Accepted Manuscript

Title: Progress in Additive Manufacturing on New Materials

Authors: Neng Li, Shuai Huang, Guodong Zhang, Renyao

Qin, Wei Liu, Huaping Xiong, Gongqi Shi, Jon Blackburn

PII: S1005-0302(18)30178-6
DOI: https://doi.org/10.1016/j.jmst.2018.09.002
Reference: JMST 1288

To appear in:

Received date: 3-4-2018

Accepted date: 16-4-2018

Please cite this article as: Li N, Huang S, Zhang G, Qin R, Liu W,

Xiong H, Shi G, Blackburn J, Progress in Additive Manufacturing on
New Materials, Journal of Materials Science and amp; Technology (2018),
https://doi.org/10.1016/j.jmst.2018.09.002

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●Invited Review

Progress in Additive Manufacturing on New Materials

Neng Lia, Shuai Huanga, Guodong Zhanga, Renyao Qina, Wei Liua, Huaping Xionga, Gongqi
Shi , Jon Blackburnb
b

a. 3D Printing Research & Engineering Technology Center, Beijing Institute of Aeronautical

Materials, Beijing 100095, China
b. TWI Ltd, Granta Park, Great Abington, Cambridge, CB21 6AL, UK

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[Received 3 April 2018; accepted 16 April 2018 ]
*Corresponding author. E-mail addresses: [email protected], [email protected] (H.P.

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Xiong)

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Abstract:
Recent efforts and advances in additive manufacturing (AM) on different types of new materials

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are presented and reviewed. Special attention is paid to the material design of cladding layers, the
choice of feedstock materials, the metallurgical behavior and synthesis principle during the AM
process, and the resulted microstructures and properties, as well as the relationship between these
factors. Thereafter, the trend of development in the future is forecasted, including: Effects of the
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particles size and size distribution of powders; Approaches for producing fine microstructures;
Opportunities for creating new materials by AM; Wide applications in reconditioning of damaged
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components; Challenges for deep understanding and applications of the AMed new materials. The idea
of “Develop Materials” or “Create Materials” by AM is highlighted, but a series of scientific,
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technological and engineering problems remain to be solved in future.
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Keywords: Additive manufacturing; Feedstock material; Laser and electron beam melting;
Microstructure; Property
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1. Introduction
In contrast to conventional processing methods, additive manufacturing (AM) is based on an
incremental layer-by-layer manufacturing. As such, most relevant AM technologies use powder or
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wire as a feedstock which is selectively melted by a focused heat source and consolidated in subsequent
cooling to form a part[1, 2]. Today, it has become possible to reliably manufacture dense parts with
certain AM processes for a number of materials, including steels, aluminium and titanium alloys,
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superalloys, metal based composites and ceramic matrix composites[3-6]. In the near future, the AM
material variety will most likely grow further, with e.g. high-performance materials such as
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intermetallic compounds and high entropy alloys already under investigation.

Thus, AM transforms more and more from rapid prototyping to rapid manufacturing
applications[7], which require not only profound knowledge of the process itself, but also of the
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microstructure resulting from the process parameters and consequently of the properties of the
manufactured parts[8]. Each AM method has its specific applications based on its own advantages.
Powder bed selective fusion methods are suitable to produce complex and high accuracy components.
While wire-fed AM methods (beam/arc) have the highest deposition rates due to the feedstock of wire
materials, which are commonly used to produce large scale components[9].
As pointed out by Gu[10], materials are the basis of AM technology and materials creation
hopefully adds new dimensions to three-dimensional printing (3DP) and extends the connotation of
this advanced technology, thereby providing new opportunities for the future development of AM/3DP.
The idea of “Create Materials” by AM/3DP is a step-by-step process based on the ideas of “Use
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Materials” and “Develop Materials”[10]. Murr et al. stated that, AM could fundamentally alter or extend
the traditional materials science and engineering paradigm relating to structure-property-processing
(synthesis)–performance[3]. Multiple materials and multiscale structures provide a possible route to
optimizing overall properties of components[11].
In this paper, the recent efforts and advances in the study of AM on new materials were reviewed.
Special attention is paid to the material design of cladding layers, the choice of feedstock materials,
the metallurgical behavior and synthesis principle during the manufacturing process, and the resulted
microstructures and properties, as well as the relationship between these factors. Totally 12 types of
new materials are discussed, and lots of encouraging research results have been achieved. On this basis,
from the authors’ viewpoint some important research directions or ideas are proposed for the future
work.

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2. Progress in additive manufacturing on new materials

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2.1 Al and Mg alloys
Modified aluminium alloys with a scandium content beyond the eutectic point offer great

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potential to become a high prioritized aerospace material. Schmidtke et al. demonstrated the
preparation of aluminium scandium alloy with the main composition of Al-4.5Mg-0.66Sc-0.51Mn-

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0.37Zr by laser AM[12]. The specimens tested parallel to the layer build up orientation, had the highest
tensile strength with over 530 MPa. The ageing treatment at 325 °C for 4 hours remarkably increased
the hardness from the as-built specimen, indicating a distinct hardening effect due to Al3Sc precipitates.

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The addition of element scandium led to not only high strength but also ductile behavior, due to grain
refinement that caused high plasticity (the elongation of 14% and the reduction of area of 20%)
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compared to other high strength Al-alloys (e.g. 7050).
Surface modification of the feedstock alloy powders has been examined for the control of the
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microstructures of the AMed components. In 2017, Martin et al.[13] reported an approach to change the
columnar grains to equiaxed grains for 3D printing of high-strength aluminium alloys, that is, pre-
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alloyed gas-atomized 7075 spherical powders with an average particle size of 45 μm were coated with
1 vol.% hydrogen-stabilized zirconium nucleants using an electrostatic assembly technique to ensure
uniform distribution in the powder bed and avoid settling. Upon melting zirconium nanoparticles were
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pulled into the melt pool and reacted with aluminium alloy to form Al3Zr. Al3Zr has more than 20
matching interfaces with the primary fcc aluminium phase, exhibiting less than 0.52% lattice mismatch
and 1% variation in atomic density, providing an ideal low-energy heterogeneous nucleation site. The
large number of the nucleation sites ahead of the solidification front induced a fine equiaxed structure
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under the same laser processing conditions as for the unmodified powder, as shown in Fig. 1(a, b, c).
Furthermore, the nucleant particles were uniformly incorporated into the microstructure, and they
could provide additional strengthening and resistance to grain growth owing to pinning effects [13].
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Such kind of approach to change the grains and tailor the resulted properties through surface
modification of the feedstock alloy powders is greatly effective and is worth extending to other
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material systems.

As one of the most promising lightweight structural materials, magnesium alloys have been
widely used in aeronautic industry. Pawlak et al. studied the selective laser melting (SLM) of AZ31
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magnesium alloy spherical powder, with the particle size of 45-100 μm[14]. Porosity levels less than
0.5% were achieved. From Fig. 2 (a), it can be found that performed microstructure analysis of melted
material shows significant refinement in comparison to cast material. Both material microstructure
(cast and melted) consists of α-Mg non-homogenous solid solution, and α+γ Mg17Al12 non-
equilibrium eutectic colonies in degenerated form located between grains of high aluminium content.

SLM of AZ91D has been carried out on the rolled AZ31B substrate plates, in which spherical gas
atomized AZ91D powders with a mean particle size of 59 μm were used as the starting material in the
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SLM experiment[15]. Nearly full dense AZ91D (99.52%) with the microhardness of 100 HV, UTS of
296 MPa and σ0.2 of 254MPa can be obtained using laser volume energy density of 166.7 J/mm3. The
SLMed AZ91D consists of equiaxed α-Mg matrix and fully divorced eutectic β-Mg17Al12[15].
According to another reference, a high power diode laser (HPDL) has been used to selectively
melt one of the phases present in the microstructure of the surface of a magnesium-aluminium alloy
(AZ91D), in which the β-phase (Mg17Al12 precipitates) is molten while α-matrix is kept solid[16].
Zhang et al. used SLM to sinter a powder mixture of Mg-9%Al[17], in which the average size of
Mg powder particle with an irregular shape and Al particles with spherical feature is 42 μm (D50) and
17 μm (D50), respectively. The sintered sample mainly consisted of Mg, intermetallic compounds
Mg17Al12, as well as MgO and Al2O3.
Besides, considering the poor corrosion and wear resistance of magnesium alloys, surface coating

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has been examined for surface production and repair[18]. Liu et al. summarized the material systems

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preplaced on magnesium alloys, including the traditional metallic materials, novel ternary alloys,
amorphous alloys and high entropy alloys. The feasibility of depositing variable thickness of cladding
material on the magnesium alloy substrate makes it possible to repair machine parts using the laser

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cladding method[19].

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2.2 Ti alloys
Fast progress has been made in the study of AM of Ti alloys, such as Ti6Al4V, TC11, TC21,
Ti5553 and Ti-8Al-1Er.

