JOM, Vol. 68, No.

3, 2016
DOI: 10.1007/s11837-015-1779-8
Ó 2016 The Minerals, Metals & Materials Society

A Combinatorial Approach to the Investigation of Metal Systems

that Form Both Bulk Metallic Glasses and High Entropy Alloys

BRIAN A. WELK,1,3 MARK A. GIBSON,2 and HAMISH L. FRASER1

1.—Department of Materials Science and Engineering, Center for the Accelerated Maturation of
Materials, The Ohio State University, 1305 Kinnear Road, Columbus, OH 43212, USA. 2.—CSIRO
Manufacturing, Private Bag 10, Clayton, VIC 3169, Australia. 3.—e-mail: welk.3@osu.edu

In this work, compositionally graded specimens were deposited using the laser
engineered net-shaping (LENSTM) additive manufacturing technique to study
the glass-forming ability of two bulk metallic glass (BMG) and high entropy
alloy (HEA) composite systems. The first graded specimen varied from
Zr57Ti5Al10Cu20Ni8 (BMG) to CoCrFeNiCu0.5 (HEA) and the second graded
specimen varied from TiZrCuNb (BMG) to (TiZrCuNb)65Ni35 (HEA). After
deposition, laser surface melting experiments were performed parallel to the
gradient to remelt and rapidly solidify the specimen. Scanning electron mi-
croscopy and energy dispersive x-ray spectroscopy were used to determine the
morphology and composition variations in the as-deposited and laser surface
melted phases. Selected area diffraction of the melt pool regions confirmed an
almost fully amorphous region in the first gradient and an amorphous matrix/
crystalline dendrite composite structure in the second gradient.

major component elements. Other equiatomic high

INTRODUCTION
High entropy alloys (HEAs), first named by Yeh1
in 2004, are defined as an alloy containing five or
more elements with equiatomic or near-equiatomic
concentrations and forming fcc and/or bcc solid
solutions. HEAs are different from typical alloy
systems as they are based on multi-principal alloy-
ing elements. Bulk metallic glasses (BMGs), how-
ever, are typically based on a single principal
element with multiple minor alloying additions.
HEAs and BMGs share similar properties such as
high strength2,3 and corrosion resistance.4,5 HEAs
have reported fracture strengths around 1000 MPa
with 20% elongation,6 while BMGs typically fail in a
brittle manner with very little elongation. Research
has shown that creating a BMG composite with
crystalline dendrites in an amorphous matrix can
improve the ductility of BMGs while maintaining
their high strength.7 There appear to be several
advantages associated with BMGs and HEAs, and
the present study has been aimed at investigating
whether there are alloy compositions where these
advantages may be captured in a composite form.
Indeed, recent work has been performed to combine
these two classes of alloys. Gao et al. 8 demonstrated
the ability to form new glassy alloys using multiple
entropy bulk metallic glasses have been reported
with critical diameters of 3 mm9 and larger than
15 mm.10 Cunliffe et al.11 selected the alloy series
(TiZrNbCu)1 xNix, where x = 0.125, 0.15, 0.20 and
0.25, because it fulfilled the requirements of a glass
former and high entropy alloy. Using melt-spun
ribbons, they detected amorphous traces in all four
alloys. Due to the similarities and potentially
advantageous properties of HEAs and BMGs, a
systematic method must be developed to investigate
the large composition space of these alloys more
efficiently.
Additive manufacturing, in particular laser pow-
der deposition techniques such as laser engineered
net-shaping (LENSTM), has emerged in the past
decade as a rapid prototyping tool to create complex
parts or to repair defects in existing parts. The
LENSTM can also be used as a research tool due to
its unique ability to deposit custom elemental
blends from multiple powder feeders to produce
compositionally graded alloys. Typically, this work
has focused on elemental binary systems,12
although other gradients have been produced vary-
ing the composition from 304L stainless steel
to Invar 35.13 The LENSTM has also been used
in previous work by the authors to study the

(Published online January 20, 2016) 1021

1022 Welk, Gibson, and Fraser

Fig. 1. Scanning electron backscattered images along the BMG–HEA 1 gradient. (a) The BMG base layer microstructure is comprised of
dendrites and two equiaxed phases. The equiaxed phases are labeled ‘‘A’’ and ‘‘B’’. The composition of each phase is shown in Table I. (b) The
BH1 Mid layer microstructure consists of three phases labeled ‘‘C’’, ‘‘D’’ and ‘‘E’’. The composition of each phase is shown Table II. (c) The HEA
layer microstructure contains equiaxed grains and a Cu-rich phase. The Cu-rich phase is indicated with an arrow.

