by the indentation tests were compared with those from CTOD
tests, as shown (see Table 2) in Fig. 5. For each BMG, the indentation
fracture toughness is determined for each of the indentations produced
in the nanoindenter, and the error bars indicate the range of the re-
sulting values. The Table 2 shows that there is approximately 10%
difference in the fracture toughness values between the indentation
tests and the CTOD tests in Fe65Mo14C15B6, Cu49Hf42Al9,
Ni40Cu5Zr28.5Ti16.5Al10, Zr55Al10Ni5Cu30 and Ce60Al20Ni10Cu10 BMGs.
Based on the data in Fig. 5, we examine the relationship between the KQ
and the KC for the investigated BMGs. Our result suggests that the KQ
linearly correlates with the KC.

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H. Guo et al. Journal of Non-Crystalline Solids 481 (2018) 321–328

Fig. 5. Correlation between the fracture toughness KC obtained from the indentation tests
and values KQ from the crack tip opening displacement (CTOD) tests for the BMGs listed
in Table 2. The dashed line indicates Eq. (11).

Fig. 4. (a) The load versus displacement (P-h) curves for the BMGs. (b) The measured
hardness versus displacement (HD-h) curves for the BMGs. The error bars indicate the
standard deviation of twelve repeated tests at each peak load.

K Q = 1.1K C − 3.7 (11)

The fitting curve of Eq. (11) was plotted in Fig. 5 as dashed line. The
correlation factor R of the line is 0.99. Certainly, this derived linear
relation can be used to directly predict fracture toughness KQ from the
CTOD tests of BMGs. We believe that our relation represents a step
forward for the predictability of fracture toughness KQ.
Al-based BMGs exhibit exceptional specific strength and good cor-
rosion resistance [61]. For these reasons, great attentions have been
attracted to investigate comprehensive properties for Al-based BMGs,
especially the property of fracture toughness. Unfortunately, the max-
imum diameter obtained so far for tested Al-rich BMGs is merely
~ 1.5 mm [62,63]. As noted, this dimension level cannot meet the
Fig. 6. The SEM image of several indentations made on the Al86Ni6Y4.5Co2La1.5 BMG at
the maximum load of 24 mN. The inset is the magnified image of the indentation. No
visible cracks are observed at this indentation depth of 500 nm.
requirement in sample size as pointed out by CTOD test. Our indenta-
tion technique can be used to predict the fracture toughness that has not
been obtained experimentally. Fig. 6 shows the SEM image of several
indentations made on the Al86Ni6Y4.5Co2La1.5 BMG at the maximum
load of 24 mN, where no visible cracks are observed. The indentation
fracture toughness KC of Al86Ni6Y4.5Co2La1.5 BMG is 35 ± 3 MPa √ m

Table 2
Summary of the power-law fitting parameters (k, n, g and m) of the load-displacement (P-h) curves (P = khn) and measured hardness-displacement (HD-h) curves (HD = ghm) for the
BMGs. The critical indentation depth h⁎ was determined from the extrapolation of the HD-h fitting curve, i.e. HD = ghm. The indentation fracture toughness KC values can be estimated
through Eq. (8) using k, n, H, E, Er and h⁎ values. Furthermore, a comparison of the fracture toughness KC obtained from the indentation tests (IT) and values KQ from the crack tip opening
displacement (CTOD) tests. Data for KQ from Refs [7–10,13].

Metallic glasses P = k× hn HD = g× hm h⁎ (nm) KC from IT (MPa√ m) KQ from CTOD (MPa √m) Difference
| KC − KQ |/KQ
−4
k (10 ) n R g m R

Fe65Mo14C15B6 15.50 1.72 0.99 73.37 − 0.32 0.99 1224 ± 147 41 ± 2 38 ± 10 8%

Cu49Hf42Al9 7.84 1.75 0.99 32.03 − 0.23 0.99 10,643 ± 1367 62 ± 3 65 ± 10 5%
Ni40Cu5Zr28.5Ti16.5Al10 6.00 1.79 0.99 29.50 − 0.25 0.99 4076 ± 494 42 ± 2 38 ± 7 10%
Zr55Al10Ni5Cu30 4.99 1.78 0.99 21.53 − 0.22 0.99 11,429 ± 2184 50 ± 4 52 ± 10 4%
Ce60Al20Ni10Cu10 2.72 1.75 0.99 13.02 − 0.30 0.99 2859 ± 457 11 ± 1 10 10%
Al86Ni6Y4.5Co2La1.5 3.26 1.79 0.99 16.75 − 0.21 0.99 7840 ± 1721 35 ± 3 – –