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First of all, Ti-6Al-4V blocks were deposited using a 3.5 kW Nd:YAG laser and Ti-6Al-4V wire
with the diameter of 1.2mm[20]. The as-deposited Ti-6Al-4V can achieve strength and ductility
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properties that is similar to the wrought Ti-6Al-4V material (AMS 4928). Furthermore, the particular
impurity levels of the deposited blocks are considerably below the acceptable levels according to
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aerospace material specifications (AMS 4911L). Butler et al.[21] evaluated the growth textures during
wire-feed electron beam directed energy deposition of Ti-6Al-4V onto a <112>β-oriented beta-single
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crystal Ti-6Al-4V substrate. It was found that a portion of the build grew epitaxially from the
substratein a single crystal fashion (region labeled “1” in Figure 3). In contrast, the other portion of
the build after two layers (~1.1 mm in build height) showed evidence of almost random nucleation and
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growth (region labeled “2”). Equiaxed grains (region 2) gradually transitioned to conventional <001>-
oriented columnar grains. In addition, as the build height increased, region 2 grains tended to
progressively consume the region 1 until a full transition to a near <001>-fiber texture was attained.
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Carroll et al. investigated the anisotropic mechanical properties of a Ti6Al4V three dimensional
cruciform component fabricated using a directed energy deposition AM process. While the average
ultimate tensile strength in both directions was 1060 MPa, the achieved elongations of 11% and 14%
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along the longitudinal and transverse directions, respectively[22]. The ability of attaining high ductility
was dependent on the prevention of lack-of-fusion defect, and the anisotropy in ductility was attributed
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to the columnar prior-β grain morphology and the presence of grain boundary α, which served as a
path along which damage could preferentially accumulate, leading to fracture. Besides, the presence
of additional oxygen, of the order of 0.0125 wt%, in the Ti6Al4V component increased both the
ultimate tensile strength and yield strength, and only slightly reduced ductility, that is, the introduced
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oxygen contamination did not lead to embrittlement of the component[22].

A typical α+β titanium alloy Ti-6.5Al-3.5Mo-1.5Zr-0.3Si (named TC11 in China) was fabricated
by laser melting deposition process[23]. The as-deposited sample exhibits a strong tensile anisotropy
due to the columnar grains morphology and the strong texture of β <001> parallel to the deposition
direction. Despite the anisotropy, the α+β annealing can increase the mechanical properties in both
strength and ductility to levels that are much higher than the specification limits of the alloy.
In the meantime, the study on direct laser deposition of Ti-6Al-2Zr-2Sn-3Mo-1.5Cr-2Nb (TC21)
alloy and Ti-5Al-5Mo-5V-3Cr (Ti5553) alloy are still in progress[24, 25]. The tensile properties of laser
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AMed TC21 samples show significant anisotropic in two different heat treatment conditions. The
horizontal samples exhibit stronger strength than the vertical sample, and the total elongation of the
horizontal sample is much inferior to that of the vertical ones[26].
Besides, oxide dispersion strengthened alloys, which benefit from rapid solidification are well
suited for AM processes[27]. Of the titanium–rare earth alloys, rapid solidification of Ti-Er received the
most attention because of the relatively large solid solubility extension of Er in titanium and the thermal
stability of Er2O3 precipitates which can refine grains and enhance the elevated temperature properties.
To determine the effectiveness of AM process, a novel composition titanium alloy of Ti-8Al-1Er was
fabricated by wire feed electron beam deposition process. The microstructure showed no evidence of
columnar grain structure, but rather a more equiaxed grain structure which is very different compared
to the Ti-6Al-4V[28, 29]. The grain size appears bi-modal in nature, with a mixture of large and small

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grains. The Er2O3 dispersoid radii are less than 0.5μm within the size range required for elevated
temperature alloys. The dispersoids are observed along grain boundaries and in parallel strings

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indicative of formation along crystallographic planes (Fig. 4)[27].

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2.3 Steels

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In the study on the laser rapid forming of 34CrNiMo6 steel, Huang et al. pointed out that cooling
condition has a significant effect on the microstructure and mechanical properties of the laser rapid
formed thin-wall component[30]. The component under the metal-cooling condition has the least tensile

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property, whereas that under the water-cooling condition is most brittle. Under the air-cooling
condition, the microstructure changes from bainite+ferrite+retained austenite in the top zone to the
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coarse ferrite+cementite in the bottom zone. The component exhibits the lowest tensile strength but
the best plasticity because of the greatest tempering effect of the laser rapid forming process[30].
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Work on the laser solid forming process of AISI 420 stainless steel, indicates that the purification
occurs when the oxygen partial pressure is lower than a certain threshold[31]. The oxygen adsorption
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mainly takes place in the molten pool stage. The decrease of the oxygen partial pressure and increase
of the contents of elements forming volatile oxides and original oxygen in the deposited material all
promote the purification[31]. According to another work, the decrease of the environment oxygen
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content resulted in the decrease of the number density of the oxide particle within the laser solid formed
sample of AISI420 stainless steel[32].
Work in the laser solid formed 300M steel, found out that the as-deposited microstructure consists
of martensite and coarse bainite, and the microstructure becomes uniform after the heat treatment,
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composed of tempered martensite, bainite and a small amount of retained austenite[33]. The change of
the microstructure also has an evident effect on the fatigue crack growth rate of the materials .
Jerrard et al.[34] and Facchini et al.[35] have fabricated 17-4PH stainless steel by SLM and they
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reported the occurrence of metastable austenite or mixtures of austenite (fcc, a=0.357 nm) and
martensite (bcc –ferrite (Fe), a=0.286 nm) to compose the microstructure for the fabricated products.
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Recently Murr et al. reported SLM fabrication of 17-4PH stainless steel components in an argon cover
gas, with directional martensite (bcc) oriented in the [200] direction, parallel to the build direction
shown by the arrow in Fig.5, for either argon or nitrogen-atomized powder[3]. Furthermore, almost in
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the meantime, Lin et al. even investigated the microstructure and mechanical properties of laser solid
formed and laser forming repaired 17-4PH stainless steel[36]. The microstructure of laser deposited
zone (LDZ) consisted of martensite laths and a small amount of second strengthening phases particles,
such as M7C3 and NbC carbides. The microstructure of HAZ consisted of the ferrite strips and
martensite laths. The comprehensive mechanical properties of the laser solid formed and laser forming
repaired 17-4PH stainless steel were equivalent with those of the wrought. Only their ductilities were
just below that of the wrought. Additionally, the tensile strength of the repaired sample is between
those of the laser solid formed and the wrought samples[36].

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2.4 Ni or Co-based superalloys
Ni-base alloys are typically used to manufacture hot-section components of gas turbine engines,
as such alloys offer higher yield strength with increasing operating temperatures primarily due to the
presence of the secondary γ’ phases.
The basic research results concerning the fabrication of Inconel 625 superalloy by electron beam
melting (EBM) have been carried out[37]. The 3D-optical metallograph composite section was
illustrated in Fig. 6 (a), and the columnar precipitates, shown in the TEM image in Fig. 6 (b), have
been identified as ’’-Ni3Nb bct platelets coincident with the NiCr fcc matrix 111 planes.
Correspondingly, the NiCr matrix grains evident in the horizontal plane of the 3D composite view in
Fig. 6 exhibit a [200] texture in the horizontal plane, and parallel to the build direction ([HKL]=[200])
and a [220] ([110]) texture in the vertical reference plane as shown in the vertical reference plane TEM

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image in Fig.6 (b).

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Many researchers paid attention to the AM of Inconel 718 alloy due to its high application
potential. A regular microstructure with good metallurgical bonding, minimal defects and fine

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dendritic grains was formed in SLMed In718 samples[38]. But after heat treatment, the regular dendritic
structure disappeared and a needle-like δ phase precipitated at grain boundaries when γ’ and γ’’ phases

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dissolved in the matrix. As reported in literature [39], Inconel 718 alloy parts were manufactured by
laser solid forming technology with two types of laser scanning paths, i.e., single direction raster
scanning (SDRS) and cross direction raster scanning (CDRS). The as-deposited grains of the CDRS

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sample are finer than those of the SDRS sample. The ultimate tensile strength of those two samples is
similar to each other, but the ductility of the CDRS sample is much better than that of the SDRS one.
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Furthermore, the influence of Laves phases on the high-cycle fatigue behavior of laser AMed Inconel
718 has also been studied[40].
Tayon et al.[41] examined the evolution of microstructure, crystallographic texture, and
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mechanical properties of Inconel 718 alloys fabricated via electron beam freeform fabrication (EBF3)
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process (Fig. 7). The microstructure of as deposited (AD) condition displays a range of strong texture
components for L orientation (deposition direction) that are largely concentrated around <001>. After
heat treatment (HT) of solution and aging, recrystallization occurred and the extent of texture
appreciably decreased. The average UTS and YS values for the L orientation in the EBF3 block (either
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in the AD or the HT condition) were greater than those for the as-cast Inconel 718 but less than those
for rolled Inconel 718. The heat treatment significantly increased both UTS and YS compared to AD
condition and reduced the anisotropy (Table 1).
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IN 718 was processed by SLM to produce columnar microstructural morphology composed of

primarily <200>-textured γ’ phase precipitate columns[42].
In another work, IN 718 was processed using laser rapid forming (LRF) and consisted of
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columnar dendrites that grew epitaxially from the substrate parallel to the deposition direction, with a
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thin layer at the top of the sample where the dendrites grew along the laser scanning direction, referred
to as direction-changing dendrites[43].
In-738LC alloy as a typical cast nickel-based superalloy, was produced by laser solid forming
(LSF). Cracking was frequently found for LSF superalloy due to the high content of Al+Ti[44, 45]. It
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was found that the crack-free sample could be obtained for In-738LC alloy with 1050 °C preheating[46].
The In-738LC obtains its strength primarily from the presence of a large amount of γ’ phases in the
nickel-based fcc matrix (γ). Compared with the cast reference, reported in Rickenbacher’s work[47],
the yield strength and ultimate tensile strength of the as-deposited samples were both 14% higher while
the elongation was 44% higher.
The scanning laser epitaxy (SLE) process has been investigated for similar-chemistry powder-
substrate and dissimilar-chemistry powder substrate combinations, and the process has yielded
encouraging results in producing epitaxial microstructural deposits even for SX alloys (Fig. 7). This
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should be of great significance for turbine hot section repair[48].