Table I. Phase compositions (at.%) of the BMG base layer

Area Zr Al Ti Ni Cu
Overall 54.2 ± 1.4 11.4 ± 0.8 6.6 ± 0.3 9.5 ± 0.3 18.3 ± 0.5
Dendrite 47.7 ± 1.6 19.4 ± 1.1 6.4 ± 0.3 8.2 ± 0.3 18.4 ± 0.6
Phase A 59.3 ± 1.5 6.5 ± 0.5 4.0 ± 0.3 11.2 ± 0.7 19.1 ± 1.4
Phase B 57.8 ± 1.4 14.3 ± 1.0 7.5 ± 0.4 10.5 ± 0.4 9.9 ± 0.5
Phases A and B are highlighted in Fig. 1a.

Table II. Phase compositions (at.%) of BH1 Mid

Area Zr Al Ti Ni Cu Cr Co Fe
Overall 35.8 ± 1.2 7.7 ± 0.7 3.9 ± 0.2 14.0 ± 0.4 18.7 ± 0.6 6.3 ± 1.3 6.2 ± 0.3 7.3 ± 0.3
Phase C 42.1 ± 1.3 1.9 ± 0.2 3.3 ± 0.2 18.2 ± 0.5 20.7 ± 0.6 0.8 ± 0.2 8.8 ± 0.3 4.1 ± 0.3
Phase D 44.0 ± 1.2 9.6 ± 0.7 4.3 ± 0.2 8.3 ± 0.4 9.0 ± 0.4 11.2 ± 0.4 4.8 ± 0.3 8.8 ± 0.3
Phase E 28.7 ± 0.9 10.8 ± 0.8 4.0 ± 0.2 9.1 ± 0.4 9.4 ± 0.4 17.9 ± 0.5 6.4 ± 0.3 13.7 ± 0.4
Phases C, D and E are highlighted in Fig. 1b.

Fig. 2. Scanning electron backscattered images of the BMG base layer. (a) The as-deposited microstructure. (b) The transition and (c) melt pool
region microstructures after laser surface melting with a laser power of 400 W and a travel speed of 166 mm/s.

