Additive Manufacturing 25 (2019) 499–510

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Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

Full Length Article

On the microstructure, mechanical properties and wear resistance of an T

additively manufactured Ti64/metallic glass composite
⁎ ⁎
Xiao-Jun Shena, Cheng Zhanga, , Yan-Ge Yangb, Lin Liua,
a
State Key Laboratory of Material Processing and Die & Mould Technology and School of Materials Science and Engineering, Huazhong University of Science and
Technology, 430074, Wuhan, China
b
Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

A R T I C LE I N FO A B S T R A C T

Keywords: Selective laser melting (SLM) provides flexibility in creating novel metal-matrix composites (MMCs) with unique
Selective laser melting microstructures and enhanced mechanical properties over conventionally manufactured MMGs. In this study, a
Titanium alloys Zr-based metallic glass (MG) decorated Ti6Al4V (Ti64) composite with a unique hybrid nanostructure and en-
Metallic glass hanced mechanical properties and wear resistance was fabricated using SLM. The results revealed that a near-full
Mechanical properties
dense and crack-free Ti-based composite was produced, with its reinforcements consisting of ultrafine β den-
Wear resistance
drites set with partially crystallized MG nanobands uniformly distributed along the boundaries of the melt pool.
The addition of MG significantly affected the solidification behavior of the Ti-liquid because of its higher dy-
namic viscosity and density as well as compositional effect on the phase stability. With such a unique nanos-
tructured reinforcement, the Ti64/MG composite exhibited an enhanced yield strength (> 1 GPa) with rea-
sonable ductility and fracture toughness. On the basis of the result of a theoretical analysis, we attributed the
main strengthening mechanism to Orowan strengthening. The wear resistance was also much improved in the
Ti64/MG composite, arising from the higher hardness of the nanostructured reinforcement and the formation of
a more protective tribo-oxide layer during sliding. The confinement of the 3D distributed reinforcement phase
played a crucial role in preventing the delamination of the tribo-layer on the matrix. This work opens a pathway
to the design of novel additively manufactured MMCs with outstanding mechanical properties.

1. Introduction
Ti-alloys are a workhorse in the modern aerospace and biomedical
industries due to their low density, excellent corrosion resistance, high
fracture toughness and good biocompatibility [1–3]. However, their
low hardness and poor wear resistance usually result in galling failure
and fretting fatigue, which are challenges for the application of Ti-al-
loys [4]. To improve the strength and wear resistance, ceramic particles
have been commonly introduced into Ti and Ti-alloys, resulting in Ti-
based metal-matrix composites (MMC). Low-density and hard ceramic
particle reinforcements [5], such as TiB, TiB2, TiC, TiN, B4C and Ti5Si3,
demonstrate the potential to improve the strength and wear perfor-
mance, but severely degrade the plasticity and toughness of Ti and Ti-
alloys because of their poor wettability with the Ti matrix [5–7] Fur-
thermore, the electrical insulativity and high melting points of the
ceramic reinforcements give rise to challenges in the machining and
processing of Ti-MMCs by using conventional manufacturing techni-
ques, such as casting and powder metallurgy [8].
Selective laser melting (SLM), one of the emerging additive manu-
facturing (AM) technologies, has become a promising route for manu-
facturing Ti-MMC parts with complex or customized geometries. During
SLM, near-net shape components are built by selective laser melting
directly from digital files [9,10]. It was reported that the advantages
stemming from AM (especially SLM) can decrease the production costs
for Ti-based components (e.g., engine brackets) by 50% by reducing
exorbitant machining costs and material loss [11]. Extensive works
have been carried out to understand the relationship between the mi-
crostructure and mechanical properties of Ti-alloys and Ti-MMCs pro-
cessed by SLM [8–18]. Typically, the high temperature gradient and
fast cooling rate inherent to the SLM process produce fine and me-
tastable microstructures (e.g., the martensitic α’ phase [18]) in the
resultant Ti-alloys. Attar et al. [19] compared the wear properties of
commercially pure Ti processed by SLM and casting, and concluded
that the SLMed Ti exhibited better wear resistance than cast CP-Ti due
to its martensitic microstructure and finer grain size. Zhu et al. [20]
reported that the wear of SLMed Ti6Al4V (Ti64 hereafter) alloy in

⁎
Corresponding authors.
E-mail addresses: czhang@hust.edu.cn (C. Zhang), lliu2000@mail.hust.edu.cn (L. Liu).