Achieving epitaxy in metal AM is challenging and requires tight control of processing parameters
such as energy source power, scanning speed, and spot diameter. Complete powder melting systems
have been significantly more successful than partial powder melting systems in the production of
epitaxial microstructure. The demonstrated potential to produce epitaxial microstructure by using a
metal AM process could open up entirely new paradigms of manufacturing if the process is
demonstrated to be repeatable and robust in the future[49].
Rene 142, a commercial, columnar grained, gas turbine airfoil Ni-based superalloy, has been
fabricated from a pre-alloyed, atomized powder by AM using electron beam melting. The fabricated

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EBM product is relatively optimized with regard to potential creeprelated behavior in turbine blade
applications without any post-fabrication heat treatment[50].

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Special emphasis is also put on the specific properties and possibilities of selective electron beam
melting (SEBM) for Co-Cr-Mo alloys. During SEBM, Co–Cr–Mo alloys solidify via the fcc γ-phase
which is not or only partially transformed into the stable ε-phase during the building process. The as-

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built samples show a pronounced texture as a result of epitaxial growth with preferred grain orientation

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of the γ-phase in <001> direction. The M23C6 precipitates (M = Cr, Mo, Si) are aligned along the build
direction with a mutual distance of about a few microns[51-53]. After adequate heat treatment (hot
isostatic pressing + homogenisation) Co–Cr–Mo alloys built by SEBM show superior properties
compared to wrought or cast alloys[51].

2.5 Intermetallic compounds U

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The recent efforts and advances in AM of mainly two types of intermetallic compounds, TiAl
based alloy and NbSi based alloy, are presented and summarized in this section.
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TiAl based alloys are highly attractive for the aeronautical industry as new high temperature light-
weight structural materials due to their low density (3.7-3.9 g/cm3), high elastic moduli, excellent
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tensile strength and creep resistance at high temperature[54-56]. Therefore, TiAl alloys have shown a
potential for the application with the service temperature of 760-850 °C. However, the room
temperature tensile elongation is very poor and only about 1%, which makes the TiAl-base alloy
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difficult to be processed into components especially the complex-shaped ones. Compared to the
traditional manufacturing methods such as cast, extrusion and forging, the additive manufacture
technologies, such as SEBM, SLM and LDMD, are the emerging near-net and net forming
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technologies and will be applied to produce the near-net-shape or net-shape TiAl based alloys
components[57]. Li et al. even developed the laser cladding TiAl intermetallic compound coatings on
the titanium alloy[58-60]. AM of TiAl based alloys has been a hot area of research in recent years.
Among these metal AM technologies, laser direct metal deposition(LDMD) was first used in the
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fabrication of TiAl based alloys. As early as 2000, Seivastava et al.[61, 62] fabricated simple shapes of
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TiAl alloy material using LDMD technology with gas atomized Ti-48Al-2Mn-2Nb powders. They
demonstrated that the microstructure of TiAl based alloy prepared by LDMD was heterogeneous in
nature and very fine, as compared to the conventional manufacturing methods[61, 62]. In addition, the
compositional heterogeneity present in the LDMD-fabricated TiAl based alloy could be eliminated by
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post heat treatment. However, the obvious grain coarsening occurred after annealing[61, 62].
Qu et al.[63, 64] successfully fabricated two types of TiAl specimens with size of approximately 40
mm × 40 mm × 3 mm, which combined with preheating before LDMD process. The microstructures
of the two as-deposited TiAl specimens were all fully lamellar structure consisting of γ-TiAl and α2-
Ti3Al. Their grain size was 50-100 μm and the ultra-fine lamellar spacing was about 0.2μm, as shown
in Fig. 8[63, 64], and their room temperature ductility was very poor, only 0.2% for Ti-47Al-2.5V-1Cr
specimen and 0.3% for Ti-40Al-2Cr specimen, which were obviously lower than that of cast TiAl
based alloy[63]. In addition, the tensile strength and ductility could be significantly enhanced by
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annealing. The tensile strength of the two TiAl based alloy specimens was improved from about
550MPa to 650MPa, and their room temperature ductility reached 0.6% after annealing at 1125 °C/30
min and followed by WQ[64].

Lober et al[65] investigated the SLM process of TiAl based alloy, and bulk cylinders and
dodecahedron unit cells of Ti-44Al-4Nb-1Mo-0.1B alloy with a relative density of around 99% were
successfully manufactured[65]. The as-fabricated microstructure was fine grained nearly lamellar β
structure, and the supplied compression strength and strain were approximately 1900MPa and 9.5%,
respectively. Additionally, the compression strain could be greatly improved to 16.5%, but its
compression strength would decrease to 1670MPa[65].
Shi et al. studied the effect of laser scanning speed and energy density input on Ti-45Al-2Cr-5Nb

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alloy processed by SLM[66, 67]. The SLM-processed alloys were dominated by high-angle grain
boundaries (HAGBs) and the content of HAGBs increased with increasing energy density inputs or

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deceasing laser scanning speed. Moreover, the increase of laser scanning speed and the decrease of
energy density input all could lead to an obvious decrease of average grains size. The SLM-produced
TiAl alloys consisted of α2 matrix, γ and B2 phases randomly distributed in the matrix, as shown in

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Fig. 9. With the increase of energy density inputs or decrease of laser scanning speed, the content of

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α2 phase increased, while the contents of γ phase and B2 phase decreased[66, 67]. Although the relative
density of the SLM-process Ti-45Al-2Cr-5Nb alloy was only around 92%, the nanohardness of the
TiAl alloy was up to 9.5 GPa , which was much higher than those of the traditional casting counterparts
(5.1 GPa) and traditional roll bonding fabricated TiB2 reinforced TiAl alloy (6.73 GPa). Moreover, its
compression strength was approximately 1250 MPa[66].
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EBM is very suitable to process high melting temperature, refractory, and/or reactive materials[68].
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Equiaxed, small-grain (~2 μm) structures with lamellar γ/a2-Ti3Al colonies with average spacing of
0.6 μm have been fabricated by AM using EBM of Ti-47Al-2Cr-2Nb (at.%) titanium aluminide powder.
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The EBM-fabricated titanium aluminide prototype density was ~3.76 g/cm3, roughly 98% of
theoretical density[69]. But, during the EBM processes, due to the vacuum environment, the preferential
vaporization of high vapor pressure elements is noticeable.
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It was reported that the atomic percentage of aluminium decreased along with the increase of
energy input. Element loss of aluminium can reach 15 at.% for Ti-47Al-2Cr-2Nb alloy[70]. By adjusting
the processing parameters including layer thickness and beam parameters and taking advantage of the
short return times, Al loss was reduced to about 0.5 at.% for this TiAl alloy[71]. Ashfaq Mohammad et
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al. studied the effect of EBM parameters on microstructure and mechanical properties of Ti-48Al-2Cr-
2Nb (at.%) titanium aluminide and the ultimate tensile strength of the EBMed specimens close to
wrought form (480 MPa) but superior to castings (275-380 MPa)[72].
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Todai et al. reported that Ti-48Al-2Cr-2Nb alloy fabricated by EBM exhibited a unique layered
microstructure composed of duplex-like region and γ bands (Fig. 10)[73]. Duplex-like region is
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predominantly composed of lamellar-structured γ/α2 fine grains and fine equiaxed γ grains, while γ
bands is composed of coarser equiaxed γ phase grains. Regardless of θ, the average layer thickness of
the duplex-like region and the γ band was approximately 60μm and 30μm, respectively. The grain size
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in the γ bands is approximately 20μm. Owing to the unique layered and finer microstructure, the yield
strength and the tensile elongation of the specimens shows the orientation dependence. But, in general,
the room temperature yield strength is good, i.e., at θ=0°, 45° and 90° it is ~605 MPa, ~556 MPa and
~587 MPa, respectively. The yield strength of the as-EBM specimens at room temperature was higher
than that prepared by casting. In addition, the room temperature ductility of the specimen at θ =45° is
over 2%, while the elongation of the specimens at θ=0° and 90° is about 0.5% and 2%.

Besides, Ma et al.[74, 75] presented an interesting method for fabrication of titanium aluminide
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components by using in-situ alloying and layer AM based on the gas tungsten arc welding (GTAW)
process combined with separate feeding of commercially pure titanium wire and pure aluminum wire.
The bottom region of the components showed a lamellar (γ/a2) structure and interlocked grain
boundaries, whereas the top region revealed systematic occurrence of interdendritic γ phase. The
ultimate tensile strength of the Y-direction and Z-direction is 549±23 MPa and 488±50 MPa,
respectively. The specimens tested in the Y-direction are found to have higher ultimate tensile strength
(UTS) and yield strength (YS) than those tested in Z-direction. However, there is no observable
difference in elongation.
In the material field, much attention has been paid to another kind of ultra-high-temperature
structural materials worldwide, Nb-Si based alloys. They have shown great potential to replace Ni-
based supreralloys due to their high melting point (>1750 °C) and low density (6.6-7.2 g/cm3) as well

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as attractive specific mechanical properties at elevated temperatures of 1200-1400 ºC[76-78]. Over the
past few years, several processing techniques including vacuum arc melting, induction melting,

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investment casting, directional solidification (DS), and powder metallurgy have been successfully
employed to fabricate Nb-Si based alloys[79-81]. Although the Nb-Si alloy prototype airfoil have been

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fabricated by a hybrid arc-melting and drop-casting technique, by overcoming the difficulties of
developing the melting capability of the appropriate scale and the matching ceramic mold materials,

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obtaining the proper dovetail geometry of an airfoil is still a complex endeavor, and requires numerous
time-consuming, post-machining operations[76]. In the light of AM technology, it could produce near
net shape components with complex shape and even with complex internal features. Additionally, due

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to the rapid melting and solidification characteristics of AM processing, it is easy to achieve finer
microstructure and to reduce composition segregation of Nb-Si based alloys, which is possible to
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improve the overall properties.
Dicks et al. deposited the alloys with the composition of Nb-22Si-26Ti-6Cr-3Hf-2Al (at.%) by
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laser directly forming using pre-alloyed gas-atomised powder, and demonstrated that direct laser
deposition was a suitable technique for the fabrication of the Nb-Si based alloy, allowing samples to
be produced with high dimensional accuracy[82]. As shown in Fig. 11(a), the microstructure of the as-
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deposited alloy consisted of bcc niobium solid-solution (NbSS) phase, Nb5Si3 intermetallic compound
and HfO2 particles, and is much finer than those of a cast alloy with similar composition. No changes
to the structure of phases present occurred during heat treatment at 1500 °C for 24 h, although the
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microstructure moved towards a more stable state (as shown in Fig. 11(b)).