glass-forming ability of a known BMG (Vitreloy advantage of the fast cooling rates achievable in
106a) by depositing a specimen and then performing the LENSTM.14 Using a combinatorial approach,
laser surface melting experiments and taking graded compositions from a BMG to HEA were
A Combinatorial Approach to the Investigation of Metal Systems that Form Both Bulk
Metallic Glasses and High Entropy Alloys
Fig. 3. Scanning electron backscattered image of the melt pool region after laser surface melting with a laser power of 400 W and a travel speed
of 166 mm/s of the (a) BMG base layer and (b) the BH1 Mid layer.
Fig. 4. Bright field TEM image of the laser surface melted BMG base
layer processed with a laser power of 400 W and a travel speed of
166 mm/s. The lower left inset shows diffuse rings of the electron
diffraction pattern of the amorphous matrix. The top right inset shows
the electron diffraction pattern of the crystalline nano-particle.
deposited using elemental powder blends. Laser
surface melting experiments were performed to
determine the microstructural changes and glass
forming ability of the alloys.
MATERIALS AND METHODS
Compositionally graded alloys were deposited in
an Optomec LENSTM model 750 using an IPG 500-
W fiber laser. The depositions were performed in an
argon atmosphere with an oxygen level below
10 ppm. The first graded deposition (Zr57Ti5Al10
Cu20Ni8 to CoCrFeNiCu0.5) was deposited with a
laser power of 250 W and a travel speed of 8 mm/s.
The second graded deposition (TiZrCuNb to
(TiZrCuNb)65Ni35) was deposited with a laser power
of 295 W and a travel speed of 8 mm/s. After
deposition, the specimens were sectioned along the
1023
longitudinal axis and then polished through 0.05-
lm colloidal silica. Laser surface melting experi-
ments were performed on the polished specimens
with different laser powers and travel speeds par-
allel to the build direction. After laser surface
melting was completed, the samples were placed
in a vibratory polisher with 0.05-lm colloidal silica
for 24 h.
The as-deposited and laser surface melted regions
were characterized along the build direction using
backscatter electron imaging (BSE) in an FEI Sirion
scanning electron microscope (SEM) equipped with
an EDAX Octane Silicon Drift Detector for XEDS
analysis. Site-specific transmission electron micro-
scopy (TEM) membranes were prepared in an FEI
Helios NanolabTM Dual-Beam FIB equipped with an
OmniProbe AutoProbe 200. Conventional TEM was
performed using an FEI/Philips CM-200T.
RESULTS AND DISCUSSION
BMG–HEA 1
The first BMG to HEA gradient had a BMG
composition base layer (Zr57Ti5Al10Cu20Ni8) and
was then compositionally graded to the HEA com-
position (CoCrFeNiCu0.5) by adjusting the powder
hoppers feed rate. The BMG microstructure, as seen
in Fig. 1a, consists of dendrites and two equiaxed
phases. The composition of each phase is shown in
Table I. As the ratio of the BMG to HEA composi-
tions in a single layer approaches 2:1 (this compo-
sition will now be referred to as BH1 Mid), the
microstructure contains three equiaxed phases (la-
beled C, D and E) as seen Fig. 1b. Table II lists the
composition of each phase from BH1 Mid. The
microstructure of the HEA composition consists of
two phases as seen in Fig. 1c. The light phase
(designated by the arrow) is Cu-rich. This is consis-
tent with results for an arc-melted and cast alloy of
similar composition.15
1024 Welk, Gibson, and Fraser

Fig. 5. Scanning electron backscattered images along the BMG–HEA 2 gradient. (a) The BMG base layer. (b) The 15 at.% Ni layer containing
Nb-rich dendrites and stringers (labeled ‘‘A’’) in a two-phase matrix. The two matrix phases are labeled ‘‘B’’ and ‘‘C’’. (c) The HEA layer with Nb-
rich dendrites and a stringer phase (labeled ‘‘D’’) in a two-phase matrix. The matrix phases are labeled ‘‘E’’ and ‘‘F’’. The composition of each
phase in (b) and (c) is shown in Table III.

Table III. Phase compositions (at.%) of (TiZrCuNb)85Ni15 and (TiZrCuNb)65Ni35 as-deposited microstructures

Area Zr Nb Ti Ni Cu
(TiZrCuNb)85Ni15
Overall 20.4 ± 0.6 24.7 ± 0.7 24.2 ± 0.8 14.9 ± 0.5 15.8 ± 0.5
Dendrite 7.1 ± 0.2 69.5 ± 1.0 20.0 ± 0.8 1.8 ± 0.3 1.7 ± 0.3
Stringer (A) 31.0 ± 1.0 2.6 ± 0.2 20.8 ± 0.6 21.3 ± 0.6 24.3 ± 0.7
Matrix (B) 36.3 ± 1.0 5.4 ± 0.3 25.1 ± 0.8 19.7 ± 0.6 13.5 ± 0.5
Matrix (C) 27.2 ± 0.9 4.7 ± 0.3 26.5 ± 0.8 20.7 ± 0.6 21.0 ± 0.6
(TiZrCuNb)65Ni35
Overall 14.9 ± 0.5 20.6 ± 0.7 18.4 ± 0.6 32.7 ± 0.8 13.4 ± 0.5
Dendrite 8.0 ± 0.3 56.5 ± 1.2 14.9 ± 0.6 15.1 ± 0.5 5.6 ± 0.5
Stringer (D) 14.3 ± 0.5 18.2 ± 0.7 20.9 ± 0.6 33.3 ± 0.8 13.3 ± 0.5
Matrix (E) 19.0 ± 0.7 5.0 ± 0.3 17.7 ± 0.5 40.8 ± 0.9 17.6 ± 0.5
Matrix (F) 15.2 ± 0.5 6.7 ± 0.4 24.1 ± 0.6 39.3 ± 0.9 14.7 ± 0.5

