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3D printing of Fe-based bulk metallic glasses and composites with large

dimension and enhanced toughness by thermal spraying

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DOI: 10.1039/C8TA00405F

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3D printing of Fe-based bulk metallic glasses and

Cite this: J. Mater. Chem. A, 2018, 6,
6800
Received 12th January 2018
Accepted 20th March 2018
composites with large dimensions and enhanced
toughness by thermal spraying†
Cheng Zhang, ‡a Wei Wang,‡a Yi-Cheng Li,a Yan-Ge Yang,b Yue Wuc and Lin Liu*a

DOI: 10.1039/c8ta00405f

rsc.li/materials-a

Large sized Fe-based bulk metallic glasses (BMGs) and BMG/stainless
steel (SS) composites with excellent mechanical properties were
successfully fabricated using a thermal spray three-dimensional (3D)
printing (TS3DP) technique. The 3D-printed BMG and BMGC (rein-
forced with 50% SS powder) parts exhibited high fracture strength (
2
GPa) and fairly good fracture toughness (13–21 MPa m1/2, which is
200–400% greater than that of the as-cast BMG of the same
composition). The enhanced fracture toughness originates from the
intrinsically layered structure of the 3D-printed BMG components,
which caused crack deflection and thus the increase of energy dissi-
pation during crack propagation. The TS3DP technique developed in
this work opens up a new avenue for the production of BMGs and
BMG composites of theoretically limitless size, and facilitates their
application as structural and functional materials.
1. Introduction
Bulk metallic glasses (BMGs) lack a crystalline lattice, which
deters the formation of large-scale defects such as grain
boundaries and dislocations, and generally imparts superior
strength and greater elasticity to these materials compared to
conventional crystalline metals.1–6 In particular, the
outstanding characteristics of Fe-based BMG systems, such as
ultrahigh yield strength (3.0–4.5 GPa), excellent corrosion
resistance and low raw material cost, have attracted consider-
able attention for their potentially widespread applications
ranging from surface coatings to magnetic devices.7,8 However,
a
School of Materials Science and Engineering, State Key Lab for Materials Processing
and Die & Mould Technology, Huazhong University of Science and Technology,
Wuhan 430074, China. E-mail: lliu2000@mail.hust.edu.cn
b
Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese
Academy of Sciences, Shenyang 110016, China
c
Department of Physics and Astronomy, University of North Carolina at Chapel Hill,
Chapel Hill, NC 27599-3255, USA
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c8ta00405f
‡ These authors contributed equally to this work.
while the outstanding characteristics of Fe-based BMGs make
their application as structural materials highly desirable, this
application is at present critically limited. First, the achievable
dimensions of fabricated components are small. Although
some centimeter Fe-based BMGs have been reported previ-
ously,9 they are usually processed under ideal fabrication
conditions. If using low-purity raw materials or under industrial
processing conditions, the critical casting dimension of BMGs
would be dramatically decreased.10 Secondly, most of the Fe-
based BMGs demonstrate little plasticity and low toughness
(less than 5 MPa m1/2 for sizes larger than 3 mm diameter) at
room temperature.8,11,12 This intrinsic brittleness forbids the use
of Fe-based BMGs in practical applications as structural
materials.
In 2013, a three-dimensional (3D) printing technique (also
known as additive manufacturing) was rst utilized by Pauly
et al.13 to fabricate 3D Fe-based BMG components. Here, the
glassy powder was employed as the starting material which was
melted by laser irradiation, and built up layer by layer into a 3D-
BMG component. However, the fabrication of dense, crack-free
and fully amorphous Fe-based BMG components remains great
challenge by using conventional laser 3D printing techniques
due to the contradiction between requirements of a high cool-
ing rate for glass formation and a slow solidication process for
ensuring a crack-free structure.14 Herein, we present an alter-
native 3D-printing-compatible approach, denoted as thermal
spray 3D printing (TS3DP), to manufacture crack-free Fe-based
BMG and BMG composite (BMGC) structures of theoretically
unlimited dimensions using a high velocity oxygen fuel (HVOF)
system. It not only breaks through the size limitation but also
creates BMG and BMGC components exhibiting high strength
and enhanced toughness compared with the as-cast BMGs. As
such, the proposed TS3DP technique shows considerable
promise for the application of BMGs and BMGCs as structural
and/or functional materials.
