Pronounced ductility in CuZrAl ternary bulk metallic glass composites with
optimized microstructure through melt adjustment
Zengqian Liu, Ran Li, Gang Liu, Kaikai Song, Simon Pauly et al.
Citation: AIP Advances 2, 032176 (2012); doi: 10.1063/1.4754853
View online: http://dx.doi.org/10.1063/1.4754853
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Published by the American Institute of Physics.
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AIP ADVANCES 2, 032176 (2012)
Pronounced ductility in CuZrAl ternary bulk metallic
glass composites with optimized microstructure
through melt adjustment
Zengqian Liu,1 Ran Li,1,a Gang Liu,2 Kaikai Song,3 Simon Pauly,3
Tao Zhang,1,b and Ju¨rgen Eckert3,4
1Key Laboratory of Aerospace Materials and Performance (Ministry of Education),
School of Materials Science and Engineering, Beihang University, Beijing 100191, China
2State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science
and Engineering, Xi’an Jiaotong University, Xi’an, 710049, China
3IFW Dresden, Institute for Complex Materials, P.O. Box 27 01 16,
D-01171 Dresden, Germany
4TU Dresden, Institute of Materials Science, D-01062 Dresden, Germany
(Received 28 June 2012; accepted 11 September 2012; published online 19 September 2012)
Microstructures and mechanical properties of as-cast Cu47.5Zr47.5Al5 bulk metal-
lic glass composites are optimized by appropriate remelting treatment of master
alloys. With increasing remelting time, the alloys exhibit homogenized size and
distribution of in situ formed B2 CuZr crystals. Pronounced tensile ductility of
∼13.6% and work-hardening ability are obtained for the composite with optimized
microstructure. The effect of remelting treatment is attributed to the suppressed het-
erogeneous nucleation and growth of the crystalline phase from undercooled liquid,
which may originate from the dissolution of oxides and nitrides as well as from
the micro-scale homogenization of the melt. Copyright 2012 Author(s). This ar-
ticle is distributed under a Creative Commons Attribution 3.0 Unported License.
[http://dx.doi.org/10.1063/1.4754853]
I. INTRODUCTION
Although bulk metallic glasses (BMGs) exhibit unique mechanical properties, such as high
strength and elastic strain limit,1, 2 their application as structural materials is strongly limited by
their low room temperature ductility and macroscopic strain softening.3, 4 To circumvent these
restrictions, BMG composites combining a glassy matrix with ductile crystalline phases have been
developed in various systems.5–10 By properly adjusting the compositions and microstructures,
improved toughness and plasticity can be readily obtained in the composites under compressive or
even tensile conditions.7, 8 However, the combination of pronounced tensile ductility and macroscopic
work-hardening ability was not obtained until the introduction of a B2 CuZr phase into the amorphous
matrix in CuZr-based BMG composites.9–12 The prominent mechanical properties of the composites
which originate mainly from the martensitic transformation of B2 CuZr to the B19’ phase make
them promising candidates for practical applications as high-performance structural materials.10–15
Due to the large temperature gradient and cooling rate variation across the samples during the
casting process, the size and distribution of in situ formed B2 CuZr crystals are typically non-uniform
throughout the composites.12–15 This deteriorates the mechanical properties and the reliability of
the composites, especially under tensile conditions. An effective adjustment of the microstructure is
nevertheless essential because of the strong structural dependence of their mechanical properties.14, 15
However, this ought to be quite challenging in such composites. On the one hand, the B2 CuZr
phase forms by polymorphous crystallization from the melt which is different from the primarily
aCorresponding author: E-mail: liran@buaa.edu.cn (R. Li);
bzhangtao@buaa.edu.cn (T. Zhang); Tel/Fax: +86-10-82339705
2158-3226/2012/2(3)/032176/8 C© Author(s) 20122, 032176-1
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032176-2 Liu et al. AIP Advances 2, 032176 (2012)
precipitated beta dendrites in the Vit-type BMG composites.8 Thus the semi-solid processing method
which utilizes the temperature span between the solidification points of crystalline phase and glassy
matrix may not be adopted.8 On the other hand, rather high cooling rates are still required for the
glass formation of the matrix upon casting, leaving just a short time window for the operational
treatment.2, 12 In addition, the crystal precipitation is very sensitive to the temperature and alloy
compositions.13, 16 So far, the desired control and adjustment of crystal nucleation and growth
upon solidification has rarely been achieved in the composites except for an inoculation strategy
proposed very recently.17 Considering the high susceptibility of the crystallization behavior of the
undercooled melt to its thermal history, an appropriate melt treatment can be a potent measure for
this processing.18–20
In this study, we report a simple but effective method to properly adjust the microstructure and
the mechanical properties of CuZr-based BMG composites using a remelting treatment. The origins
of the effect are investigated from the viewpoint of thermodynamics and kinetics for crystallization
of the B2 CuZr phase.