https://doi.org/10.1016/j.addma.2018.12.006
Received 10 September 2018; Received in revised form 9 November 2018; Accepted 8 December 2018
Available online 10 December 2018
2214-8604/ © 2018 Elsevier B.V. All rights reserved.
X.-J. Shen et al.
contact with hardened 38CrMoAl alloy is severe, dominated by oxida-
tive, abrasion, and delamination wear mechanisms. Recently, there
have been many attempts to enhance the mechanical and wear prop-
erties of SLMed Ti-alloys by making different Ti-MMC structures
[8,21–25]. Yet, the common problem persisting through these attempts
is the high residual porosity (1.7–15%) of the obtained MMC compo-
nents, as a result of the poor wettability between the metal and ceramic
particles, as well as insufficient time for pore filling between large
ceramic particles due to the extremely short interval (< 1 ms) of the
liquid phase during SLM [21,26]. As a consequence of the very large
temperature gradient, thermal stress concentrations always emerge at
the ceramic/metal interface, which initiate cracks and debonding upon
loading [23,27].
Metallic glasses (MGs) have attracted increasing interest as a new
type of advanced reinforcement because of their superior mechanical
properties compared to their crystalline counterparts [28–32], as well
as better ductility and wettability with the metal matrix compared to
ceramic reinforcements [33]. In particular, Zhang et al. [32] found that
the refinement of the MG micro-particles to nano-particles results in
MMCs with high strength and plasticity. To date, the majority of MG-
reinforced MMCs have been fabricated based on powder metallurgy,
and few studies have attempted to manufacture MG-reinforced MMCs
by AM technologies. Very recently, Zhang et al. [34] carried out pre-
liminary work on the fabrication of a Fe-based MG-strengthened
stainless steel composite by SLM, and found that the tensile strength of
the as-printed composite increased from 819 MPa to 1090 MPa while its
elongation decreased from 24.7% to 9.8%. However, the underlying
strengthening mechanism associated with the addition of MG particles
remained elusive. Our recent works have verified that fully densified
Zr-based MG components with a high amorphous phase content
(> 90%) and complex geometries can be readily 3D-printed by SLM
[35], providing us the possibility to fabricate Zr-based MG-reinforced
Ti-alloy composites by SLM and investigate the relation between the
microstructure and mechanical properties.
With this aim, this study investigates the microstructural evolution,
mechanical properties and wear performance of an MG reinforced Ti64
composite prepared by SLM. Here, a Zr-based MG system with a nom-
inal composition of Zr55Cu30Ni5Al10 is selected as the reinforcement
due to its high glass-forming ability, good printability, and comparable
Young’s modulus and coefficient of thermal expansion (CTE) with the
Ti64 alloy [35,36]. It is shown that the addition of MG particles led to
the formation of a unique nanostructured reinforcement, which re-
sulted in the enhancement of the strength and wear resistance of the
Ti64 alloy while maintaining good plasticity and fracture toughness.
The strengthening mechanisms and origins of the enhancement of the
wear resistance of the as-printed composite are discussed in detail.
2. Experimental procedures
2.1. Powder materials and SLM processing
Commercial Ti6Al4V (Ti64) alloy powder (< 53 μm, provided by
Falcon Tech Co, Ltd.) and a gas-atomized Zr55Cu30Ni5Al10 (at%) MG
powder (< 53 μm, provided by Nanjing MeiRui Wear-resistant
Materials Tech Co. Ltd.) were used in this study. The SEM morphologies
of the two types of powder are shown in Fig. 1a and b, revealing good
spherical shapes. The glassy nature of the MG powders prepared was
confirmed by X-ray diffraction measurement (see inset in Fig. 1b). The
two powders were mixed together through low-energy ball-milling
using a planetary mill to obtain a Ti64/MG mixture powder. SEM and
EDX mapping (Fig. 1c–f) verified the homogeneous distribution of MG
powder in the mixture. Here, the optimal addition of MG powder was
determined to be 10 wt% since any further increase resulted in a sig-
nificant decrease in the ductility of the resultant composites. The SLM
experiments were performed with a commercial SLM machine (For-
wedo LM-120, China, Fig. 1g) containing a fiber laser with a
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Additive Manufacturing 25 (2019) 499–510
wavelength of 1.06 μm, a maximum output power of 500 W and a laser
spot diameter of 80 μm. The chamber was first purged to vacuum and
then filled with argon gas, maintaining the oxygen content below
100 ppm during the entire process. All samples were produced using
pre-optimized processing parameters: a laser power P of 175 W, a
scanning speed v of 1000 mm s−1, a 100 μm hatch spacing h and a
40 μm layer thickness t. The layers were scanned in a continuous laser
mode according to a zigzag pattern, rotating 90° after each layer, as
illustrated in Fig. 1h. The appearance of a representative composite
component prepared by SLM is presented in Fig. 1i.
2.2. Microstructural characterization
The phase identification of the as-printed samples was performed by
X-ray diffraction (XRD, 7000SX, Shimadzu) with Cu Kα radiation. For
microscopic studies, longitudinal and transverse section of the as-
printed parts were prepared by conventional grinding, polishing and
chemical etching with Kroll’s reagent (1 ml HF, 2 ml HNO3 and 50 ml
deionized H2O). The metallurgical defects and microstructures were
investigated by optical microscopy (OM, Leica DFC 450), three-di-
mensional X-ray tomography (XRT, Xradia versa XRM 500) and scan-
ning electron microscopy (SEM, Zeiss Gemini 300) coupled with en-
ergy-dispersive X-ray spectroscopy (EDX). The interfacial structures
between the matrix and reinforcement phase were characterized
through transmission electron microscopy (TEM, FEI Titan Themis
200). The TEM thin foil was prepared by a focused ion beam (FIB, FEI