The principle of the proposed TS3DP technique is sche-
matically illustrated in Fig. 1a, where the glassy powder was
brought into a semi-molten state when injected into an ignited

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Fig. 1 (a) Illustration of the thermal spraying 3D printing (TS3DP)
process using a HVOF system, wherein micro-sized glassy powder is
delivered into an HVOF gun and partially melted by an ignited
combustion gas and oxygen mixture. The semi-molten particles are
then projected towards the substrate surface at ultrasonic velocity and
flattened into well-bonded glassy lamellae. Three-dimensional Fe-
based BMG and BMGC components were created through multilayer
deposition. (b and c) Examples of large sized BMG and BMGC (with
50 wt% 316L stainless steel) components prepared by using the TS3DP
technique (after polishing).
combustion gas and oxygen mixture, and the semi-molten
particles are subsequently deposited at supersonic velocity
(600–1000 m s1) on a substrate in the form of lamellae. Typically,
the surface temperature of BMG particles during HVOF reaches
as high as 1773–2473 K, while the particles could remain in
a semi-solid state due to the extremely short in-ight duration
(
0.5 ms). BMG components with theoretically limitless size can
be sequentially built up in a layer-by-layer fashion because no
mold, other than a substrate, is required. The main advantage of
this approach over conventional 3D printing techniques using
laser or plasma systems is that TS3DP alleviates the cracking
problem owing to a signicant reduction in the thermal stress
during preparation, while maintaining the amorphous structure
of the original glassy powder due to only surface melting of the
powder and the high cooling rate (
106 K s1) achievable in the
thermal spray process.15 More importantly, the workow allows
the exible modication of the alloy composition and structure
using mixtures of various powders, thereby creating BMG and
BMGC components with superior properties.
2. Experimental section
Materials preparation
In this study, a Fe-based BMG system with a composition of
Fe48C15B6Mo14Cr15Y2 (at%) was selected due to its high glass-
forming ability (GFA) and excellent corrosion resistance.16,17 The
Fe48C15B6Mo14Cr15Y2 powder was produced by high pressure Ar
gas atomization and fully amorphous particles with diameters of
33–55 mm were separated by sieving for employment in the
TS3DP processing of BMG components. For BMG composites,
mixtures of the amorphous powder with various fractions (10–
50 wt%) of commercial 316L SS powder (with a size range of 33–
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Journal of Materials Chemistry A
55 mm, provided by Changsha Hualiu Metallurgy Powder Co., Ltd)
were obtained by low energy ball milling for 5 h, ensuring
a homogeneous mixing of the two kinds of powders. Then, the
BMG and BMGC components were formed by thermal spraying
the powder and powder mixtures onto mild-steel substrates with
a high velocity oxygen fuel (HVOF, (UniCoatPro-WokaStar 610))
system. The parameters used for TS3DP were as follows: kerosene
and oxygen ow rates were 23 L h1 and 900 L min1, respec-
tively; the spraying distance was 350 mm and the powder feed
was 30 g min1. The thickness of each layer was optimized to be
around 40 mm. Aer processing, the components were separated
from the substrate by wire-cutting, ground by using SiC papers
(from 80 to 2000 grids) and then polished to a mirror nish. For
comparison, Fe-based BMG rods with the same composition and
diameters of 4–10 mm were fabricated by means of a copper-
mold casting technique.7,18 The details of the mold casting
process can be found in the literature.18
Microstructure characterization
The microstructure of the samples was examined by X-ray
diffraction (XRD) using Cu Ka radiation and scanning elec-
tron microscopy (SEM, Quanta 2000) coupled with energy
dispersive X-ray spectroscopy (EDX). The thermal behavior of
the 3D-printed BMGs and the as-cast BMG was studied by
differential thermal analysis (DTA, TA Q600SDT) under a ow of
nitrogen with a heating rate of 20 K min1. The porosity was
measured by X-ray tomography (Versa XRM-500) using 1 mm
rod samples which were prepared by wire-cutting from the 3D-
printed BMG and BMGC parts. The interface structures between
glass splats in the TS3DP-BMG and between the glass splat and
SS splat in the TS3DP-BMGC were examined by transmission
electron microscopy (TEM, FEI Tecnai G2 F20). The TEM
samples containing the interfaces were prepared by ion milling
(Gatan 691). The oxygen content of the TS3DP samples was
examined by LECO, revealing approximately 0.2 wt% oxygen
increment during the thermal spray process.