Liu et al.[83] fabricated Nb-17Si-23Ti (at.%) ternary alloys using in-situ reaction laser melting
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deposition (LMD) from Nb-28 at.% Ti powder mixture and pure Si powder (Fig. 12). The as-deposited
samples mainly consisted of NbSS, metastable Nb3Si and Ti-rich NbSS. As shown in Fig. 13, the in-situ
reaction LMD processing resulted in remarkable refinement of microstructure and the average size of
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NbSS was about 1-3 μm, which was further refined in comparison with that of the LMD Nb-26Ti-22Si-
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3Hf-2Al (at.%) alloy from the corresponding gas-atomised alloy powder[82]. With the increase of the
laser power from 1 kW to 2 kW, the NbSS morphology changed from discontinuous dendritic to near
equiaxed, and the microhardness increased from 822 HV to 951 HV, meanwhile, the indentation
fracture toughness was improved from 12.3 MPa·m1/2 to 14.1 MPa·m1/2. Furthermore, the fine
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directional solidification (DS) microstructure were achieved by LMD as well, and presented
remarkable mechanical properties. Its micro-hardness was as high as 1075 HV and indentation fracture
toughness was up to 20.3 MPa·m1/2, where the toughening effect was mainly attributed to the
directional growth of fine NbSS and Nb3Si phases.

Guo et al. [84] investigated the microstructure, hardness and oxidation behavior of Nb-18Si-24Ti-
2Cr-2Al-2Hf (at.%) alloy fabricated by SLM using pre-alloyed powder. Results showed that the as-
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built alloy consisted of Nbss, α-Nb5Si3, β-Nb5Si3 and Nb3Si. Sphere shaped Nbss phases with a
maximum diameter of 300 nm were obtained. After heat treatment at 1500 °C for 4 h, the Nbss phases
interconnected to form a continuous matrix with discontinuous α-Nb5Si3 phases, and the average
hardness of the SLM parts decreased from 810 HV to 542 HV. Compared with the oxide scale on arc-
melted alloy, oxide scale formed on SLM-processed after oxidation at 1300 °C for 0.5 h was more
compact with fewer holes, combined with the formation of a more continuous SiO2 layer at the initial
oxidation stage.
To date, the related studies of Nb-Si based alloys prepared by AM technique have been carried
out and extremely finer microstructure, higher hardness, higher room temperature toughness and better
oxidation resistance at high temperature could be obtained by AM [82-84]. However, due to the intrinsic
brittleness of Nb-Si based alloys, and the rapid melting and solidification process during AM, micro-

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cracks tend to appear in the preparation of larger scale samples. In our opinion, to realize the
application of AMed Nb-Si based alloys, further research work is highly needed for composition

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optimization by adjusting the level of Si and adding the alloying elements of Ti, Hf, and etc., as well
as processing optimization such as preheating during AM.

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2.6. Metal matrix composites

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Lots of research work focused on AM of metal matrix composites (MMCs), including Al, Ti, Co,
Fe matrix ones, and the achieved results were fruitful, in which the in-situ reactions for the synthesized
products were impressive.

2.6.1 Al matrix composites

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To improve the mechanical properties of aluminum matrix, the aluminum borate whisker
Al18B4O3 of 0.5-1 μm in diameter and 10-30 μm in length was used via laser surface melting[85]. The
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results showed that microhardness of the laser layer (294 HV) was improved 65% compared to
aluminum matrix (178 HV), because of the presence of Al2O3 particles, solid solution hardness and
the grain refinement of the laser layer following rapid quenching associated with the processes[85].
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Besides, the whiskers were decomposed and γ-Al2O3 appeared at the surface of the composite after the
laser surface melting. A great deal of γ-Al2O3 existed at the bottom of the laser pool.
Kang et al. reported a novel Al-based composite reinforced by nano-sized Al91Fe4Cr5 quasicrystal
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(QC) on Al substrate by SLM[86]. This composite material was prepared from the mixture of pure
aluminum and Al65Cu20Fe10Cr5 QC powders, which could produce parts with sophisticated form and
fine microstructure with near-zero material waste. Additionally, the sample obtained at relatively low
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laser power presented a mixed microstructure including partially melted QC, micro-QC and nano-QC.
The instrumented indentation test indicated that the partially melted QC particle presented higher
hardness (8.59 GPa) than that of the other structure in the composite (4.58 GPa or 3.37 GPa). However,
due to the ultra-low ductility of the QC alloy, SLMed QC/Al composite was easy to crack[86]. Besides,
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they also studied the microstructure and wear behavior of hypereutectic Al-Si alloy, in situ fabricated
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using SLM of a mixture of eutectic Al-12Si (wt%) and pure Si powders, and fairly dense hypereutectic
Al-Si alloys were obtained[87].
Yang et al. studied the effect of different Si content on wear resistance of AZ31D magnesium
alloys by laser cladding with Al-Si powders[88]. Al and Si powders were mixed with the weight ratio
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of Si 8.0 wt%, 12.5 wt% and 60 wt%, and mixed with resin PVA , and then placed on the substrate
surface with a thickness of about 0.5 mm. The clad layer with the Si content of 12.5% exhibited the
optimum wear resistance. The major reinforcing phase Mg2Si particulate with eutectic Mg17Al12 phase
was found in the clad layer, and the micro-hardness increased 4.85 times due to the presence of this
intermetallic phase[88].
Anandkumar et al. fabricated the coating composite consisting of an Al-Si matrix reinforced with
SiC particles by laser cladding on UNS A03560 cast Al-alloy substrates from the mixture of powders
of Al-12 wt% Si alloy and SiC[89]. The undissolved SiC particles were mainly found at the bottom of
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the clad tracks, where the maximum temperature reached during the processing was lower, and Al4SiC4
and Si particles dispersed in a matrix of α-Al+Si eutectic. These results show that Al4SiC4 and Si
increase the hardness from 90 HV to 250 HV of the material by dispersion hardening but not contribute
to its abrasive wear resistance, because they are softer than the abrasive particles[89].
Moreover, Riquelme et al. reported the deposition of Al/SiCp coatings on AA6082 aluminum
alloy using laser cladding[90]. The employed method consists of the addition of different alloying
elements (Si or Ti) to the composite matrix powder to modify the equilibrium of the detrimental Al4C3
formation reaction. Al40Si/SiC is the hardest coating because of the higher percentage of SiC and
primary and partially dissolved Si than the others. Fig. 14 shows a schematic figure that explains the
reaction process, in which SiC particles are completely dissolved and it only can be seen that a ring of
TiC forms in the surroundings of a smaller SiC particle. Besides, the molten Ti reacts with the Si and

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forms TiSi2. The formation of these products decreases the reinforcement amount[90].

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Lijay et al. synthesized aluminum alloys AA6061 reinforced with various amounts (0, 2.5% and
5%, mass fraction) of TiC particles by in situ reaction of inorganic salt K 2TiF6 and ceramic particle

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SiC with molten aluminum [91]. The in situ formed TiC particles act as effective grain refiner and refine
the grains of cast aluminum matrix from ~90 μm to ~30 μm (Fig. 15), and they completely change the

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dendritic structure of as-cast AA6061[91]. This may be due to that TiC particles acted as grain
nucleation sites and refined the grains of aluminum matrix effectively. Besides, possible intermetallic
compounds including Al3Ti and Al4C3were detected in significant quantity in the AMCs.

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2.6.2 Ti matrix composites
Discontinuously reinforced Ti6Al4V/TiB composites were fabricated using direct laser
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deposition by injection of premixed powders of TiB2 and Ti6Al4V[92]. Additionally, (TiB+TiC)
reinforced Ti matrix composites were prepared by SLM using spherical commercially pure titanium
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(CP-Ti) powder with the particle size distribution of 15-45 μm and polyhedron-shaped reinforcing B4C
particles with a mean particle size of 5 μm [93]. The TiC and TiB phases were formed by in situ reaction
in a route of 5Ti+B4C→4TiB+TiC. Moreover, the in-situ whisker-like TiB and granular TiC phases
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significantly grew and coarsened with the increase of the laser power (Fig. 16), and this would result
in the decrease of the composite hardness[93].
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A compositionally graded TiC/Ti6Al4V material was successfully fabricated by direct laser

fabrication with TiC powder with particle size ranging from 100 to 200 μm and Ti6Al4V wire with a
diameter of 0.45mm[94]. This design of the feedstock material combination of TiC powder and Ti6Al4V
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wire is interesting. After the laser processing, the TiC particles are distributed uniformly in the
Ti6Al4V matrix, and along most of the length of the compositionally graded sample TiC was
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completely melted and formed primary TiC, eutectic TiC and secondary TiC. When the volume
fraction of TiC particles reached 74%, some unmelted TiC was retained. The sliding wear test showed
that the sample with 24 vol.% TiC exhibited the optimum balance of the tribological properties[94].
Surface modification of Ti6Al4V alloy was conducted by AM using ball milling treated mixtures
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of Ti and SiC powder particles. Two laser cladded layers of 90%Ti+10%SiC and 80%Ti+20%SiC were
deposited onto the Ti6Al4V substrate. Chemical reactions took place between the Ti and SiC particles
in the composite layers, and the reaction products consisted of TiC and Ti 5Si3. The formed Ti5Si3
particles present an average size of about 200 nm and TiC ones about 1μm. The 80%Ti+20%SiC
cladded layer increased the hardness of the Ti6Al4V matrix from 339.1 HV to 932.2 HV, and this was
mainly attributed to the high hardness of the TiC and Ti5Si3. In particular, the hardness of TiC is high
up to 2856HV-3060HV[95].
A novel oxide dispersion strengthened (ODS) titanium aluminide alloy (Ti-45Al-3Nb-＜0.2Y2O3
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at.%) was developed for powder-based processing technologies with a focus on spark plasma sintering
and AM[96]. The ODS particles were homogeneously distributed in the alloy matrix after processing in
the liquid state. A significantly reduced texture formation was observed with this novel alloy.
Ti-Co elemental powder blends in nominal chemical compositions of 60Ti-40Co (wt.%) with a
particle size of 140-320 mesh were selected as raw material, and TiCo/Ti2Co dual-phase intermetallic
coatings consisting of TiCo block primary phase and Ti2Co continuous matrix were fabricated by laser
cladding on a commercial α+β titanium alloy BT9[97]. The coatings exhibited an average hardness of
about 720 HV and excellent wear resistance under dry sliding wear test conditions.