Helios 450S).
2.3. Mechanical property measurements
Compressive mechanical testing was carried out on cylindrical parts
(Φ 3 mm × 6 mm) along the SLM building direction (Z) using a uni-
versal testing machine (Zwick/Roell 020) at a constant strain rate of
1.0 × 10−4 s-1. The two ends of the specimens were polished carefully
to ensure their parallelism. Three-point bending tests were performed at
a displacement rate of 0.5 mm s-1, and the tested samples had dimen-
sions of 37 × 4.8 × 2 mm3. The span was set to be 30 mm. Afterwards,
the surfaces of the fractured samples were observed by SEM. At least 3
tests were repeated for each sample to ensure the repeatability of the
data. The notch fracture toughness (KQ) of the samples was measured
via a three-point bending test at a displacement rate of 0.1 mm min-1, in
which specimens with dimensions of 4.5 mm × 9 mm × 36 mm and a
notch with a depth of 4.5 mm and a root radius of approximately
144 μm (cut by a low-speed diamond saw) were used. The fracture
toughness (KQ) values were calculated by using standard references for
this geometry [37].
2.4. Hardness and wear tests
Vickers hardness testing was performed on polished samples using a
microhardness tester with a 300 g load and 10 s dwelling time. To probe
the possible difference in the mechanical properties of the matrix and
reinforcement phase, a nanoindentation test was conducted using a
Triboindenter (Hysitron TI750, USA) equipped with a Berkovich geo-
metry diamond tip. The indentations were performed to a maximum
load of 5 mN with a loading rate of 1 mN s−1, and the measurements
were performed at least 25 times to ensure data reliability. The wear
and friction performance of the Ti64 and Ti64/MG composite was
evaluated at room temperature using a UMT-3 Instruments ball-on-
plate wear tester in air and 0.1 M NaCl solution. Tribo tests were con-
ducted against a Si3N4 ceramic ball with a diameter of 6.35 mm using
the following parameters: a normal load (N) of 10 N, a sliding velocity
of 10 mm s−1, a 5 mm oscillating stroke and a 30 min total sliding
duration (S). New balls were used for each test. The wear tracks were
analyzed using an optical interferometer (VK-X200) to determine the
wear volume loss (V). The wear rate, Q, was then calculated by the
X.-J. Shen et al.
Fig. 1. (a, b) The SEM morphologies of the Ti64 and metallic glass (MG) powder. Inset in (b) is the XRD pattern of the MG powder. (c–f) The SEM and EDX mapping
of Ti64/MG powder mixture. (g, h) The SLM processing and scanning strategy used for the SLM experiments. (i) The appearance of an as-polished Ti64/MG
composite component.
following equation: Q = V/NS. The surfaces of the worn tracks were
observed by SEM. Microscratching was performed with a 200 mN load
with a sliding speed of 20 μm s−1 by using a diamond probe with a
radius of 100 μm to evaluate the phase-specific coefficient of friction
and wear resistance.
3. Results
3.1. Phase identification and microstructures
The XRD pattern of the as-printed Ti64/MG composite is depicted in
Fig. 2, compared with that of the as-printed Ti64 alloy. The samples
exhibit similar diffraction peaks corresponding to primary α′ martensite
and minor β phases, which are typical phase constituents in SLMed Ti-
based alloys. The formation of α′ martensite originates from the high
cooling rate associated with the SLM process [18]. Compared to the
Ti64 alloy, the peaks of the β and α′ phases in the Ti64/MG composite
specimen are broadened and have a lower intensity. More importantly,
the peaks of the β phase and α′ martensite in the composite shifted to a
lower 2θ regime compared to the Ti64 alloy. The insets in Fig. 2 show
comparisons of a single peak of the β phase and an α′ phase peak in the
Ti64 and Ti64/MG composite as an example. The results indicate that
the Ti64/MG composite had a finer grain size with an increased lattice
parameter in both the β and α′ phases. Given that Cu and Ni are β
stabilizers while Al is α stabilizer, the slightly increased lattice para-
meter mostly arises from the solution of MG constituents (i.e., with Cu,
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Additive Manufacturing 25 (2019) 499–510
Ni, and Al as the solutes) into the β phase and α′ martensite. In addi-
tion, no diffraction halo for the amorphous phase was observed in the
pattern of the Ti64/MG composite, probably due to the small volume
fraction of the amorphous phase and/or overlap between the amor-
phous halo and diffraction peaks at 38-39°.
Fig. 3a–d show SEM micrographs of the microstructural features in
the as-printed Ti64/MG composite and Ti64 alloy. The microstructure
of Ti64 alloy consists of predominantly fine α′ acicular martensite with
a width of ∼1 μm and a length of ∼5 μm (Fig. 3c), similar to the
findings in previous work [10,38]. The chemical composition of the
Ti64 alloy determined by EDX analysis is 86.41at% Ti, 9.94 at% Al and
3.65 at% V, which agrees well with its nominal composition. No oxygen
content was detected in the as-printed Ti64 part. On the other hand, the
microstructure of the fabricated Ti64/MG composite has an elliptical
melt pool, with white-contrast regions mainly distributed along the
boundaries of the melt pool (Fig. 3b). A higher-magnification SEM
image (Fig. 3d) further revealed the presence of ultrafine white-contrast
dendrite-like regions with intercellular spacing. The EDX mapping in
Fig. 3e–g confirmed that those white-contrast regions are enriched in
the MG components (e.g., Zr, Cu, Ni and Al) and Ti. Inside the melt
pool, some convection swirls are clearly observed, probably resulting
from the flow of the mixture of MG and the Ti64 melt during SLM. A
similar swirling morphology has been observed during the laser
welding of Zr-based MG and Ti64 alloy [39]. No oxygen trace was
presented on the surface of the as-printed Ti64/MG composite, as
verified by EDX analysis.
X.-J. Shen et al. Additive Manufacturing 25 (2019) 499–510