Measurement of mechanical properties
The conventional mechanical properties of the different
samples were measured by uniaxial compression with a Zwick/
Roell 020 testing machine at a strain rate of 104 s1. The
samples employed for compression testing had dimensions of
F 3 mm  6 mm, which were extracted from as-cast rods and
TS3DP components by wire-cutting. Fracture toughness was
measured by three-point bending tests using the as-cast BMG
and the TS3DP samples with equivalent dimensions of 25 mm
 3 mm  1.5 mm.19 A notch with a root radius of 144 mm and
a depth of 0.75 mm was produced by low-speed wire cutting. At
least three tests were performed to ensure data reliability. The
surface morphology aer fracture was examined by SEM and
laser scanning confocal microscopy.
3. Results and discussion
The scale of the Fe-based BMG components prepared with the
TS3DP technique (hereaer denoted as TS3DP-BMG) is
J. Mater. Chem. A, 2018, 6, 6800–6805 | 6801

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demonstrated in Fig. 1b and c. As can be observed, the 3D-
printed TS3DP-BMG components (aer polishing) have very
large dimensions, e.g., the dimension of the TS3DP-BMG cube
is 20 mm  20 mm  20 mm (Fig. 1b) and that of the TS3DP-
BMG plate is 100 mm  100 mm  5 mm (Fig. 1c). Both of
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these components far exceed the maximum attainable size of
Fe-based BMGs developed thus far by casting. Furthermore, to
toughen the TS3DP-BMG, we employed a mixture of the selected
Fe-based amorphous powder and 316L stainless steel (SS)
powder to prepare Fe-based BMG composites (hereaer deno-
ted as TS3DP-BMGC). The volume fraction of the SS phase can
be nely tuned over a broad range from 0–100% by simply
varying the fraction of SS powder in the powder mixture. The
prismatoid-like component shown in Fig. 1b represents a large
sized TS3DP-BMGC reinforced with 50 wt% 316L SS powder as
an example. In addition, the build rate in the present TS3DP
process is estimated to be 1.2 kg h1 at a powder feed rate of 30
g min1, which is signicantly fast relative to the previously
reported 3D printing processes for the fabrication of BMG
materials, i.e., 0.3 kg h1 for selective laser melting and 0.1 kg
h1 for laser foil printing.20
The amorphous phase fraction of the as-fabricated TS3DP-
BMG was identied by X-ray diffraction (XRD) and differential
thermal analysis (DTA), which indicated that the resulting
TS3DP-BMG sample contained approximately 95% amorphous
phase, while the TS3DP-BMGC sample (reinforced with 50 wt%
SS) contained 43% amorphous phase co-existing with the crys-
talline austenite SS phase (ESI, Fig. S1 and S2†). For compar-
ison, Fe-based BMG rods of the same composition were
prepared by copper-mold casting. It was found that the as-cast
BMG rod with a diameter of 6 mm was fully amorphous,
while the sample with a diameter of 10 mm was nearly fully
crystallized (ESI, Fig. S1†), which is consistent with a previous
study, indicating that the critical size for glass formation of this
alloy is about 9 mm.12 To ensure the homogeneity of 3D printed
samples, three different zones of a 3 mm-diameter TS3DP-BMG
rod (i.e., top, middle and bottom) were intentionally extracted
out and examined by DTA. It is found that three DTA plots
almost coincided with the same crystalline temperature and
nearly the same crystallization enthalpy (ESI, Fig. S3†),
demonstrating a homogenous structure in the whole sample.