II. EXPERIMENTAL
Alloy ingots (∼40 g for each sample) with nominal composition of Cu47.5Zr47.5Al5 were prepared
by are-melting the pure constituents (purity 99.5∼99.99 wt.%) in Ti-gettered high-purity argon
atmosphere. The ingots were remelted for 4, 8, 12 and 20 times, respectively, with ∼1 min duration
for each time under a fixed melting current of 410 A. The oxygen and nitrogen contents in the
alloy ingots were measured by the inert gas fusion technique using a LECO-TC436 O/N analyzer
with an error of less than 10%. The master alloys were then remelted in a quartz tube and injected
under the same pressure into copper molds with cylindrical cavities of 3 mm diameter. The casting
temperatures were kept almost constant for all the alloys with deviations of less than 50 K. For
comparison, amorphous ribbons with a thickness of ∼30 μm and a width of ∼1 mm were prepared
by melt spinning. The microstructures of the as-cast rods were analyzed by X-ray diffraction (XRD)
and scanning electron microscopy (SEM). Tensile tests were performed on specimens with a gauge
dimension of � 1.5 mm × 6 mm machined from the � 3 mm rods at a strain rate of 3 × 10-4 s-1
at room temperature. The morphologies of the tensile fractured samples were characterized by a
high-resolution SEM equipped with a field emission gun. The crystallization behavior of the glassy
ribbons was examined using a differential scanning calorimeter (DSC) at a heating rate of 0.167 K/s.
Isothermal annealing at temperatures of 708, 713, and 718 K, respectively, was also carried out in
the DSC. The melting and solidification behavior was analyzed at a constant rate of 0.33 K/s using
the ingots.
III. RESULTS AND DISCUSSION
Figure 1 shows the typical microstructures of the as-cast � 3 mm rods for the alloys remelted
for different times. The central regions used for the tensile tests are marked by dashed circles.
Crystalline particles in different morphologies and distributions are embedded in the amorphous
matrix for all the alloys. The crystals were identified as the B2 CuZr phase by XRD (results not
shown here). For the sample remelted for 4 times, a gradient microstructure was observed with the
crystalline volume fraction and particle size decreasing radially from the center to the surface of the
rod. The crystals are severely impinged in the center. In addition, coarse grains tend to precipitate
in the sample with a dendrite substructure resolvable by SEM, as indicated by the white arrow in
Fig. 1(a). The non-uniform features concerning the size and distribution of the B2 CuZr precipitates
agree well with the widely reported results typically observed for CuZr-based BMG composites.12–15
With increasing remelting time, the samples exhibit lower volume fractions of B2 CuZr phase and
reduced crystal sizes, pointing to an improved glass-forming ability (GFA) of the alloys. Furthermore,
the distribution of the crystals is effectively homogenized by the remelting treatment. An optimized
composite structure with ∼13-75 μm large B2 CuZr crystals that are homogeneously distributed
within the continuous glassy matrix is obtained after 12 times remelting. The average inter-particle
spacing is ∼53 μm. For the alloy remelted for 20 times, however, the crystalline volume fraction
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032176-3 Liu et al. AIP Advances 2, 032176 (2012)
FIG. 1. SEM images of the as-cast 3 mm diameter BMG composites for the alloys remelted for different times. The central
region used for the tensile tests is marked by a dashed circle for each sample.