2.6.3 Ni matrix composites

Concerning the AM of Ni matrix composites, series of material reaction systems were used for

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different purposes, including Ni-Ti-C, Inconel 690-TiC, Ni-TiC, NiCr-Cr2O3-La2O3, Ni60-BN, Ni-Mn-
Si, WC-NiBSi, etc..

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Ni alloy composite coating reinforced by in situ reacted TiC particles with a gradient distribution
was prepared using one-step laser cladding with a pre-placed mixture on a 5CrMnMo steel substrate[98].

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Titanium and graphite particles were used as raw reaction material, with the average size of 2 μm and
4 μm respectively. They were mixed with Ni alloy powder, in which the titanium graphite powder was

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30 vol.%. The mixed powders were painted on the substrate to give a thickness of about 0.8 mm. Laser
cladding was carried out with a 3kW continuous wave CO2 laser to produce a series of single clad
tracks without overlap. The phases of the laser cladded coating consist of γ-Ni, TiC, Cr23(C, B)6, Ni5Si2

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and Cr2B, without the presence of Ni-Ti binary compounds. A large number of formed TiC particles
are uniformly distributed in the interdendritic regions, which means that TiC particles have been
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trapped by the rapid advancing solid-liquid interface. The size distribution of the TiC particle is of the
order of nanometers, as shown in Fig. 17(a). It is also noticeable that the interface between the TiC and
the γ-Ni austenite remains clean and free from any deleterious phase due to interface reactions (Fig.
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17(b)). Because of the high solidification speed the interface reaction between the particle and the
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molten alloy is completely restrained.

An interesting phenomenon was observed that, the volume fraction of TiC particles exhibited a
smooth gradient distribution as a function of the coating depth, that is, the volume fraction of TiC
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particle changed from 1.86% at the bottom to 38.4% at the top surface layer. This gradient distribution
of TiC particles should be attributed to the relative lower density of TiC compared with the Ni alloy.
In other words, it is understandable that the TiC particles tend to segregate to the upper regions in the
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particle-reinforced MMC layer. Fig.18 shows that, the volume fraction of TiC particles and the
microhardness of the coating varied gradually with the coating depth, and the highest value of the
microhardness reached 1250 HV0.2[98].
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Titanium carbide (TiC) reinforcement particles were incorporated into Inconel 690 alloy with
laser direct deposition to build functionally gradient MMCs[99]. The used raw materials included the
Inconel 690 spherical particles of diameter 44 μm to 149 μm with a typical alloy composition of 27.0
Cr, 8.0 Fe, 0.05 C, 0.50 Si, 0.50 Mn, 0.50 Cu, bal. Ni, and the irregularly shaped TiC particles of the
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similar size. The composition varied from 100% Inconel 690 at layers 1 and 2 to increasing
concentrations of TiC for the subsequent 18 layers. High temperature dissolution of TiC was not
detected under the processing conditions including the laser power of 350W, laser scanning speed of
17 mm/s and layer thickness of 0.254 mm. It was found that increasing the amount of TiC particles
altered the microstructure of the Inconel 690 matrix (Fig. 19). The microstructure became more refined
as the amount of TiC increased, and the predominant grain shape shifted from columnar to equiaxed.
Furthermore, a finely dispersed dendritic TiC phase appeared when TiC above 30.0% by volume was
present. Wear results showed an average of 42% decreased in volume loss on the disk by increasing
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content to 40 vol.% TiC.

Concerning the refining effect of the microstructures in the laser cladded layers, presently it is
well known that the addition of rare earth elements is an effective approach, for example, evident
refinement and spheroidzation of the primary phase of the laser clad composite coatings was reported
by addition of La2O3 in the NiCr-Cr2C3 precursor mixed powders, and in this case the volume fraction
of primary blocky Cr7C3 and Cr7C3/γ eulectics was also relatively decreased [100]. Besides, Liu et al.
investigated the effects of La2O3 addition on the microstructure and wear properties of laser clad
γ/Cr7C3/TiC composite coatings on γ-TiAl intermetallics alloy substrate with NiCr-Cr3C2 precursor
mixed powders[100]. The addition of rare-earth oxide La2O3 led to obvious refinement and

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spheroidization of the primary phase of the laser clad composite coatings and relative decrease in
volume fraction of primary blocky Cr7C3 to Cr7C3/γ eutectics, as well as increase of the coating

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microhardness. When the addition of La2O3 was approximately 4 wt.% the laser clad composite
coating possessed the highest hardness, and toughness and thus the best enhancement of wear

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resistance of about 30%[100].
The refinement phenomenon was also observed in the laser cladded Ni-TiC coating deposited on

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AISI 4140 steel[101]. There was an improvement in 15%-20% of relative wear resistance for the
claddeed coating compared with the bare steel substrate. TEM results in Fig. 20 revealed deformation
twinning in γ-Ni and the presence of high dislocation density. In addition to TiC phase, spherical

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multiphase nano-crystalline area was detected in the vicinity of interdendritic regions. The formation
of the greater number of nuclei and a reduction in nuclei growth was attributed to lanthanum ion, which
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partially dissolved in the nuclei and reduced crystal growth velocity. Furthermore, larger numbers of
defects were generated at the interface of TiC and γ-nickel. La atoms were captured by these defects
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causing an increase in the nucleation rate and decrease in surface energy of crystallization.
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With regard to Ni-based composite coatings, Luo et al. fabricated the 30 wt% WC/70 wt% (Ni-
NiCrBSi) coating on the Ti-6Al-4V substrate by laser cladding[102]. The content of the NiCrBSi had a
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remarkable influence on the phase constituents and the microhardness as well as the fracture toughness
of the coatings.
For laser cladding of the Ni60-hBN coating on a medium carbon steel, the high-energy ball
milling of nano-Ni onto nano-h-BN was conducted with the aim to enhance the compatibility between
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the h-BN and the Ni-based alloy (Ni60) matrix during laser cladding processing[103]. The main phases
in the laser clad coating were composed of hard precipitates CrB, Ni3B, Cr7C3, and nickel based solid
solution (γ), which were mostly distributed in the upper layer of laser cladding zone, and greatly
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increased the microhardness of the coatings[103].

Zhang et al. synthesized three Ni-Mn-Si coatings on copper substrate by laser cladding [104]. The
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highest hardness of about 1100 HV occurred in the clad layer of coating Ni (40 at.%)-Mn (20 at.%)-Si
(40 at.%), and Ni-and-Mn silicides were the major factors in increasing the hardness of the coatings,
in which Ni-Si phases played a more important role than Mn-Si in increasing the hardness and
decreasing the friction coefficient of coatings[104].
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Wang et al. reported the design and fabrication of Ni60.16Zr33.84Al6 alloy coating on a AZ91HP
magnesium surface by laser cladding[105]. The coating layer mainly consists of amorphous, two ternary
intermetallic phases with Ni10Zr7 and Ni21Zr8 type structure. These phases make the coating exhibit
high hardness (930HV) , good wear resistance and corrosion resistance.
Another important research result should be mentioned here. Benefited from the unique
preheating process, dense and crack-free WCp/NiBSi metal matrix composite MMC samples were
obtained successfully by EBM[106]. The WC reinforcements in the EBM specimens were evenly
distributed in both the vertical and horizontal planes. Although dissolution occurred at different
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degrees, the reinforcements still maintained spherical morphology under a thermal shock by an
electron beam radiation. The typical thickness of the dissolution band was about 5μm (Fig. 21). The
average macro-hardness of the MMC reached 58HRC in both the horizontal and vertical directions.
The measured flexural strength, impact toughness and compressive strength were 930 MPa, 3.6 J/cm2
and 1850 MPa, respectively.