Fig. 2a and b show typical microstructures of the as-prepared
TS3DP-BMG and TS3DP-BMGC samples. Both samples exhibit
very dense and lamellar structures with no indication of
cracking. The back-scattering SEM images in Fig. 2b clearly
show two kinds of phases with different contrasts: the white one
corresponds to the BMG phase, while the grey one corresponds
to stainless steel, which were identied by EDX examinations
(see the inset in Fig. 2b). The 316L SS lamellae were homoge-
nously distributed in the amorphous matrix, which resulted in
the formation of a layered structure with alternating hard and
so phases (ESI, Fig. S4†). Three-dimensional X-ray tomography
revealed that the TS3DP-BMG and TS3DP-BMGC samples had
porosities of approximately 0.38% and 0.35%, respectively,
indicating that the TS3DP products are nearly fully densied.
Fig. 2c presents a transmission electron microscopy (TEM)
micrograph taken from an interfacial region between two
6802 | J. Mater. Chem. A, 2018, 6, 6800–6805
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Fig. 2 (a) and (b) are the SEM images of the as-fabricated TS3DP-BMG
and TS3DP-BMGC. Insets in (b) show a typical layered microstructure
of the lamellae and the EDX composition from the dark region. (c) and
(d) show the TEM micrographs of an interface of two amorphous
lamellae in the TS3DP-BMG and an interface of a glassy lamella/SS
lamella in the TS3DP-BMGC, respectively. The insets in (c) are the
SAED patterns taken from the amorphous lamellae and the interface
examined, while the inset in (d) presents a high-resolution image taken
from the interfacial region examined and the FFT pattern from the SS
phase.
amorphous lamellae in the TS3DP-BMG sample. The bright
contrast in the interfacial region in Fig. 2c might come from the
diffraction contrast or thickness variation. The maze-like
morphology in the bright-eld image and the diffused rings
in the corresponding selected area electron diffraction (SAED)
pattern indicate clearly that both the lamella and the interface
have a fully amorphous structure. Fig. 2d shows the TEM and
HRTEM (see the inset in Fig. 2d) images of an interface between
an amorphous lamella and a 316L SS lamella in the TS3DP-
BMGC sample, which shows compact binding between the two.
Fig. 3a shows representative stress versus strain curves of
TS3DP-BMG and TS3DP-BMGC samples under compression.
For comparison, as-cast BMG rods of equivalent dimensions
were tested under equivalent conditions. At least three tests
were performed to ensure data reliability. As expected, the as-
cast BMG failed via catastrophic fragmentation owing to
extreme brittleness despite its exceptionally high fracture
strength of 3.25 GPa. In contrast, the TS3DP-BMG sample
exhibited a fracture strength of nearly 2.06 GPa, which is lower
than that of the as-cast sample, but still sufficiently high (higher
than those of most high-strength steels21).