Fig. 2. The XRD patterns of the as-printed Ti64 alloy and Ti64/MG composite. Insets are XRD patterns of the two peaks recorded with a scan rate of 0.4°/min.

To probe the microstructural evolution of the Ti64/MG composite in for the Ti64 alloy, indicative of near-full dense parts being prepared.
more detail, especially in the interfacial regions between the matrix and The density of the present as-printed composite is higher than that of
reinforcement, TEM observation was carried out. Herein, the interfacial the SLMed Ti-MMCs reported previously [21]. According to the statis-
region was carefully extracted by FIB. Fig. 4a shows a representative tical results, the majority of the pores have a size in the range of
high-angle annular dark-field (HAADF) TEM image of the interfacial 5–20 μm, and there are fewer pores in the Ti64/MG composite than in
structure between the matrix and reinforcement. The matrix region the Ti64 alloy.
(right side in Fig. 4a) is characteristic of fine acicular α′ martensite,
while the reinforcement region (left side in Fig. 4a) manifests dendrites
3.2. Mechanical properties
and nanobands. Since the contrast in HAADF mode is due to changes in
the average atomic weight, the nanobands in bright contrast might
Fig. 6a shows representative true stress-strain curves for the as-
thereby correspond to MG regions because of the higher atomic num-
printed Ti64/MG composite and Ti64 alloy under compression. As ex-
bers of Zr, Cu and Ni compared to those of Ti and Al. The square-shaped
pected, the yield strength (σY = 1041 ± 22 MPa) and ultimate strength
dendrites were confirmed to be β phase according to the corresponding
(σU = 1455 ± 28 MPa) of the Ti64/MG composite are significantly
selective area electron diffraction (SAED) pattern (see inset in Fig. 4b).
higher than those of the Ti64 alloy (σY = 903 ± 16 MPa). The strain
The nanobands were confirmed to be the amorphous phase with minor
hardening rates obtained from compressive loading experiments are
nanocrystals, as evidenced by the high-resolution TEM observations
illustrated in Fig. 6b, which clearly demonstrates a higher strain
and SAED patterns shown in Figs. 4c and 5 d. The nanocrystal was
hardenability and strengthening effect in the Ti64/MG composite. The
indexed to the CuZr2 phase (PDF#652647, d112 = 0.2109 nm) ac-
as-printed Ti64/MG composite also remains a pronounced compressive
cording to the IFFT pattern. Fig. 4e schematically shows the distribution
plasticity (20%), indicative of the good ductility of the composite pre-
of the various phases formed in the SLMed Ti64/MG composite. α′
pared.
martensite constitutes the matrix region, while ultrafine β phase den-
In addition to compression tests, three-point bending tests were also
drites and partially crystallized MG nanobands constitute the nanos-
performed on the Ti64/MG composite and Ti64 alloy. Fig. 7 shows the
tructured reinforcement in the resultant composite. Owing to changes
bending strength-displacement curves of the two samples. The flexural
in the thermodynamics and kinetics of the solidification process upon
yield strength of the composite exceeds 1000 MPa, a much higher value
MG addition, the solidification of the mixture melt might follow a
than that of the Ti64 alloy (880 MPa). The Ti64/MG composite also
dendrite-solidification mode, wherein wherein the β phase stabilized by
displays appropriate bendability (see inset in Fig. 7), albeit lower than
Cu and Ni solidifies first due to its higher melting point, and serves as
that of the Ti64 alloy. Fractographs of the bending fractured samples
the nucleators and dendrite centers. The dendritic liquation increases
were observed by SEM, as shown in Fig. 8. The Ti64 alloy exhibits a
the intercellular concentration of MG elements, benefiting the forma-
macroscopically rough fracture surface (Fig. 8a) and microscopic
tion of an amorphous phase as a result of concentration overcooling.
dimple ruptures (Fig. 8b), which are characteristics of ductile fracture.
Partial crystallization occurs in MG nanobands due to a reheating effect
In contrast, the Ti64/MG composite displays a mixture of the features of
upon the layer-by-layer deposition [35,36]. A more detailed discussion
ductile and brittle fracture including dimple zone, vein-like pattern and
on the formation of such unique microstructure will be presented in
decohesive pattern, as depicted in Fig. 8c and d. The inhomogeneous
later section.
fracture surface is attributed to the interaction between the reinforce-
Fig. 5 shows the three-dimensional X-ray tomography images of the
ment and Ti64 matrix. The vein-like pattern, a typical fracture char-
as-printed parts, in which no cracks are observed except for a small
acteristic of ductile MGs, formed due to the instantaneous increase in
number of micropores. Based on the micro-CT data, the relative density
the temperature at the final fracture (adiabatic heating) [40,41]. The
was calculated to be 99.83% for the Ti64/MG composite and 99.79%
decohesive pattern arose from the docohesion fracture of the matrix/