326
H. Guo et al.
when the h⁎ is up to 7840 ± 1721 nm. According to Eq. (11), the
fracture toughness KQ of Al86Ni6Y4.5Co2La1.5 BMG is predicted to be
~ 35 MPa √ m, which is comparable to that of high strength aluminum
alloys [64].
Finally, we need to point out that the premise of the indentation
technique (Eq. (8)) is that the indentation deformation energy per unit
area absorbed to a critical indentation depth could be correlated with
the fracture energy for fracture initiation. Different from the conven-
tional CTOD testing procedures, the current indentation technique
provides a new protocol to estimate the indentation fracture toughness.
In addition, we have observed the correlation between fracture
toughness values estimated from the indentation tests and the CTOD
tests in Fig. 5. Although at present such a correlation still lack the en-
ough support of underlying physics, the approximately 10% difference
in the fracture toughness values between the indentation tests and the
CTOD tests reflects that to some extent the indentation technique is
reasonable. Next much more investigations in the inherent physical
correlation are highly needed.
5. Conclusions
(1) Using the P-h curves, a nanoindentation technique has been de-
veloped to evaluate the fracture toughness of BMGs. The concept of
CDM theory is introduced to determine the characteristic fracture
initiation point during indentation.
(2) The values of indentation fracture toughness of BMGs were esti-
mated and compared with those from CTOD tests. For the BMGs
(KC < 80 MPa √ m), the experimental results show a good agree-
ment in fracture toughness values between the indentation and
CTOD tests within an approximately relative difference of 10%.
(3) The fracture toughness KQ from the CTOD tests scales with
the indentation fracture toughness KC, which is expressed
as KQ = 1.1KC − 3.7. The fracture toughness KQ of
Al86Ni6Y4.5Co2La1.5 BMG is predicted to be ~35 MPa √m.
Acknowledgements
This work was supported by the National Key Research and
Development Program of China (No. 2016YFB1100204) and National
Natural Science Foundation of China (Nos. 51131006, 51471166).
Special thanks are indebted to Prof. J. Xu, Prof. G.P. Zhang, Dr. Z.Q.
Song and Dr. S. P. Wang for helpful discussions, Master J.L. Zhang for
the preparing of the alloy ingots.
References
[1] L.A. Davis, Fracture of Ni-Fe base metallic glasses, J. Mater. Sci. 10 (1975)
1557–1564.
[2] H. Kimura, T. Masumoto, Fracture toughness of amorphous metals, Scr. Metall. 9
(1975) 221–222.
[3] A.T. Alpas, L. Edwards, C.N. Reid, Fracture and fatigue crack propagation in a
nickel-base metallic glass, Metall. Trans. A. 20A (1989) 1395–1409.
[4] W. Chen, Z. Liu, J. Ketkaew, R.M.O. Mota, S. Kim, M. Power, W. Samela,
J. Schroers, Flaw tolerance of metallic glasses, Acta Mater. 107 (2016) 220–228.
[5] Q. He, Y.Q. Cheng, E. Ma, J. Xu, Locating bulk metallic glasses with high fracture
toughness: chemical effects and composition optimization, Acta Mater. 59 (2011)
202–215.
[6] M.D. Demetriou, M.E. Launey, G. Garrett, J.P. Schramm, D.C. Hofmann,
W.L. Johnson, R.O. Ritchie, A damage-tolerant glass, Nat. Mater. 10 (2011)
123–128.
[7] J.J. Lewandowski, X.J. Gu, A. Shamimi Nouri, S.J. Poon, G.J. Shiflet, Tough Fe-