In addition, the apparent Young's modulus of the TS3DP-
BMG and TS3DP-BMGC was measured to be approximately
123 and 103 GPa, respectively, which are lower than that of the
as-cast BMG sample (235 GPa). The reduced modulus mainly
results from the intersplat structures (e.g., locally imperfect
bonding) and porosity (around 0.35%) of the TS3DP-BMG and
TS3DP-BMGC materials. Although the TS3DP-BMG sample
retains brittle characteristics, it was not catastrophically
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Fig. 3 (a) The representative stress–strain curves of as-cast BMG, TS3DP-BMG and TS3DP-BMGC samples under uniaxial compression. The
insets present images of the fractured samples after compression failure, wherein the as-cast BMG sample suffered catastrophic fragmentation,
while the TS3DP-BMGC underwent standard shear fracture. (b) Force-displacement curves for notched samples under 3-point bending. The
inset presents an image of the TS3DP-BMGC sample after failure. (c) The fracture toughness (KJ) of the samples calculated on the basis of the
ATSM standard.
fractured into fragments, as observed for the as-cast BMG,
which is indicative of an enhanced toughness. The most
intriguing nding is that the TS3DP-BMGC sample reinforced
with 50% SS exhibited a high strength of 1.85 GPa and an
appreciable plastic strain of around 2%. This composite dis-
played a fracture behavior very similar to so-called “ductile” Zr-
based BMG materials, i.e., shear fracture with a shear angle of
41 (see the inset in Fig. 3a). These results indicate that,
compared to the TS3DP-BMG, the TS3DP-BMGC sample
demonstrated fairly good toughness.
The fracture toughness of the three different types of samples
was then measured via single-edge notched beam (SENB) testing,
and the corresponding force–displacement curves are plotted in
Fig. 3b. As expected, the as-cast BMG exhibited a purely elastic
response prior to catastrophic failure, which is a typical charac-
teristic of extremely brittle materials. In contrast, the TS3DP-BMG
and TS3DP-BMGC samples exhibited remarkably higher exural
force and noticeable strain-to-failure behavior. The inset in
Fig. 3b shows an image of the TS3DP-BMGC sample aer failure,
which indicated that the TS3DP-BMGC sample was not fully
broken aer being exposed to a displacement of 1.8 mm (corre-
sponding to a strain of 1.5%). According to the ASTM standard,22
the J-integral fracture toughness KJ can be calculated by using the
following equations:
1:9A
J¼ (1)
BðW  aÞ
 0:5
JE
KJ ¼ (2)
1  v2
where J is the fracture energy, E is the Young's modulus, A is the
total area under the force–displacement curves as shown in
Fig. 3b, Poisson's ratio n was 0.3 for all samples, and a thickness B
¼ 1.5 mm, width W ¼ 3 mm and notch depth a ¼ 750 mm was
uniformly employed in this work. Based on the obtained data, KJ
for the three samples is plotted in Fig. 3c. For the as-cast BMG, KJ
is 5.1 MPa m1/2, which is very small and similar to previously
published results for brittle Fe-based BMG materials prepared by
casting.23,24 In contrast, KJ is about 13 MPa m1/2 for the TS3DP-
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Journal of Materials Chemistry A
BMG and 21 MPa m1/2 for the TS3DP-BMGC, which are 200–
400% greater than that of the as-cast BMG. It is expected that the
toughness of the TS3DP-BMGCs can be further enhanced via
modication of the reinforcements employed in terms of both
composition and component fractions. This is an important
advantage of the TS3DP technique developed in this work.
To further understand the toughening mechanism of the
TS3DP-BMG and TS3DP-BMGC materials, the fracture surfaces
of the samples were further characterized by scanning electron
microscopy (SEM) and laser scanning confocal microscopy, and
compared to the fracture surface of the as-cast BMG material.
The results are shown in Fig. 4a–f. It can be seen that the
fracture surface of the as-cast BMG sample exhibited a very
smooth morphology with a surface roughness (Ra) of less than 4
mm due to catastrophic fracture with an ultrafast crack propa-
gation velocity, which coincides with previous observations
regarding extremely brittle Fe-based BMGs.11 The fracture
surface thus exhibits no indication whatsoever of crack deec-
tion. In contrast, both TS3DP-BMG and TS3DP-BMGC samples
exhibit a step-shaped morphology aer fracture with Ra values
of 41 mm and 82 mm, respectively, demonstrating that
substantial crack deection occurred during crack propagation
in the two samples as shown in Fig. 4b, c, e, f. The relationship
between the fracture toughness and the reduced roughness (Ra/
R0, where R0 is the roughness value of the fracture surface for
the as-cast BMG) is plotted in Fig. 4g, showing that the fracture
toughness increases with increasing fracture surface roughness.