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X.-J. Shen et al.
Fig. 3. The SEM micrographs showing the typical microstructural features in (a, c) the Ti64 alloy and (b, d) Ti64/MG composite. (e–g) The EDX composition mapping
of the reinforcement near the melt pool boundary.
reinforcement interfaces [42]. Generally, the β-phase is relatively soft
and ductile when compared to the MG and α′ martensite, whose plastic
deformation characteristics involve shear localization [43]. Upon
plastic straining, the strain incompatibility that develops at the matrix/
reinforcement and MG nanobands/β grains could weaken the inter-
faces, which consequently result in the pull-off of the reinforcements
from the matrix.
Since the ductility per se is not of major concern in the context of
additively manufactured materials, we further measured the notch
fracture toughness (KQ) of the Ti64 alloy and Ti64/MG composite. The
Ti64 alloy shows a high KQ value of 70 ± 3 MPa m1/2, consistent with
previously reported values for additively manufactured Ti64 alloy [44].
By contrast, the Ti64/MG composite exhibits a slightly reduced fracture
toughness of 42 ± 1 MPa m1/2, which is likely due to the existence of
brittle intermetallic compounds and/or refined α′ martensite. Never-
theless, the fracture toughness for the current 3D printed Ti64/MG
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Additive Manufacturing 25 (2019) 499–510
composite is high when compared with those of other additively
manufactured alloys and MMCs, e.g., TiAl alloys (18.6-26.7 MPa m1/2)
[45], AlSi alloys (19.3-47.0 MPa m1/2) [46], MoSiB alloys (12-18 MPa
m1/2) [47] and Ti/HA composites (1.0-3.5 MPa m1/2) [48].
3.3. Wear resistance
Prior to the wear tests, the hardness of the Ti64/MG composite was
measured. The mean Vickers microhardness of the Ti64/MG composite
is 382 ± 13 HV0.3, which is 11% larger than that of the Ti64 alloy
(344 ± 11 HV0.3). In addition, an instrumented nanoindentation test
was carried out to probe the hardness of the reinforcement and matrix
regions. The load-depth curves shown in Fig. 9 indicate a much lower
maximum penetration depth of the MG-rich reinforcement, indicating
that the reinforcement is harder and stronger than the matrix. The as-
measured nanohardness is 6.3 ± 0.24 GPa and 5.1 ± 0.24 GPa for the
X.-J. Shen et al. Additive Manufacturing 25 (2019) 499–510

Fig. 4. (a, b) The HAADF-STEM micrograph shows the interface between matrix and MG-rich reinforcement lamellae, the inset is the SAED pattern from as-boxed
region “B”. HRTEM images of region “A” that contains (c) amorphous phase and (d) nanocrystal. Inset is the IFFT pattern of the CuZr2 nanocrystal. (e) Schematic
microstructure of the as-printed Ti64/MG composite.

reinforcement and matrix, respectively. Accordingly, the reinforcement (5.0 ± 0.23 GPa), arising from a grain refinement effect and solid so-
could act as a stress-bearing site to enhance the mechanical perfor- lution strengthening in the composite.
mance. Notably, the nanohardness of the matrix region of the Ti64/MG Fig. 10 compares the wear rates of the Ti64/MG composite and Ti64
composite is slightly higher than that of the Ti64 alloy alloy in different environment. Overall, the Ti64/MG composite