based bulk metallic glasses, Appl. Phys. Lett. 92 (2008) 091918–091920.
[8] P. Jia, Z.D. Zhu, E. Ma, J. Xu, Notch toughness of Cu-based bulk metallic glasses,
Scr. Mater. 61 (2009) 137–140.
[9] Z.D. Zhu, P. Jia, J. Xu, Optimization for toughness in metalloid-free Ni-based bulk
metallic glasses, Scr. Mater. 64 (2011) 785–788.
[10] A. Kawashima, H. Kurishita, H. Kimura, T. Zhang, A. Inoue, Fracture toughness of
Zr55Al10Ni5Cu30 bulk metallic glass by 3-point bend testing, Mater. Trans. 46 (2005)
1725–1732.
[11] C.P. Kim, J.Y. Suh, A. Wiest, M.L. Lind, R.D. Conner, W.L. Johnson, Fracture
toughness study of new Zr-based Be-bearing bulk metallic glasses, Scr. Mater. 60
327
Journal of Non-Crystalline Solids 481 (2018) 321–328
(2009) 80–83.
[12] C.J. Gilbert, R.O. Ritchie, W.L. Johnson, Fracture toughness and fatigue-crack
propagation in a Zr–Ti–Ni–Cu–Be bulk metallic glass, Appl. Phys. Lett. 71 (1997)
476–478.
[13] X.K. Xi, D.Q. Zhao, M.X. Pan, W.H. Wang, Y. Wu, J.J. Lewandowski, Fracture of
brittle metallic glasses: brittleness or plasticity, Phys. Rev. Lett. 94 (2005)
125510–125513.
[14] A.G. Evans, E.A. Charles, Fracture toughness determinations by indentation, J. Am.
Ceram. Soc. 59 (1976) 371–372.
[15] M. Sebastiani, K.E. Johanns, E.G. Herbert, G.M. Pharr, Measurement of fracture
toughness by nanoindentation methods: recent advances and future challenges,
Curr. Opin. Solid ST. M. 19 (2015) 324–333.
[16] V. Keryvin, V.H. Hoang, J. Shen, Hardness, toughness, brittleness and cracking
systems in an iron-based bulk metallic glass by indentation, Intermetallics 17
(2009) 211–217.
[17] X.D. Li, D.F. Diao, B. Bhushan, Fracture mechanisms of thin amorphous carbon
films in nanoindentation, Acta Mater. 45 (1997) 4453–4461.
[18] S. Frank, U.A. Handge, S. Olliges, R. Spolenak, The relationship between thin film
fragmentation and buckle formation: synchrotron-based in situ studies and two-
dimensional stress analysis, Acta Mater. 57 (2009) 1442–1453.
[19] F.F. Schlich, R. Spolenak, Size- and phase-dependent mechanical properties of ul-
trathin Si films on polyimide substrates, Acta Mater. 110 (2016) 122–130.
[20] G.D. Quinn, R.C. Bradt, On the Vickers indentation fracture toughness test, J. Am.
Ceram. Soc. 90 (2007) 673–680.
[21] P.A. Hess, S.J. Poon, G.J. Shiflet, R.H. Dauskardt, Indentation fracture toughness of
amorphous steel, J. Mater. Res. 20 (2005) 783–786.
[22] D.C. Qiao, G.Y. Wang, P.K. Liaw, V. Ponnambalam, S.J. Poon, G.J. Shiflet, Fatigue
behavior of an Fe48Cr15Mo14Er2C15B6 amorphous steel, J. Mater. Res. 22 (2006)
544–550.
[23] H. Zhang, X. Jing, G. Subhash, L.J. Kecskes, R.J. Dowding, Investigation of shear
band evolution in amorphous alloys beneath a Vickers indentation, Acta Mater. 53
(2005) 3849–3859.
[24] J.C. Qiao, Y. Yao, J.M. Pelletier, L.M. Keer, Understanding of micro-alloying on
plasticity in Cu46Zr47 − xAl7Dyx (0 ≤ x ≤8) bulk metallic glasses under compres-
sion: based on mechanical relaxations and theoretical analysis, Int. J. Plast. 82
(2016) 62–75.
[25] Y. Tong, J.C. Qiao, C. Zhang, J.M. Pelletier, Y. Yao, Mechanical properties of
Ti16.7Zr16.7Hf16.7Cu16.7Ni16.7Be16.7 high-entropy bulk metallic glass, J. Non-Cryst.
Solids 452 (2016) 57–61.