Because the roughness of the fracture surface is closely related
to the pathway of crack propagation, larger roughness indicates
larger deection (or twisting) and a longer trajectory during
crack propagation, leading to an increased energy dissipation
on the basis of the fact that the energy dissipation for crack
propagation is proportional to the crack length.25
To quantitatively assess the contribution of crack deection
to toughness, we further calculated the fracture toughness of
the three different samples according to the crack-deection
and crack-twisting mechanics proposed by Kotoul et al.26 (see
details in the ESI†), and the results are also shown in Fig. 4g.
Interestingly, the calculated toughness of the three samples
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Journal of Materials Chemistry A Communication

at%). However, the BMGs of these systems are intrinsically

brittle with zero plasticity. The present work demonstrates that
the TS3DP technique can solve these problems; especially it is
very helpful in producing Fe-based BMG composites with
various secondary crystalline phases. As compared to conven-
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tional laser-based 3D printing techniques (e.g. selective laser

melting-SLM, laser engineering near-net shaping-LENS, and
laser foil printing-LFP), the TS3DP technique shows advantages
in reducing thermal stress and alleviating the heat effect in the
3D printing process. For example, the SLM approach that is
currently widely used to prepare BMG parts always results in
cracking problems due to the huge thermal stress caused by
steep temperature gradients,31 and crystallization problems in
HAZs caused by multi-layer laser scanning. However, the TS3DP
technique developed in this work can prepare BMG parts with
almost fully amorphous structure and free of cracks. More
importantly, this technique allows preparing BMG composites
reinforced with various kinds of secondary phases by simply
mixing different feedstock powders to obtain the desirable
properties. It is believed that the proposed TS3DP technology
can open up a door to a new avenue for designing large scale
Fig. 4 3D profiles and SEM fracture morphologies of (a and d) the as- BMG materials with high toughness for structural applications.
cast BMG, (b and e) TS3DP-BMG, and (c and f) TS3DP-BMGC samples
after 3-point bending tests. (g) Correlation between the fracture
To demonstrate the applicability of the TS3DP technique
toughness and the relative roughness (Ra/R0) for the three different developed in this study to the manufacturing of real mechanical
samples, wherein the calculated results match well with the experi- parts with different geometries, we fabricated a few mechanical
mental data. (h–j) SEM image and a schematic showing a zigzag parts with the help of a mask mold. The principle is illustrated
pathway of crack propagation in the TS3DP-BMGC sample. in Fig. 5a, wherein a mask with hollow geometries was put
between the spraying gun and the substrate. Fig. 5b and c
display, respectively, exemplary as-printed Fe-based BMGC
matches well with the experimental values, conrming that the gears and the one being simply polished. Herein, the mask is
roughness-induced by crack deection (and/or twisting) is the made of 5 mm-thick mild steel. The dimensional accuracy is
dominant factor for the toughness enhancement of the TS3DP- largely dependent on the beam size of the ame (controlled by
BMG and TS3DP-BMGC samples. Compared to the as-cast BMG, the diameter of the gun nozzle and processing parameters) and
the higher crack deections and rougher fracture surfaces of the
TS3DP-BMG and TS3DP-BMGC samples are mainly due to the
heterogeneous structures (e.g., layered and alternating structure)
created using the TS3DP technique. Although the amorphous
lamellae remain brittle, the interfacial regions of the TS3DP-BMG
materials and the stainless steel lamellae in TS3DP-BMGC mate-
rials may act as a secondary phase with different mechanical
properties, and may have a different mechanical response when
meeting a crack tip, resulting in crack deection or/and multiple
cracking (see Fig. 4h–j). This is quite analogous to the toughening
mechanism proposed in so-called nacre-like or bio-inspired
composites,19,27,28 where the particular topological arrangement
of brittle constituents can cause crack deection and thus greatly
diminish the local stress intensity at the crack tip.