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X.-J. Shen et al.
Fig. 5. The pore size and distribution in the Ti64 alloy and Ti64/MG composite. Insets are the micro-CT reconstructed images showing the defect characteristics
inside the two samples.
exhibits considerably lower wear rates when compared with the Ti64
alloy, indicative of improved wear resistance. For example, under dry-
wear condition, the wear rate was measured to be 2.33 × 10−4 mm3 N-
1
m-1, approximately 24% lower than that of the monolithic Ti64 alloy
and 69–82% lower than that of SLMed Ti-TiB MMC [24]. In 0.1 M NaCl
solution, the Ti64/MG composite also displays a lower wear rate
(1.71 × 10−4 mm3 N-1 m-1) compared to that of the Ti64 alloy
(2.25 × 10−4 mm3 N-1 m-1), indicating that the Ti64/MG composite
performs better even under a corrosion-wear environment.
The wear tracks of the Ti64/MG composite and Ti64 alloy observed
by SEM are shown in Fig. 11. In the case of dry-wear, the wear tracks of
both materials present typical ploughing grooves and flake-shaped wear
debris (see insets in Fig. 11a and b), representing abrasive wear and
delamination wear mechanisms, respectively. In addition, an EDX
analysis shows oxygen content along the wear surfaces. Since no oxygen
trace is detected on the surface of the as-printed samples, the appear-
ance of oxidation is most likely due to the temperature rise at the
Fig. 6. (a) True stress-strain curves for the Ti64 alloy and Ti64/MG composite under compression. (b) Comparison of the strain hardening rate between the two
materials.
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sliding interface between the ball and disk. Compared to the wear
surface of the Ti64 alloy, less wear debris (caused by delamination) and
mixed oxides appeared on the surface of the Ti64/MG composite, cor-
responding to a better wear resistance. In the case of corrosion-wear,
the wear tracks are manifested by the presence of an adherent tribo-
layer enriched with oxygen and slight ploughing grooves, which re-
present a coupled mechanism of adhesion wear, oxidation wear and
abrasion wear. The tribolayer formed on the Ti64/MG composite is
more smooth and has a lower oxygen content compared with that on
the Ti64 alloy, and is expected to be more protective against wear,
which accounts for the lower wear rate in the 0.1 M NaCl solution.
4. Discussion
4.1. On the microstructure of the as-printed Ti64/MG composite
In the realm of the SLM of Ti-alloys and Ti-based MMCs, substantial
X.-J. Shen et al.
Fig. 7. Bending strength-deformation curves for the Ti64 alloy and Ti64/MG
composite. The inset shows the picture of as-bended Ti64/MG composite during
loading.
efforts have been invested in tailoring the types, morphology, grain size
and characteristic length scales of the constituent phases (α, β, α′) to
mitigate the strength-ductility trade-off [10,14,17,18]. This work has
shown that the introduction of a multicomponent Zr-based MG can not
only result in a novel nanostructured reinforcement but also provide a
new route for tailoring the microstructure of the Ti alloy (i.e., stabili-
zation of β phase, refinement and solution of β and α′ phases), which
can provide high strength and good ductility to the as-fabricated MMC
part. As mentioned earlier, it is recognized that the refinement of the
MG from micro-particles to nano-particles is beneficial to obtain high
strength and plasticity simultaneously [28–32]. We therefore supposed
that the formation of a unique nanostructured reinforcement (i.e., MG
Fig. 8. The SEM images showing the fractographs of the bending fractured samples. (a, b) Ti64 alloy and (c, d) Ti64/MG composite.
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Additive Manufacturing 25 (2019) 499–510
Fig. 9. Load-depth curves of the matrix and reinforcement regions in the Ti64/
MG composite and Ti64 alloy.
nanobands and ultrafine β grains) could play a crucial role in the im-
proved mechanical properties and wear resistance of the resultant
Ti64/MG composite.
The MG nanobands, having a distinctly different morphology from
the starting spherical morphology of the powder, is direct evidence for
the occurrence of the complete melting of the MG during SLM.
Consequently, the formation of MG nanobands might be processed via a
dissolution/re-solidification mechanism. Typically, the solidification of
the Ti64 liquid occurs via planar solidification as a result of the small
variation between the liquidus and solidus temperatures (TL-TS = 5°
[49]). However, adding 10% MG to the Ti64 could disturb this equili-
brium, triggering a transition from planar mode to dendritic solidifi-
cation mode. Such a transition occurs when the thermal gradient in the
X.-J. Shen et al. Additive Manufacturing 25 (2019) 499–510

affect the first term in Eq. (1), and the enlarged TL-TS range due to the
addition of Zr or Al could affect the second term in Eq. (1) [49], both of
which can lead to an increase in the critical thermal gradient. This
ultimately results in a dendritic solidification of the mixed liquids of
Ti64 and the MG.
It is noted that the variations of the density and viscosity between
the Ti64 and MG liquids have a consequence on the resultant solidified
microstructure. First, given a substantial variation in the density be-
tween the Ti64 and MG melts, i.e., ∼4.0 g cm−3 for the Ti64 liquid [51]
and ∼6.8 g cm−3 for the MG [52], a gravity effect will cause the ma-
jority of the MG melt to settle to the bottom of the melt pool. Second,
the dynamic viscosity μ of a liquid is given by Eq. (2) [13]:

16 m
μ= γ
15 KB T (2)

Fig. 10. Comparison of the wear rates between the Ti64 alloy and Ti64/MG where m is the atomic mass, γ is the surface tension (γ), T is the tem-
composite samples in air and 0.1 M NaCl solution. perature and KB is the Boltzmann constant. The Ti64 and MG liquids
exhibit almost the same surface tension (γ), with a value of ∼1.5 N m−1
liquid phase at the solidification front is below a critical value, δT
, [53,54], while the much larger m value of the MG gives rise to a higher
δXcrit μ with respect to that of the Ti64 liquid according to Eq. (2). In prin-
expressed by the following Eq. (1) [49]:
ciple, the higher density and viscosity of the MG melt allow in its se-
δT C 1 − k δTL paration from the Ti64 melt. The β phase stabilized by Cu and Ni so-
=− 0 lidifies first due to its higher melting point. The dendrites reject the
δXcrit DL / R k δC (1)
solutes (Cu, Ni and Al) across the solid/liquid interface into the su-
Wherein C0 is the overall solute concentration, DL is the solute diffusion percooled liquid, and thus the liquid becomes enriched with MG ele-
coefficient in Ti liquid, R is the solidification rate, and k is the solute ments benefiting the formation of an amorphous phase. In our recent
partition coefficient related to the solidification range between the li- work [35,36], it was proven that the local rapid cooling rate (103-106 K
quidus and solidus temperatures. The much slower diffusion coeffi- s-1) in association with the SLM process is sufficiently high for the
cients of Cu and Ni in liquid Ti [50] with respect to Al and V could formation of an amorphous structure of the current Zr-based system.