becomes too low despite of the uniform distribution, which is expected to be deleterious to the
mechanical properties of the composites.14, 15
The mechanical properties of the composites were evaluated by tensile tests on the dog-bone
shaped samples. As shown in Fig. 2, the samples exhibit distinct tensile properties with the increase
in remelting time. The longer the remelting time, the higher is the yield strength and the less
pronounced is the work-hardening behavior of the composites. This can be attributed to the difference
in microstructure, and mainly corresponds to the volume fractions of the B2 CuZr phase. As
demonstrated by Pauly et al., the compressive yield strength of the composites, which can be
evaluated by either the rule of mixtures or the load-bearing model depending on the crystalline
volume fraction present in the material, decreases quickly with an increase in the volume fraction of
B2 CuZr phase.14, 15 Based on our results, this trend is applicable to the tensile conditions although
further more detailed analysis is required to validate the quantitative relations. On the other hand, as
the work-hardening ability originates mainly from the martensitic transformation of B2 CuZr to the
B19’ phase,10–15 the crystalline volume fraction should be a key factor governing the work-hardening
behavior of such composites. The work-hardening ability is expected to increase monotonically with
the increase in B2 CuZr volume fraction, which is consistent with the results obtained by compression
tests.14, 15 Furthermore, the tensile ductility of the composites shows a strong dependence on the
remelting time as well, but in a different manner. With increasing remelting time, the samples first
exhibit both improved plastic strain and enhanced strength. The tensile ductility reaches a maximum
value (∼13.6%) for the 12-times-remelted alloy. The yield strength and average strain-hardening
exponent of the sample are ∼1190 MPa and ∼0.25, respectively. The tensile ductility and work-
hardening ability of the composite are more pronounced while the yield strength is comparably
high when compared with those of the reported BMG composites toughened by solid solutions or
B2 CuZr phase.6–12 For the alloy remelted for 20 times, however, only almost negligable ductility
was found due to the high glassy volume fraction. These findings prove that the microstructure and
mechanical properties of the composites can be effectively adjusted by controlling the remelting
time of master alloys. An optimized combination of high yield strength, prominent tensile ductility,
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032176-4 Liu et al. AIP Advances 2, 032176 (2012)
FIG. 2. True tensile stress-strain curves of the BMG composites for the alloys remelted for different times.
and pronounced work-hardening ability can be readily obtained in the as-cast alloys remelted for 12
times under the present conditions.
Figure 3 shows SEM images of a tensile fractured specimen for the 12-times-remelted alloy.
The sample exhibits apparent necking just before the final fracture corresponding to the stress-drop
segment on the stress-strain curve. Aside from the accumulation of shear bands in the necked region,
a high density of multiple shear bands can be observed across the whole gauge section (Fig. 3(a)).