It is noted that a few Fe-based BMGs and composites with
good compressive plasticity and fracture toughness have been
reported, some of them even exhibit over 50% of plastic strain
and 50 MPa m1/2 of fracture toughness.29,30 All these systems
contain high Fe content (>65 at% Fe) with very limited GFA
(critical diameter for glass formation is normally less then 4
mm). Actually, these systems cannot be applied for 3D printing Fig. 5 (a) Schematic illustration of TS3D printing of BMG/BMGC parts
due to their poor GFA, which would denitely cause crystalli- with complex geometries, wherein a mask with hollow geometries is
put between the spray gun and the substrate; (b) photograph of as-
zation. The Fe-based systems with good GFA (critical diameter
deposited Fe-based BMGC gears; (c) photograph of one Fe-based
for glass formation >10 mm) usually contain low Fe content (<50 BMGC gear being simply polished.

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masks used. At present, the resolution for our TS3DP technique
can reach around 1 mm, which is still larger compared to the
laser 3D printing methods, e.g., the beam size for selective laser
melting and laser foil printing is only 80 mm and 430 mm,20
respectively. The resolution of the TS3DP technique can be
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further improved by exploring ne spraying nozzles. It is worth
mentioning that, in addition to structural applications, the
present TS3DP technique could also be feasible in manufacturing
functional BMG and BMGC parts, including porous catalysts with
a high specic surface area for wastewater treatment or water
splitting, biomedical or biodegradable implants and magnetic
devices, which will be explored in our future work.
4. Conclusions
In summary, we presented a novel thermal spray 3D printing
methodology for creating Fe-based BMG and BMGC compo-
nents with very large dimensions and good mechanical prop-
erties. The printed Fe48Mo14Cr15Y2C15B6 BMG and BMGC
(reinforced with 50% SS powder) samples exhibited high frac-
ture strength (
2 GPa) and good toughness (13–21 MPa m1/2,
which is 200–400% greater than that of the as-cast BMG of the
same composition). The improved toughness is mainly attrib-
uted to crack deections associated with the layered architec-
ture of the heterogeneous structures. The proposed fabrication
technique allows for the preparation of BMG and BMGC
components with theoretically limitless dimensions and
complex geometries. More importantly, because powders are
employed as starting materials in the TS3DP process, it is easy
to tailor the compositions and structures of the printed prod-
ucts by adjusting the amorphous powder and crystalline powder
compositions in starting powder mixtures. We believe that the
proposed TS3D process opens up a door to a new avenue for the
design and large scale fabrication of advanced BMG materials
for both structural and functional applications.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (Grant No. 51531003 and
51471074) and National Program on Key Basic Research Project
(973 Program) (Grant No. 2015C856801). The authors are
grateful to the Analytical and Testing Center, Huazhong
University of Science and Technology for technical assistance.
References
1 A. L. Greer, Mater. Today, 2009, 12, 14–22.
2 M. W. Chen, Annu. Rev. Mater. Res., 2008, 38, 445.
3 M. D. Demetriou, M. E. Launey, G. Garrett, J. P. Schramm,
D. C. Hofmann, W. L. Johnson and R. O. Ritchie, Nat.
Mater., 2011, 10, 123–128.
4 J. Schroers, Phys. Today, 2013, 66, 32.
This journal is © The Royal Society of Chemistry 2018
View publication stats
View Article Online
Journal of Materials Chemistry A
5 E. Ma and J. Ding, Mater. Today, 2016, 19, 568–579.
6 D. C. Hofmann, L. M. Andersen, J. Kolodziejska,
S. N. Roberts, J. P. Borgonia, W. L. Johnson, K. S. Vecchio
and A. Kennett, Adv. Eng. Mater., 2017, 19, 1600541.