Fig. 11. The worn surface SEM morphologies and EDX analysis of the (a, c) Ti64 alloy and (b, d) Ti64/MG composite samples after wear tests in air and 0.1 M NaCl
solution. Insets in (a, b) show the SEM images of wear debris.

507
X.-J. Shen et al.
The rapid cooling limits the length scale of the amorphous phase
formed, yielding the MG nanobands observed in Figs. 3d and 4 b. Yet,
the MG nanobands could be partially crystallized due to repeated
heating (> Tx temperature) upon the layer-by-layer deposition. As a
result, unique “hard/soft” nanostructured reinforcements consisting of
partially crystallized MG nanobands (hard phase) entrapped in β-grains
(soft phase) formed in the Ti64/MG composite.
4.2. Strengthening mechanisms in the as-printed Ti64/MG composite
The strength increment in the as-printed Ti64/MG composite can be
rationalized by several contributions: the mismatch of the coefficients
of thermal expansion (CTE) between Ti64 and MG, Hall-Petch
strengthening, the load transfer effect, an Orowan strengthening
[32,55].
First, based on the TEM results, no apparent dislocation was ob-
served in the as-printed Ti64/MG composite around the reinforcements.
Therefore, the increased dislocation density strengthening due to the
CTE mismatch can be neglected. In fact, the CTE values of the Ti64
alloy (∼9 × 10−6 K-1) and Zr-based MG (∼10 × 10−6 K-1) are quite
small. Second, nanoindentation measurements revealed only a slight
increase in the nanohardness of the matrix of the Ti64/MG composite,
suggesting that the Hall-Petch strengthening owing to grain refinement
might not be so significant. Third, for fiber- or whisker-reinforced
MMCs, load transfer is considered one of the most important
strengthening mechanisms, wherein load transfer from a relatively soft
matrix to a stiff second phase under an applied external load con-
tributes to the strengthening of the base material. The strengthening
effect due to load transfer in an MMC can be calculated as below [56]:
l
ΔσLT = σm Vm + σf Vf ⎛1 − c ⎞ − σm (l > lc )
⎝ 2l ⎠ (3)
l test was performed on Ti64/MG composite and Ti64 alloy to obtain
ΔσLT = σm Vm + σf Vf ⎛ c ⎞ − σm (l < lc )
⎝ 2l ⎠ (4)
σf df
lc =
2τm (5)
where σm and σf are the yield strengths of the matrix (903 MPa) and
reinforcements (1500 MPa [36]), respectively. Vm and Vp are the vo-
lume fraction of the matrix and reinforcement (5.56% in this study). l
and lc represent the actual and critical lengths of the reinforcements. df
is the average diameter of the reinforcements (∼50 nm for an MG na-
noband). τm is the ultimate shear strength of the matrix (0.65 σm
≈587 MPa). The calculated lc is 64 nm by Eq. (5), which is much lower
than the actual length of MG nanoband (∼500 nm). As such, the cal-
culated value of Δσload is 28 MPa according to Eq. (3). Finally, Orowan
strengthening results from the interaction between dislocation and the
reinforcements. The contribution of the Orowan strengthening me-
chanism can be estimated by the following equation [57]:
0.13Gm b dp
ΔσOrowan = ln
λ 2b (6)
where Gm is the shear modulus (38 GPa for Ti64 [58]), dp is the dia-
meter of the reinforcement, b is the Burgers vector (0.3 nm for Ti64
[58]), and λ is the interparticle distance (λ = dp [ 3 1 − 1]). The cal-
2Vp
culated ΔσOrowan due to the nanostructured reinforcements is
∼101 MPa. Since the total increment of the yield strength is approxi-
mately 138 MPa, the Orowan strengthening represents most of the
contribution to the increased yield strength.
In addition to the high strength, the present Ti64/MG composite
also exhibits good ductility and fracture toughness, although being in-
ferior to those of the as-printed Ti64 alloy due to the existence of grain-
refined martensite and a brittle intermetallic phase (CuZr2).
Nevertheless, the unique composite structure of MG nanobands coupled
with a ductile β phase shows advantages to those of strong yet brittle
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Additive Manufacturing 25 (2019) 499–510
reinforcements (e.g., MG micro-particles and ceramic phases) in terms
of the ductility and toughness. The internal confinement between na-
noscale constituent phases could effectively prevent the brittle inter-
metallic component, MG and martensite from premature fracture. This
provides an opportunity for plastic deformation, which is evident from
the fracture morphology observations (Fig. 8d). In fact, previous works
have readily confirmed that the confinement effect and nanoscale di-
mensions could make the brittle intermetallic and amorphous phases
deformable [59–61]. Furthermore, the unique hybrid microstructures,
including grain boundaries, β-phase/MG nanoband interface and melt
zone boundaries, could make the crack propagation rather difficult
[18], thus improving the fracture toughness. It is expected that the
mechanical properties of the present composites could be further im-
proved via tailoring these structural features through processing opti-
mization. In a preliminary attempt, we have performed a post heat
treatment (annealing at 500 ℃ for 2 h in vacuum) on the composite via
the fully crystallization of the MG. However, the results of compressive
tests indicated that such heat-treatment did not increase the strength
much; and instead, remarkably decreased the ductility (εp = 12%),
which is probably due to the formation of brittle intermetallic com-
pounds in the Ti64/MG composite. Therefore, other post-processing
routes should be explored in future study.