[26] T.S. Byun, J.W. Kim, J.H. Hong, A theoretical model for determination of fracture
toughness of reactor pressure vessel steels in the transition region from automated
ball indentation test, J. Nucl. Mater. 252 (1998) 187–194.
[27] F.M. Haggag, T.S. Byun, J.H. Hong, P.Q. Miraglia, K.L. Murty, Indentation-energy-
to-fracture (IEF) parameter for characterization of DBTT in carbon steels using
nondestructive automated ball indentation (ABI) technique, Scr. Mater. 38 (1998)
645–651.
[28] J.S. Lee, J.i. Jang, B.W. Lee, Y. Choi, S.G. Lee, D. Kwon, An instrumented in-
dentation technique for estimating fracture toughness of ductile materials: a critical
indentation energy model based on continuum damage mechanics, Acta Mater. 54
(2006) 1101–1109.
[29] M. He, F.G. Li, N. Ali, A normalized damage variable for ductile metals based on
toughness performance, Mater. Sci. Eng. A 528 (2011) 832–837.
[30] P. Maimí, P.P. Camanho, J.A. Mayugo, C.G. Dávila, A continuum damage model for
composite laminates: part I – Constitutive model, Mech. Mater. 39 (2007) 897–908.
[31] S. Kamat, H. Kessler, R. Ballarini, M. Nassirou, A.H. Heuer, Fracture mechanisms of
the Strombus gigas conch shell: II-micromechanics analyses of multiple cracking and
large-scale crack bridging, Acta Mater. 52 (2004) 2395–2406.
[32] H. Guo, C.B. Jiang, B.J. Yang, J.Q. Wang, Deformation behavior of Al-rich metallic
glasses under nanoindentation, J. Mater. Sci. Technol. (2017), http://dx.doi.org/
10.1016/j.jmst.2016.10.014.
[33] G. Wanlin, Elasto-plastic three-dimensional crack border field—III. Fracture para-
meters, Eng. Fract. Mech. 51 (1995) 51–71.
[34] J. Lemaitre, A continuous damage mechanics model for ductile fracture, J. Eng.
Mater. Technol. 107 (1985) 83–89.
[35] J. Cao, F.G. Li, P. Li, X.K. Ma, J.H. Li, Analysis of ductile–brittle competitive fracture
criteria for tension process of 7050 aluminum alloy based on elastic strain energy
density, Mater. Sci. Eng. A 637 (2015) 201–214.
[36] J.H. Lee, Y.F. Gao, K.E. Johanns, G.M. Pharr, Cohesive interface simulations of
indentation cracking as a fracture toughness measurement method for brittle ma-
terials, Acta Mater. 60 (2012) 5448–5467.
[37] S.S. Chiang, D.B. Marshall, A.G. Evans, The response of solids to elastic/plastic
indentation. I. Stresses and residual stresses, J. Appl. Phys. 53 (1982) 298–311.
[38] S.S. Chiang, D.B. Marshall, A.G. Evans, The response of solids to elastic/plastic
indentation. II. Fracture initiation, J. Appl. Phys. 53 (1982) 312–317.
[39] B.R. Lawn, A.G. Evans, A model for crack initiation in elastic-plastic indentation
fields, J. Mater. Sci. 12 (1977) 2195–2199.
[40] Y.J. Yang, J. Luo, L.P. Huang, G.L. Hu, K.D. Vargheese, Y.F. Shi, J.C. Mauro, Crack
initiation in metallic glasses under nanoindentation, Acta Mater. 115 (2016)
413–422.
[41] J.D. Toonder, J. Malzbender, G.D. With, R. Balkenende, Fracture toughness and
adhesion energy of sol-gel coatings on glass, J. Mater. Res. 17 (2002) 224–233.
[42] S. Zhang, D. Sun, Y.Q. Fu, H.J. Du, Toughness measurement of thin films: a critical
review, Surf. Coat. Technol. 198 (2005) 74–84.
[43] J. Chen, S.J. Bull, Assessment of the toughness of thin coatings using na-
noindentation under displacement control, Thin Solid Films 494 (2006) 1–7.