2.6.4 Co matrix composites

Weng et al. produced MMC coatings on Ti-6Al-4V titanium alloy by laser cladding with the pre-
placed powders of Co42 Co-based self-fluxing alloy, B4C, SiC and Y2O3[107]. The composite laser
cladding coatings were mainly reinforced by CoTi, CoTi2, NiTi, TiC, TiB2, TiB, Cr7C3, and Ti5Si3,
resulting from the in situ reactions in the molten pool. The average micro-hardness of the cladding

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zone was even high up to 1134 HV0.2, and thus the wear resistance was enhanced by over 10 times
compared with the substrate. However, it was also pointed out that too much SiC (14 wt.%) would

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lead to coarse microstructure and a rise in brittleness, and was not propitious to the wear resistance[107].
Ti5Si3/TiC reinforced Co-based composite coatings were also fabricated on Ti-6Al-4V alloy by laser

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cladding with Co42 and SiC mixture[108]. In this case the microhardness of the coatings was enhanced
to over 3 times the substrate. Similarly, too much SiC (20%) addition led to cracks in the cladding

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layer, and they were detrimental to further improvement of the wear property.
Besides, composite coatings on titanium alloy were attempted by laser cladding with Co42+TiN
mixed powders[109]. The coatings were comprised γ-Co/Ni, CoTi, CoTi2, Co3Ti, NiTi, TiN, CrB, Cr7C3,

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TiC, TiB, and TiC0.3N0.7 phases. The dissolution and re-precipitation of TiN occurred during the laser
cladding process. The in situ formed TiC tended to grow on the surface of the undissolved TiN, and
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TiCo0.3N0.7 was produced from the reaction between TiC and TiN with the addition of 30 wt.% TiN.
The wear resistance of the cladding coating under dry sliding wear test was increased to 18.2 times the
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Ti-6Al-4V substrate.
Although Stellite 6 with the unique chemical composition (29%Cr, 4.5%W, 1.5%Mo,1.2%C, Co
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balance, in weight), is the most popular Stellite alloy employed in various field of industry, it was
found deficient due to insufficient hardness and wear resistance especially in some applications where
metal-to-metal sealing hardfacing was subjected to high loading and high-cycle operating. Therefore,
to enhance the hardness and wear resistance of Stellite 6, a Stellite alloy mixture hardfacing consisting
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of 70% Stellite 3 and 30% Stellite 21was created via laser cladding for control value seat sealing
surface[110]. The microstructure of the Stellite alloy mixture hardfacing was composed of fcc Co solid
solution, M7C3 carbide, (W, Co)6C and (Co, Mo)3C carbides, indicating a hypereutectic microstructure
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with the carbides as the primary phase. Furthermore, the volume fraction of total carbides in this alloy
was estimated 40%. This mixture hardfacing surpassed Stellite 6 and Stellite 3 in combined properties
of hardness, wear resistance and laser processing, and according to the test result of the industry
application, no leakage was found on the corresponding sealing surface under the specified duration
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of 30,000 cycles[110].
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Ding et al. studied the effect of aging treatment on the microstructure and wear resistance of VN
alloy reinforced Co-based laser cladding composite coatings with the aging temperature ranging from
550 °C to 750 °C [111]. The phase constituents of the composite coatings after aging treatment at 550 °C
and 650 °C were not changed and mainly composed of γ-Co, Cr23C6, Co5.47N, σ-FeV and VN phase,
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but σ-FeV phase disappeared after the aging treatment at 750 °C. The volume fraction of Cr23C6 and
VN was gradually increased as aging treatment temperature increased, resulting in about 10%
improvement in both the microhardness and the wear resistance[111].
To improve the wear resistance of clad material Co-based alloy, VN alloy/Co-based composite
coatings modified by Ti was prepared on a mild steel using laser cladding. The mixed powders used
were 5.0 wt% VN alloy powders (2.5-7.5 μm), Ti powders (1.2 wt%-9.6 wt%, 2-10 μm) and balance
of Co-based powders (53-120 μm). The VN/Co-based coatings were mainly composed of γ-Co, Cr23C6,
Co5.47N, σ-FeV and VN phases, and new TiN and VC phases as the reaction products:
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TiC+VN=TiN+VC, were detected in the composite coatings after adding Ti [112]. The formation of TiN,
VC and other intermetallic compounds in the composite coatings after adding Ti retarded the growth
of dendrites, promoted the transformation of long rod-like dendrites into short rod-like dendrites and
the formation of fine grains and a large number of equiaxed grains, and hindered the formation of
cross-slip and jog of the dislocations. The action mechanism of Ti on the microstructure and VN/Co-
based composite coatings was illustrated in Fig. 22.

2.6.5 Fe matrix composites

Qin et al. fabricated high Co-Ni secondary hardening steel coating (mainly containing about 13
wt% Co, 10 wt% Ni and 2 wt% Cr) on the 18Cr2Ni4WA steel (low alloy hardened steel) by laser

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deposition method to improve the wear resistance of substrate surface [113]. The microstructure of high

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Co-Ni secondary hardening steel coating was displayed in Fig. 23, mainly consisting of martensite,
lath retained austenite, Fe(Cr, Co, Ni)3C cementite and fine-scale (less than 0.1 μm in length) M2C
carbides. It was believed that the enhanced hardness of the laser cladded coating was attributed to the

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strong secondary hardening of fine M2C carbides, solid-solution strengthening of Co and Ni additions,
precipitation hardening of M3C cementite, and transformation strengthening of martensite [113].

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Currently, this laser repair technology has been used to the maintenance of the aircraft parts, as shown
in Fig.1(d).

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SLM was used to fabricated 316L stainless steel (SS) and hydroxyapatite (HA) powders mixture
with an objective to develop load-bearing and bioactive implants[114]. To produce the composite, the
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316L SS powders (50 μm) were mixed with 5 vol.% HA particles (5 μm) using a bespoke made blender.
The microhardness of 316L SS/HA composite fabricated using SLM is 241.4 HV, higher than that of
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the SS (212.1 HV), and this was due to that 316L SS/HA has a finer grain size than that of 316L SS.
Here, the grain refinement was attributed to the role of HA particles as nuclei to facilitate
heterogeneous nucleation (Fig. 24). Besides, the SS/HA composite fabricated using SLM exhibited a
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tensile strength of 95 MPa which is adequate for load-bearing application and also is not too stiff to
prevent stress stress shielding[114].

Guan et al.[115] reported the 316L matrix composite produced using the polycarbosilane (PCS) -
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316L. The sintered grains and pores of the pure 316L was presented in Fig. 25 (a). In Fig. 25(b) and
(c), a typical structure with steel matrix grains surrounded by a network of white precipitates was
observed, with various PCS contents. The microstructure of the composite material is uniform, with
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homogeneously distributed reinforcements of M7C3 and iron silicides phase, which was generated by
in situ reaction of the metal alloy elements with PCS-derived SiC. The maximum yield strength (YS),
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ultimate tensile strength (UTS) values about 526 MPa and 898 MPa are achieved with the addition of
3 wt% PCS, which is due to a multiple strengthening effect including solid solution strengthening, load
transfer between matrix and reinforcement, grain refinement and grain boundary strengthening[115].
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Some researchers investigated the AM of ceramic-reinforced Fe-based matrix composites, for

example, gas atomized powder blends of AISI 316L stainless steel (particle size of 45-60 μm) and SiC
(particle size: 25-40 μm) in the weight ratio of 95:5 and 80:20 were used as feedstock material. A
defect free and homogeneous composite layer was formed under optimum processing condition. The
microhardness of the clad layer increases to 340 VHN (for 5% SiC dispersed) and 800 VHN (for 20%
SiC dispersed) as compared to 150 VHN of commercially available AISI stainless steel [116]. The
improved hardness and wear resistance are attributed to dispersion of SiC and precipitations of Cr2C3
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and Fe2Si in the microstructure.
Furthermore, Li et al.[117] investigated the effect of NbC content on the microstructure and wear
resistance of Fe-based composite coatings. It was found that α-(Fe, Cr) , (Fe, Cr)7C3, NbC existed in
all coatings. NbC particles formed by the chemical reaction of Nb and C dissolved in the molten pool.
With the increase of NbC content, both the size and the amount of NbC increased obviously, and the
particle morphology transformed from quadrangle to the petaloid shape gradually. Moreover, with the
increase of NbC content, the average micro-hardness increased from 819.3 HV0.2 (5 wt%) to 900.5
HV0.2 (20 wt%).
Multiple carbides reinforced Fe-based surface composite coatings were fabricated successfully
by laser cladding a precursor mixture of graphite, ferrotitanium (Fe-Ti30) and ferromolybdenum (Fe-
Mo70) powders[118]. (Ti, Mo) C multiple carbides showing an fcc crystalline structure, were in situ

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formed in the coating with flower-like dendrites or cubic shape, and they were homogeneously
distributed in the matrix. Furthermore, the fabrication of nanometer Al2O3 dispersion strengthened Fe-

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Cr-Mo composite coatings by crosscurrent CO2 laser on 316L steel was also reported[119].
Besides, a novel Fe85Cr4Mo8V2C1 (wt%) wire material was successfully applied on a carbon-

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rich 1.2379 tool steel by a manual laser cladding process[120]. A fine, homogeneous microstructure
composed of martensite, austenite as well as VC- and Mo2C-type carbides was formed. The generated

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FeCrMoVC coatings were uniform and crack-free exhibiting an increased microhardness (from 627
HV0.1 to 829 HV0.1) and an enhanced abrasive wear resistance compared to the substrate material.
The surfaces of AISI 5115 steel samples were successfully alloyed using FeCrC powder and the
plasma transferred arc (PTA) cladding method[121]. The highest hardness was ~886 HV in the alloying
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zone, compared to the hardness in substrate material (192 HV). The increase in hardness was explained
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by the presence of hard phases, such as the martensitic phase, Cr7C3, Fe23C6 and iron carbides, in the
microstructure.
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In short conclusion, for AM of Fe matrix composites, a great deal of research work focused on
how to design the feedstock materials and choose a suitable processing method, in order to promote
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the formation of high-hardness carbides within the Fe-matrix composite coatings.