4.3. On the enhanced wear resistance of the as-printed Ti64/MG composite
According to the Archard equation [62], which predicts that the
wear resistance of a material is proportional to its hardness, it is natural
to consider that the improved wear resistance (by 24–35%) of the Ti64/
MG composite can be ascribed to its higher hardness then that of the
Ti64 alloy (increase by 11%). However, the macroscopic worn surface
observations cannot provide direct evidence regarding the role of the
hard reinforcement in reducing wear loss. To this end, a micro-scratch
phase-specific friction/wear properties. The results of the scratch test
are presented in Fig. 12. The Ti64/MG composite displays a much lower
average COF value (∼0.45) coupled with a narrower scratch width (see
inset in Fig. 12a) compared to the Ti64 alloy (COF∼0.75), again de-
monstrating the superior friction and wear resistance of the as-printed
Ti64/MG composite. The SEM observation (Fig. 12b) of the micro-
scratches on the Ti64 matrix and reinforcement in the composite
sample revealed a non-uniform wear track, wherein the scratch was
wider on the matrix regions accompanied by severe plastic deformation
on the edges; however, the scratch became narrowed when en-
countering hard reinforcement phases coupled with many fewer plastic
deformation traces. The findings here thus directly point to the positive
role of the strong, nanostructured reinforcement in the enhanced wear
resistance of the Ti64/MG composite. On the other hand, because of the
high oxygen affinity of Ti or Zr, a passive oxide film always exists on
their surface. Since the Ti64 matrix is relatively soft and deformable,
the strain mismatch between the subsurface and brittle and less-de-
formable oxidized layer under a high load rubbing would lead to crack
initiation and delamination (formed as flake-like debris), as observed in
Fig. 11a. Differently, due to the confinement effect of the hard re-
inforcement that three-dimensionally distributed near the melt
boundaries against the subsurface deformation and delamination of
tribo-oxide layer, the wear loss of the Ti64/MG composite is much less
than that of the Ti64 alloy.
When the as-printed parts slid in 0.1 M NaCl solution, an adhesion
and strain hardening tribo-layer was formed on both materials.
Generally, the tribo-oxides fulfilled a protective role and reduced wear
under dry-sliding and lubrication conditions, as reported for many
other materials [19]. Compared with that formed on the Ti64 alloy, the
tribo-layer on the composite appeared to be more smooth and con-
tained less oxygen, indicating a higher protectiveness and lower brit-
tleness, which, in turn, delivered a superior wet-wear resistance for the
Ti64/MG composite in the 0.1 M NaCl solution. No significant corrosion
X.-J. Shen et al.
Fig. 12. (a) Coefficient of the friction (COF) as a function of the scratch distance during the micro-scratch experiment. Insets show the OM images of the scratches on
the Ti64 alloy and Ti64/MG composite. (b) SEM image of a scratched region composing of Ti64 matrix and MG-rich region in the composite.
pits could be observed on the wear tracks of the Ti64/MG composite,
demonstrating that the addition of MGs of good corrosion resistance
does not significantly degrade the anticorrosion performance of Ti-al-
loys.
5. Conclusions
In this study, a Ti64 composite reinforced with Zr-based metallic
glass (MG) was fabricated via selective laser melting (SLM). The mi-
crostructure, mechanical properties and wear behaviors of the as-
printed Ti64/MG composite were investigated and compared to the
Ti64 alloy, suggesting the following findings:
1 The addition of MG (10 wt%) densified the as-printed Ti64 alloy,
resulting in a near-full Ti64/MG composite with an absence of
cracks. A unique microstructure with reinforcement consisting of
partially crystallized MG nanobands and fine β grains formed and
distributed along the melt pool boundaries in the Ti64/MG com-
posite.
2 The Ti64/MG composite exhibited a high yield strength of larger
than 1 GPa under compression and bending, excellent compressive
ductility (20%) and fairly good fracture toughness (Kq = 42 MPa
m1/2). Based on a theoretical analysis, the increased strength is
mainly attributed to the Orowan strengthening mechanism, while
the good ductility and fracture toughness result from the ductile β
phase and the confinement effects between the nanoscale con-
stituent phases and various types of interfaces in the composite.
3 The hardness and wear performance was also improved in the re-
sultant Ti64/MG composite. The hard nanostructured reinforce-
ments had been directly proven through micro-scratch tests to re-
duce the COF and wear volume. 3D uniformly distributed
reinforcements are able to reduce the delamination wear caused by
the subsurface plastic deformation of the matrix and also generate
509
Additive Manufacturing 25 (2019) 499–510
more protective tribo-oxide layers against corrosion wear, thus
providing superior wear resistance compared to the unreinforced
Ti64 alloy.
Acknowledgements
This work was financially supported by the National Key R&D
Program of China (No. 2016YFB1100101); National Nature Science
Foundation of China (Grant Nos. 51531003 and 51771077); and the
Hubei Provincial Natural Science Foundation of China (No.
2018CFA003). The authors are grateful to the Analytical and Testing
Center, Huazhong University of Science and Technology for technical
assistance.
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