Fig. 6. Scanning electron backscattered images of the 15 at.% Ni layer. (a) The as-deposited microstructure containing Nb-rich dendrites and
stringers (labeled ‘‘A’’) in a matrix containing two phases labeled ‘‘B’’ and ‘‘C’’. The composition of each phase is shown in Table III.
(b) Microstructure containing refined dendrites in a uniform contrast matrix after laser surface melting with a laser power of 325 W and a travel
speed of 21 mm/s. (c) Microstructure comprised of dendrites in a uniform contrast matrix after the laser surface melting with a laser power of
325 W and a travel speed of 83 mm/s. The composition of each phase in (b) and (c) is shown in Table IV.

After laser surface melting, performed with a
laser power of 400 W and a travel speed of 166 mm/
s, three distinct regions were seen in the BMG base
layer (Fig. 2). These are the as-deposited (Fig. 2a),
transition (Fig. 2b) and melt pool (Fig. 2c) regions.
These three regions were present in previous laser
surface melting experiments performed by the
authors on Vitreloy 106a.14 The as-deposited region
contains three phases as previously stated. The
transition region (Fig. 2b) contains dendrites in a
A Combinatorial Approach to the Investigation of Metal Systems that Form Both Bulk 1025
Metallic Glasses and High Entropy Alloys

Table IV. Phase compositions (at.%) of the 325-W 21-mm/s melt pool and 325-W 83-mm/s melt pool measured
by SEM XEDS

Area Zr Nb Ti Ni Cu
325 W 21 mm/s melt pool
Overall 17.0 ± 0.6 27.7 ± 1.0 26.3 ± 1.0 15.0 ± 0.5 13.9 ± 0.5
Dendrites 16.2 ± 0.6 30.6 ± 1.1 26.5 ± 1.0 13.8 ± 0.5 12.9 ± 0.5
Matrix 19.1 ± 0.8 19.8 ± 0.9 25.7 ± 1.0 18.4 ± 0.6 17.1 ± 0.5
325 W 83 mm/s melt pool
Overall 18.3 ± 0.7 22.7 ± 0.9 27.0 ± 0.9 14.9 ± 0.4 17.1 ± 0.5
Dendrite 15.0 ± 0.6 34.4 ± 1.1 27.5 ± 1.0 10.7 ± 0.4 12.4 ± 0.5
Matrix 20.4 ± 0.8 16.2 ± 0.8 26.7 ± 0.9 16.6 ± 0.5 20.2 ± 0.6

Fig. 7. (a) TEM BF image of the laser surface melted region processed with a laser power of 325 W and a travel speed of 83 mm/s and (b) TEM
BF image with the corresponding electron diffraction pattern of the crystalline dendrite (lower left inset) and amorphous matrix (upper right inset).