2.7 Laser cladding amorphous coatings

Amorphous materials have been a hot topic owing to the excellent mechanical, electrical and
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magnetic properties. It is propitious to the formation of amorphous phases due to the high heating and
cooling rates during laser cladding. With regard to some certain cladding materials with better glass
forming ability (GFA), amorphous phases are easier to form in the cladding coatings[122]. Up to now,
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amorphous alloys such as Ni-Fe-B-Si-Nb, Fe-Co-B-Si-Nb, Fe-Cr-Mo-Y-B-C and Co-Fe-based

amorphous phases, have been obtained in laser cladding coatings on steels[123-125]. Al-Ni-Y and Fe-Si-
B amorphous alloys were also fabricated by laser cladding on Ti-6Al-4V alloy for the improvement in
wear resistance of the coatings[126, 127].
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Iron-based amorphous materials, owing to their high hardness, elastic modulus, wear resistance,
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and corrosion resistance, can be potential materials for surface modification and engineering of many
structural alloys. A novel functional coating was synthesized via laser cladding of an iron-based
(Fe48Cr15Mo14Y2C15B) amorphous precursor powder on AISI 4130 steel substrate. The formed
composite coating consisted of Fe-based nano-crystalline dendrites and amorphous matrix [128]. The
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formation of the amorphous/nanocrystalline phases were due to the action of the sufficiently rapid
heating and cooling of the laser technique and a number of elements with short atomic radius, such as
B, C and N [128]. Additionally, Fe-Co-B-Si-Nb amorphous composite coating was fabricated by high
power diode laser cladding, and both dilution ratio and scanning speed are the two decisive factors for
the fabrication of amorphous coatings[129].
Shu et al. successfully synthesized an amorphous coating on Q235 steel (low carbon steel) by
laser cladding Co-based self-fluxed alloy powder[130]. The size of the preplaced alloy powder was 100-
250 μm. Near the interface a dendrite zone was formed, with the thickness of only 10 μm, and an
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amorphous layer with the thickness of approximately 400 μm appeared over the distance of 10μm from
the interface. In this coating layer, though the XRD peaks associated with (Co, Fe) solid solution was
identified, the volume fraction of amorphous phase was up to 85.1% .
Amorphous-nanocrystals reinforced coating could be formed on TA2 alloy by laser cladding of
Fe3Al-B4C-TiN mixed powders. The TiB2 nanocrystals were produced through the in situ metallurgical
reaction, which blocked the motion of dislocation[131]. In the meantime, the Al3Ti+TiB2/(Ni coated WC)
laser clad coating on the Ti-6Al-4V alloy can increase microhardness and wear resistance of the
substrate. With addition of Al2O3/nano-Y2O3, the SiO2-Al2O3-Y2O3 system and the Al-Ni-Y
amorphous alloys were produced, which were beneficial to the wear resistance. Furthermore, the M6C
(Ni2W4C) content in the coating decreased due to the action of Al2O3/nano-Y2O3, and the finer
microstructure was obtained[126]. The corresponding microhardness of the Al2O3/nano-Y2O3 added

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coating was increased to 1300-1400 HV0.2. It will be a trend for laser cladding amorphous coatings on
titanium alloys.

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Zhang et al. reported the preparation of Zr55Cu30Al10Ni5 bulk metallic glasses (BMGs) using laser
solid forming (LSF) process from the plasma rotating electrode process (PREP) powder[132]. The as-

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prepared powders were composed of amorphous phase and Al5Ni3Zr2-type phase. The Zr55Cu30Al10Ni5
deposit with five layers fabricated by the finest powder with the size range of 53-75 μm exhibited a

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large volume fraction of amorphous phase (78.7 vol.%). The residual Al5Ni3Zr2 type phase could be
observed in remelted zone only if the powder size was larger than 106 μm. The volume fraction of
crystallization in the deposit increased with the increase in powder size.

2.8 Polymeric materials

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N
Polymers and reinforced plastics are used in a variety of load bearing applications, from
household goods to aerospace products. These materials are lightweight, strong and relatively
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inexpensive, but difficult to create intricate geometries. However, the development of AM has made it
easier to produce reinforced plastics in complex geometries.
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Pure polymers are no longer able to meet the increasing strength requirements, so additives are
incorporated into the polymer to enhance the strength of the polymer. For example, the use of poly
vinyl alcohol (PVA) and exploded nanodiamond (DND) dispersions as a new type of ink for 3D
printing was reported[133]. Poly vinyl alcohol (PVA) solution was added to detonation nanodiamond
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(DND) dispersions in order to obtain aqueous PVA-DND dispersions with a final concentration of
10%w/w of PVA and of 0.1, 0.5, 1 and 5 % w/w of DND with respect to PVA. The results showed that
the mean indentation modulus was improved by 22%, 44% and 200%, respectively. The melting
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temperature (Tm) and degree of the crystallinity (χc) changed with the DND concentration, and the
addiction of DND in PVA matrix produced an enhancement of the structural and thermal properties[133].
Besides, Torrado et al. evaluated the effect of additives on the anisotropy observed in the
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mechanical properties of tensile test specimens printed from acrylonitrile butadiene styrene (ABS)
based material systems[134]. In this study, a total of six ABS-based polymer matrix composites and four
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polymer blends were created and evaluated. The maximum ultimate tensile stress (UTS), 32.9 MPa,
corresponded to the ABS/TiO2 composite. Additionally, a ternary blend of ABS combined with styrene
ethylene butadiene styrene and ultra high molecular weight polyethylene lowered the mechanical
property anisotropy in terms of relative UTS to a difference of 22 as compared to 47 for samples
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printed from ABS [134].

Carbon fiber-reinforced polymer has been studied systematically[135-137]. Rapid fabrication of
carbon fiber reinforced PLA composites has been realized by using continuous carbon fiber as
reinforcement phase and plastics as matrix (Fig. 26). Temperature and pressure are critical parameters
to the forming process. Impregnation of plastics into the fiber bundle could be achieved when the
temperature of liquefier was in the range of 200-240 °C. With the optimized process parameters, 3D
printed composites with a fiber content of 27% could achieve the maximum flexural strength of 335
MPa and flexural modulus of 30GPa, and they should have further potential application as light
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structures in the fields of aviation and aerospace[135].

An important part of modern established implants and stem cell-based tissue is the generation of
feature that has a close naturalness. Based on Danilevicius’s report, the pre-polymer were
photosensitized by adding 1-3 wt% of thioxanthen-9-one or 2-Benzyl-dimethylamino-1-butanone-1
photoinitiators. Poly DiMethyl Siloxane thermo elastomer was used for producing transparent mask
for UV micromolding, in which it was mixed with matched curing agent using weight ratio 10:1. As
shown in Fig. 27, An example could be a chain-mail structure consisting of intertwined rings which
are not directly connected to each other. Such a scaffold could be used for skin tissue engineering,
providing great flexibility and mechanical strength[138].

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2.9 Ceramics
AM of ceramic components was widely investigated in the past decade due to the requirement of
high-performance ceramic components with complex structure, which is difficult and even impossible

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to produce by traditional methods. The main challenge in the laser fabrication of ceramic parts is the
intrinsic brittleness of ceramic during the process. So unlike laser metal deposition, suitable processing

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parameters for direct ceramic fabrication are extremely limited[139].
Concerning the AM of ceramics, a great deal of research work focused on Al2O3 or Al2O3-ZrO2
system ceramics. Yves-Christian et al.[140] investigated the processing parameters for forming Al2O3–

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ZrO2 by SLM. Dry mixed ceramic powder ratio of 58.5 wt% Al2O3 and 41.5 wt% ZrO2 was selected
as the raw material. The ZrO2 includes 6 wt% Y2O3 for partly stabilization of the ZrO2 at room
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temperature. But it was difficult to find the optimal processing parameters to eliminate cracks under
general conditions, and therefore the preheating of the ceramic to a temperature of at least 1600 °C
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was needed during the fabricating process. Shishkovsky et al.[141] synthesized ceramics by SLM with
another composition of ZrO2 and Al2O3 powders. The powder mixture was prepared from YSZ (ZrO2
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90 wt%, Y2O3 10 wt%) and Al2O3 in the ratio of 4:1. In order to minimize shrinkage and eliminate
cracking and delaminating, a narrow process parameter window was merely determined for layer-by-
layer laser melting.
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An approach by Wilkes et al.[142] produced net-shaped parts with flexural strengths of above 500
MPa. They used a eutectic mixture of pure alumina (Al2O3) and zirconia (ZrO2) with the ratio of 58.5
wt% Al2O3 and 41.5 wt% ZrO2 (Stabilized by 3 mol% of Y2O3), which were completely molten, while
crack formation was prevented by high temperature (1715 °C) CO2 laser preheating. The eutectic
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material ratio exhibits a rather lower melting temperature of 1860 °C, compared to the single phases
(Fig. 28). Applications of this technology comprise high-tech engineering ceramics, exploiting the
possibilities of fabricating complex geometries for the medical, automotive or aerospace sectors[143].
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Liu et al.[144] manufactured Al2O3/ZrO2 eutectic ceramic samples with suppressed cracks by
adopting assistant heating laser 3D printing. The powders of 58.5 wt% Al2O3 and 41.5 wt% ZrO2
(Stabilized by 8 wt% of Y2O3) compositions with the sizes of 150 μm and spherical shapes were used
as raw materials. The laser power was 200 W to 500 W with a scanning velocity of 50-300 μm/s. Once
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again, the preheating temperature of 1000 °C was needed to prevent the cracks. The laser beam was
directed to the substrate to create a molten pool into which the eutectic powders were injected through
the powder feed nozzle. The eutectic microstructure of the clad layer exhibits complex regular
characteristics. The average hardness and fracture toughness are 16.7 GPa and 4.5 MPa m 1/2,
respectively. Formation of the typical solidification defect, shrinkage porosity, can be significantly
suppressed by adopting a scanning rate smaller than 100 μm s-1 and a laser power larger than 400 W.
Wang et al.[145] fabricated self-lubrication wear-resistant ceramic matrix composite coatings on
substrates of Al2O3 by laser cladding CaF2–30%Al2O3 mixed powder blends. The laser clad
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CaF2/Al2O3 composite coatings have a unique microstructure consisting of plate-like framework of
Al2O3 primary phase and isolated spherical CaF2 solid lubrication particles uniformly dispersed in the
inter-framework regions (Fig. 29). Compared with laser clad monolithic Al2O3 coatings, the
CaF2/Al2O3 coating exhibits much superior wear resistance and noticeably lower friction coefficient
under dry sliding wear test conditions.