[44] G.R. Irwin, Analysis of stresses and strains near the end of a crack traversing a plate,
H. Guo et al.
J. Appl. Mech. 24 (1957) 361–364.
[45] F. Erdogan, Fracture mechanics, Int. J. Solids Struct. 37 (2000) 171–183.
[46] B.A. Sun, W.H. Wang, The fracture of bulk metallic glasses, Prog. Mater. Sci. 74
(2015) 211–307.
[47] J.H. Li, F.G. Li, X.K. Ma, Q.R. Wang, J.Z. Dong, Z.W. Yuan, F.M. Xue, A strain-
dependent ductile damage model and its application in the derivation of fracture
toughness by micro-indentation, Mater. Des. 67 (2015) 623–630.
[48] Y.T. Cheng, C.M. Cheng, Relationships between hardness, elastic modulus, and the
work of indentation, Appl. Phys. Lett. 73 (1998) 614–616.
[49] Y.T. Cheng, Z.Y. Li, C.M. Cheng, Scaling relationships for indentation measure-
ments, Philos. Mag. A 82 (2002) 1821–1829.
[50] C. Gao, M. Liu, Instrumented indentation of fused silica by Berkovich indenter, J.
Non-Cryst. Solids 475 (2017) 151–160.
[51] C.C. Tasan, J.P.M. Hoefnagels, M.G.D. Geers, Identification of the continuum da-
mage parameter: an experimental challenge in modeling damage evolution, Acta
Mater. 60 (2012) 3581–3589.
[52] L.M. Kachanov, Introduction to Continuum Damage Mechanics, Martinus Nijhoff,
Dordrecht, 1986.
[53] J. Lemaiter, J. Dufailly, Damage measurements, Eng. Fract. Mech. 28 (1987)
643–661.
[54] J.G. Swadener, E.P. George, G.M. Pharr, The correlation of the indentation size
effect measured with indenters of various shapes, J. Mech. Phys. Solids 50 (2002)
681–694.
[55] H. Andersson, Analysis of a model for void growth and coalescence ahead of a
328
Journal of Non-Crystalline Solids 481 (2018) 321–328
moving crack tip, J. Mech. Phys. Solids 25 (1977) 217–233.
[56] L. Xue, Constitutive modeling of void shearing effect in ductile fracture of porous
materials, Eng. Fract. Mech. 75 (2008) 3343–3366.
[57] P. Murali, T.F. Guo, Y.W. Zhang, R. Narasimhan, Y. Li, H.J. Gao, Atomic scale
fluctuations govern brittle fracture and cavitation behavior in metallic glasses,
Phys. Rev. Lett. 107 (2011) 215501–215505.
[58] P. Guan, S. Lu, M.J. Spector, P.K. Valavala, M.L. Falk, Cavitation in amorphous
solids, Phys. Rev. Lett. 110 (2013) 185502–185506.
[59] R. Maaß, P. Birckigt, C. Borchers, K. Samwer, C.A. Volkert, Long range stress fields
and cavitation along a shear band in a metallic glass: the local origin of fracture,
Acta Mater. 98 (2015) 94–102.
[60] W.C. Oliver, G.M. Pharr, An improved technique for determining hardness and
elastic modulus using load and displacement sensing indentation experiments, J.
Mater. Res. 7 (1992) 1564–1583.
[61] B.J. Yang, J.H. Yao, J. Zhang, H.W. Yang, J.Q. Wang, E. Ma, Al-rich bulk metallic
glasses with plasticity and ultrahigh specific strength, Scr. Mater. 61 (2009)
423–426.
[62] J.P. Liao, B.J. Yang, Y. Zhang, W.Y. Lu, X.J. Gu, J.Q. Wang, Evaluation of glass
formation and critical casting diameter in Al-based metallic glasses, Mater. Des. 88
(2015) 222–226.
[63] N.C. Wu, L. Zuo, J.Q. Wang, E. Ma, Designing aluminum-rich bulk metallic glasses
via electronic-structure-guided microalloying, Acta Mater. 108 (2016) 143–151.
[64] N. Tsangarakis, All modes fracture toughness of two aluminium alloys, Eng. Fract.
Mech. 26 (1987) 313–321.