During plastic deformation, the propagation of shear bands in the glassy matrix is hindered and
arrested by the homogeneously dispersed crystalline precipitates, resulting in the multiplication of
shear bands, as shown in Figs. 3(b)–3(d). Furthermore, through the martensitic transformation of
the B2 CuZr phase, not only local stress concentrations at the two-phase interface are released,10–15
but also the applied strain can be accommodated by the ductile crystals.14, 15 As the deformed
crystalline particles which have experienced the transformation become harder than the undeformed
regions,12, 15 further plastic strain is accommodated by the undeformed crystals. The necking occurs
only after nearly all the crystals have completed the transformation. Therefore, the sample exhibits
a rather uniform plastic deformation along the whole gauge length after yielding. The restrained
necking in the present sample indicates a significantly improved stability of plastic deformation in
the composites.11
It has been demonstrated that the plastic deformation in BMGs/BMG composites depends
strongly on a characteristic plastic zone size Rp which can be expressed as
Rp = K 2IC/2πσ 2y , (1)
where KIC and σy are the plain-strain fracture toughness and the yield strength of the glassy matrix,
respectively.2, 3, 8 Shear bands can be stabilized against developing into cracks by a second phase
when the length-scale of the microstructural inhomogeneity L is smaller than but comparable to Rp
in the composites.2, 3, 8 For the present CuZr-based metallic glass, Rp is estimated to be ∼240 μm by
adopting the values of KIC ≈ 70 M Pa
√
m and σy ≈ 1800 M Pa.2, 3, 13 Therefore, the crystal size as
well as the inter-particle spacing are both smaller than but of the same order of magnitude as Rp for
the 12-times-remelted sample. This promotes the stabilization of shear bands and contributes to the
enhanced tensile ductility. On the other hand, the fracture strain of the composites can be described
as
εc = fαεα + fβεβ + K fαβεαβ, (2)
where εα , εβ and εαβ are the fracture strain of the single glassy phase, the crystalline phase and
the ideal homogeneous “glassy + crystalline” composite, respectively. fα , fβ and fαβ are the cor-
responding volume fractions of the three microstructural constituents, and K is a dimensionless
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032176-5 Liu et al. AIP Advances 2, 032176 (2012)
FIG. 3. Morphologies of the lateral (a, c, d) and fracture (b) surfaces of a tensile fractured sample for the alloy remelted for
12 times.
constant.14, 15 Because εαβ is much higher than εα and εβ in tension, the homogenization in size
and distribution of B2 CuZr particles which results in a larger fαβ for the same crystalline volume
fraction will validly contribute to the tensile ductility of the composites. Therefore, the optimized mi-
crostructure with fαβ approaching 100 vol.% is very effective for obtaining the enhanced mechanical
performance of the 12-times-remelted composites.
It is known that the thermodynamics and kinetics of crystallization from the undercooled melt
are highly sensitive to inherent factors, such as inclusions, compositions and thermal history of the
alloy.18–24 The structure and properties of cast alloys can be strongly affected by melt treatment.22–24
In this study, the varying trend of the microstructural features on the remelting time in the obtained
BMG composites is definitely validated although the optimum remelting time may vary for different
melting parameters and conditions. The effect of the remelting treatment may be understood from
the following aspects. Firstly, inclusions such as refractory oxides and nitrides or oxygen/nitrogen
stabilized phases may initiate heterogeneous crystal nucleation during the solidification process,
especially in glass-forming systems.25–27 It has been reported that the detriments of oxides and
other contaminants can be mitigated or eliminated by adopting remelting, overheating or successive
heating-cooling thermal cycling treatments on the melt.18–27 In this study, the oxides and nitrides
which may act as heterogeneous nucleation sites are expected to be broken down and dissolved
by the remelting process. This can be manifested by the increased contents of oxygen and nitrogen
measured for the remelted alloys, as shown in Fig. 4(a). The possibility of the contamination of leaked
air into the arc-furnace can be ruled out because the oxygen tends to be saturated eventually. Thus the
heterogeneous nucleation of B2 CuZr crystals is suppressed, contributing to the homogenization in
the size and distribution of B2 CuZr particles as well as the improved GFA. Secondly, the benefits of
minor doping of oxygen and nitrogen on the GFA have been validated in the CuZr-based alloys.16, 28
It is reported that the dissolution of trace contents of oxygen and nitrogen in the liquid state can
generate a wider atom size distribution and more efficient atomic packing structure in the alloys.16, 28
As a result, the undercooled melt may exhibit a somewhat lower atomic diffusivity which leads to
sluggish nucleation and growth kinetics of crystallization. This could give an explanation for the
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032176-6 Liu et al. AIP Advances 2, 032176 (2012)
FIG. 4. Variation in the measured oxygen and nitrogen contents with remelting time (a) and schematic illustration of time-
temperature-transformation diagrams for the alloys remelted for different times (b) with the isothermal annealing curves at
708 K shown in the inset.
improved GFA in the remelting treated alloys. Thirdly, micro-chemical or topologic
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