7 Z. P. Lu, C. T. Liu, J. R. Thompson and W. D. Porter, Phys.
Rev. Lett., 2004, 92, 245503.
8 C. Suryanarayana and A. Inoue, Int. Mater. Rev., 2013, 58,
131.
9 J. Shen, Q. J. Chen, J. F. Sun, H. B. Fan and G. Wang, Appl.
Phys. Lett., 2005, 86, 151907.
10 J. Schroers, Y. Wu, R. Busch and W. L. Johnson, Acta Mater.,
2001, 49, 2773.
11 G. Wang, D. Q. Zhao, H. Y. Bai, M. X. Pan, A. L. Xia, B. S. Han,
X. K. Xi, Y. Wu and W. H. Wang, Phys. Rev. Lett., 2007, 98,
235501.
12 X. J. Gu, S. J. Poon and G. J. Shiet, J. Mater. Res., 2007, 22,
344.
13 S. Pauly, L. Lober, R. Petters, M. Stoica, S. Scudino, U. Kuhn
and J. Eckert, Mater. Today, 2013, 16, 37–41.
14 H. Y. Jung, S. J. Choi, K. G. Prashanth, M. Stoica, S. Scudino,
S. H. Yi, U. Kuhn, D. H. Kim, K. B. Kim and J. Eckert, Mater.
Des., 2015, 86, 703–708.
15 D. A. Stewart, P. H. Shipway and D. G. McCartney, Acta
Mater., 2000, 48, 1593–1604.
16 V. Ponnambalam, S. J. Poon and G. J. Shiet, J. Mater. Res.,
2004, 19, 1320.
17 C. Zhang, Y. Wu and L. Liu, Appl. Phys. Lett., 2012, 101,
121603.
18 J. W. Qiao, H. L. Jia and P. K. Liaw, Mater. Sci. Eng., R, 2016,
100, 1.
19 G. Dwivedi, K. Flynn, M. Resnick, S. Sampath and
A. Gouldstone, Adv. Mater., 2015, 27, 3073.
20 Y. Y. Shen, Y. Q. Li, C. Chen and H. L. Tsai, Mater. Des., 2017,
117, 213–222.
21 Z. B. Jiao, J. H. Luan, W. Guo, J. D. Poplawsky and C. T. Liu,
Acta Mater., 2016, 120, 216–227.
22 E08 Committee, E1820–11e2 standard test method for
measurement of fracture toughness, ASTM International,
West Conshohocken, PA, 2011.
23 P. A. Hess, S. J. Poon, G. J. Shiet and R. H. Dauskardt, J.
Mater. Res., 2005, 20, 783.
24 J. H. Yao, J. Q. Wang and Y. Li, Appl. Phys. Lett., 2008, 92,
251906.
25 B. A. Sun and W. H. Wang, Prog. Mater. Sci., 2015, 74, 211–
307.
26 M. Kotoul, J. Pokluda, P. Sandera, I. Dlouhy, Z. Chlup and
A. R. Boccaccini, Acta Mater., 2008, 56, 2908–2918.
27 C. Q. Zhang, D. A. Mcadams II and J. C. Grunlan, Adv. Mater.,
2016, 28, 6292.
28 R. Wilkerson, B. Gludovatz, J. Watts, A. P. Tomsia,
G. E. Hilmas and R. O. Ritchie, Adv. Mater., 2016, 28, 10061.
29 S. F. Guo, J. L. Qiu, P. Yu, S. H. Xie and W. Chen, Appl. Phys.
Lett., 2014, 105, 161901.
30 S. F. Guo, K. C. Chan and L. Liu, J. Alloys Compd., 2011, 509,
9441.
31 N. Li, J. J. Zhang, W. Xing, D. Ouyang and L. Liu, Mater. Des.,
2018, 143, 285.
J. Mater. Chem. A, 2018, 6, 6800–6805 | 6805