matrix exhibiting uniform contrast. The dendrites
appear to have the same contrast as seen in Fig. 2a.
It is possible that the temperature reached within
the transition region during laser surface melting
was not high enough to melt the dendrites existing
from the as-deposited condition. The melt pool
region appears featureless and of uniform contrast.
FIB foils were extracted from the melt pool
regions of the BMG base layer and BH1 Mid layer.
Figure 3a shows the uniform contrast from the
BMG base layer and Fig. 3b shows dendrites in a
uniform contrast matrix from BH1 Mid. TEM
characterization of the BMG base layer showed a
single nano-particle surrounded by a uniform con-
trast matrix (Fig. 4). The nano-particle was not seen
in the BSE image. Further analysis to determine if
the nano-particle nucleated on cooling or if it is a
remnant of the dendrites seen in the transition
region has not been completed. The insets in Fig. 4
show the electron diffraction pattern for the nano-
particle and matrix. The uniform matrix has diffuse
rings associated with amorphous alloys while the
nano-particle is crystalline. The amorphous rings in
the particle diffraction pattern are most likely due
to the amorphous matrix being above and/or below
the particle. The BH1 Mid layer (Fig. 3b) has a
refined microstructure as compared with the as-
deposited microstructure. This implies that the melt
pool region was completely molten and the den-
drites nucleated on cooling. Electron diffraction
determined that the two phases were crystalline.
This indicates that the glass-forming ability, under
the same processing conditions, is decreased for the
BH1 Mid composition as compared with the BMG
base layer composition. Further studies with
decreased laser power or increased travel speed will
need to be completed to determine the glass-forming
ability of the BH1 Mid composition.
BMG–HEA 2
The second graded alloy, based off of the work by
Cunliffe et al.,11 has a base layer of TiZrCuNb and is
compositionally graded to (TiZrCuNb)65Ni35. The
as-deposited microstructure along the gradient can
1026
be seen in Fig. 5. The TiZrCuNb microstructure
(Fig. 5a) contains Nb-rich dendrites in a two-
phase matrix. Increasing the nickel content to
approximately 15 at.%, produces a microstructure
consisting of Nb-rich dendrites and stringers (la-
beled A) in a two-phase matrix (Fig. 5b). The matrix
phases are labeled B and C in Fig. 5b. The compo-
sition of each phase is shown in Table III. Figure 5c
shows the microstructure of the (TiZrCuNb)65Ni35
composition. The volume fraction of the Nb-rich
dendrites has decreased along with the volume
fraction of the stringer phase (labeled D). The
matrix consists of two phases labeled E and F. The
composition of each phase is shown in Table III.
Areas of interest from the as-deposited and two
laser surface melted tracks, with a nickel content of
15 at.%, were selected for further analysis. The as-
deposited microstructure (Fig. 6a) contains den-
drites that are rich in Nb, stringers (labeled A) that
are rich in Zr, Ni and Cu, and the two matrix phases
(labeled B and C) contain similar amounts of Nb, Ti
and Ni but different amounts of Zr and Cu. The
composition of each phase in the as-deposited
microstructure is shown in Table III. The 325-W
21-mm/s surface melting treatment produced
refined dendrites within a single composition matrix
(Fig. 6b). As seen in Table IV, the dendrites were
slightly rich in Nb while the matrix had an increase
in Zr, Ni and Cu as compared with the dendrites.
Increasing the travel speed to 83 mm/s (Fig. 6c)
produced a microstructure similar to the 21-mm/s
melt pool. The Zr, Nb, Ni and Cu concentrations
show the same trend as the 21-mm/s melt pool as
seen in Table IV.
Site-specific FIB foils were extracted from the
three regions shown in Fig. 6. The as-deposited and
21-mm/s laser surface melting region produced
crystalline phases as determined by electron diffrac-
tion. The 83-mm/s laser surface melting region can
be seen in the TEM bright field image in Fig. 7a.
The Nb-rich dendrite is surrounded by a uniform
contrast matrix with homogeneously distributed
nano-sized particles. Electron diffraction confirmed
that the dendrite is crystalline and that the uniform
contrast matrix is amorphous (Fig. 7b). This is
consistent with the work of Cunliffe et al.11 The
glass-forming ability of the two laser surface melt-
ing experiments could be attributed to the slight
difference in Nb and Cu concentrations; however,
the difference in the laser line energy is most likely
causing the difference. The 83-mm/s travel speed
has a laser line energy one-fourth that of the 21-
mm/s travel speed producing a faster cooling rate.
Welk, Gibson, and Fraser
Further studies along the graded deposition will be
carried out to determine the glass-forming ability
along the entire gradient.
SUMMARY
Compositionally graded alloys along with laser
surface melting have been combined to rapidly
characterize two multicomponent BMG–HEA com-
posite systems. The response of the as-deposited
microstructure to laser surface melting demonstrated
the importance of heat input (i.e. laser power or travel
speed) to form a glassy structure. The glass-forming
ability of an alloy composition is important; however,
determining a composition that forms a BMG com-
posite (amorphous matrix with a uniform distribution
of crystalline particles) microstructure could lead to
new alloys with enhanced mechanical properties.
ACKNOWLEDGEMENTS
This research has been supported by an ex-
ploratory research grant provided by the Center for
the Accelerated Maturation of Materials (CAMM) of
the Ohio State University. MAG acknowledges the
support of CSIRO through the Office of the Chief
Executive (OCE) Science Program.
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