Recently an attempt was also made to fabricate Ti3SiC2-or-SiC-containing ceramic matrix

composites by in-situ reaction laser cladding technique using Ti and SiC powders[146]. The particle size
of spherical Ti powder and irregular SiC powder was approximately 50-100 μm and 30-60 μm,
respectively. When the SiC volume was 40%, the microstructure (Fig. 30 (a)) of the deposited layer
was mainly composed of Ti5Si4, TiSi2 and Ti3SiC2 phases as well as Ti5Si3Cx. The main reaction

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products in those gradient layers from 50%SiC to 80%SiC are almost identical, composed of TiC, TiSi2
and Ti3SiC2 and SiC (Fig. 30 (b) and (c)). From the thermodynamical viewpoint the following chemical

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reactions can occur spontaneously, with the formation of TiC and titanium silicides: Ti(l)+SiC(s) =
TiC(s)+Si(s) ; 5/3Ti(l)+Si(s) = 1/3Ti5Si3; 1/2Ti(l)+Si(s) =1/2TiSi2(s). Additionally, the reaction

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product of Ti3SiC2 can also be achieved by the following reaction: Ti+Si+2TiC =Ti3SiC2[147]. It should
be pointed out that the ternary Ti3SiC2 phase, due to its hexagonal crystal structure which is formed by

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Si atom layer linked to octahedral TiC，exhibits a Young’s modulus of 326 GPa and a low Vickers
hardness of 4-6 GPa[148, 149], and it shows fracture toughness of 6.0-7.9MPa·m1/2[150, 151]. The
mechanical properties of Ti3SiC2 are somewhat similar to those of ductile metals and therefore it is
thought as a damage-tolerant material or “ductile” ceramic. Furthermore, when the added SiC volume
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was increased from 50% to 80%, the volume content of the residual SiC within the clad layers was
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increased from 7.4% to 24.8%. The residual SiC, and all of these reaction products exhibit high melting
point, and they can be thought as refractory ceramic matrix composites.
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The in-situ reactions not only caused fine grains of the reaction products, but also improved the
fluidility of ceramic particles during the laser cladding process[146]. Additionally, fine reaction products
by the laser cladding were also observed in the Nb-SiC reaction system[152].
Lusquiños et al.[153] explored the potential of laser cladding to repair silicon infiltrated silicon
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carbide ceramics by applying a layer of SiC particles reinforced Si composite. The SiC+ Si mixture
caused the formation of sound coatings without substrate damage. The coatings showed homogeneous
and continuous interfaces without defects of cracks, porosities or inclusions. In the coatings, the
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production of silicon carbides was surrounded by a metallic silicon matrix (Fig. 31). According to the
nanoidentation tests, the Young Modulus (480 GPa) and the hardness (42 GPa) of SiC grains obtained
are slightly higher than the values reported in the handbook, and this is due to the rapid solidification
of the laser assisted process. But the mechanical properties of the laser cladded SiC+Si composite
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coating are not reported in this reference.

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2.10 Gradient materials

The concept of functionally graded materials (FGMs) was first proposed in 1987 to develop heat-
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resistant materials for the propulsion system and airframe of space planes[154]. Since then, lots of
research has been conducted to develop FGMs for various applications by using gradients in physical,
chemical, biochemical, and mechanical properties[155, 156]. Furthermore, much attention has been paid
to the fabrication of FGMs by AM technology due to its series of advantages, and the AMed FGM
systems include Ti-Co, different Ti alloys, Ti-TiAl, Ti-TiC, Ni-TiC, Ti-SiC, etc..
Attempts have been made to fabricate Co layers on the surface of Ti-6Al-4V substrate with a
compositionally graded interface by direct laser cladding[157]. Elemental powders of Ti (particle size
2-5 μm) and Co (particle size 5-8 μm) at different weight ratio were mixed in a ball mill to form
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precursors. The powder blend was prepared by dispersing the powder mixture in alcohol with organic
binder, and it was pre-placed on the substrate by spraying with a thickness of 250 μm. The precursors
powder composition of the 5 gradient layers varied from 90 wt% Ti +10 wt% Co (on Ti-6Al-4V
substrate) to 10 wt% Ti + 90 wt% Co prior to the final layer of 100% Co. The interfaces between the
successive layers are well adherent and continuous in nature (Fig. 32). Furthermore, the microstructure
is highly refined and they grow in columnar and dendritic fashion in the direction opposite to the
direction of heat flow. The XRD analysis results identified the formation of Ti2Co, CoTi and Co2Ti
intermetallics, and the volume fraction of individual phase varied with the depth from the Co-clad zone.
A significant improvement in microhardness (600-900 VHN) was achieved at the interfacial region,
and the graded interface possessed a superior biocompatibility to that of Ti-6Al-4V sample[157].

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Graded structural material of Ti-6Al-4V/Ti-6.5Al-3.5Mo-1.5Zr-0.3Si was designed and
fabricated by laser melting deposition method, and it exhibited good tensile properties and a good

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metallurgical bonding in the gradient zone[158]. But in this graded structure the compositions of the two
titanium alloys are close to each other. Further, Ti/TiAl structural gradient material was studied by

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LMD manufacturing process from the raw materials of spherical powders of Ti-47Al-2.5V-Cr and Ti-
6Al-2Zr-Mo-1V[159 ]. The purpose of this research was to provide new candidate aero-engine turbine

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blades and turbine disc materials. But in this material combination a great difference existed in the
compositions and mechanical properties. Fully lamellar (FL) microstructure consisted of -TiAl and
2–Ti3Al was formed on the Ti-47Al-2.5V-Cr side, while coarse basket weave microstructure on the
Ti-6Al-2Zr-Mo-1V side (Fig. 33). No cracking was found in the gradient zone after aging at 800oC for
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48h. The room temperature tensile strength of the Ti/TiAl FGM specimen is up to approximately
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1198.8MPa in the longitudinal direction, but the fracture surface exhibits brittle characteristics and the
ultimate tensile elongation on both directions is only 0.4%.
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To improve the wear resistance and hardness of the 20CrMnTi low carbon alloy steel, a gradient
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composite coating was manufactured by laser cladding Co50 alloy with addition of different percents
of Ni/WC powders (0 wt%, 3 wt%, 5 wt%, and 10 wt%) from bonding layer to wear resistance layer[160],
as shown in Fig. 34. The gradient composite coatings mainly consist of γ-Co, M23C6 and Co3B. The
interlayer and wear resistance layer also contain the WC and W2C phases. As shown in Fig. 34 (b, c),
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WC particles are embedded in the Co50 matrix. It is clear that the edges of the WC particles have been
molten partially during the laser cladding. The epitaxial growth of needle-like dendrites can realize
dispersion strengthening of the coating on the edge of the WC particles, and they also reveal a gradient
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transition from the Co50 matrix to the WC particles. It is believed that this structure is favorable to
inhibiting the formation of the cracks within the coatings. In fact, the hardness of gradient composites
coating is about 3 times as much as that of the 20CrMnTi substrate, and the wear resistance of the
gradient composite coating has been enhanced by 36.4 times as compared with that of 20CrMnTi[160].
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Liu et al. fabricated the defect-free functionally graded Ti6Al4V-TiC composites with 0 to 40 vol.%
TiC via laser direct deposition using the raw materials of spherical Ti64 powders and irregularly shaped
TiC particles [161]. Furthermore, in this work, the melting degree of TiC reinforcements could be
controlled by properly adjusting the deposition conditions and the particle size of the TiC
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reinforcements. That is, 90-150 μm TiC particulates were used for the least melting control of
embedded TiC, while ＜45 μm TiC particles were used for the most melting control of TiC. The results
showed that, it was difficult to avoid the formation of dendritic carbides when the premixed TiC is
larger than 15 vol.%. By proper controlling the input laser energy density, the Ti6Al4V-TiC composites
with 5-15% vol% TiC were free from dendritic carbides. The primary strengthening mechanism for
composites with the most control of TiC was the solid solution strengthening induced by carbon, while
that for the least melting control was dominated by the unmelted TiC particulates and the refined
microstructure resulting from the resolidified carbides[161].
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 Crack-free functionally graded TiC/Ti composite materials were fabricated by laser engineered
net shaping using TiC and Ti powder, with compositions changing from pure Ti to approximately 95
vol.% TiC[162]. In comparison to homogeneous composite deposits of high TiC contents, the FGM
fabrication effectively prevented the crack formation.
Direct laser fabrication (DLF) has been used to deposit Ni/TiC FGMs with compositions changing
from pure Ni to Ni plus TiC 90 vol.% on a low carbon steel substrate. Nickel, titanium and carbon
powders with the size from 74m to 178m in diameter were used as deposition reactants. TiC
particles were produced by in-situ reaction of titanium and graphite during the laser deposition, rather
than TiC particles being directly injected into the laser melted pool. Naturally the micro-hardness
exhibited a gradient, with the maximum value of 2350 HV0.3[163, 164].
Ti/SiC system gradient materials were designed and a FGM sample with the composition

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changing from TC4 substrate to 90%SiC, was successfully fabricated by in-situ reaction laser cladding
technique using Ti and SiC powder[146], with a planar size of 18 mm × 10 mm and the total thickness

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of 1.5 mm (Fig. 35). The particle size of the used powders was 50-100 μm for Ti and 30-60 μm for
SiC. It was noticeable that some residual SiC particles were remained in the gradient layers with SiC

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volume of no less than 50% (Fig. 35), and the volume content of the residual SiC within the clad layers
was increased from 7.4% to 24.8% when the added SiC volume was increased from 50% to 80%. The

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in-situ reactions also improved the fluidility of ceramic particles during the laser cladding process.
This work verified the feasibility of fabricating light-weight heat-resistant metal/ceramic gradient
materials by in-situ reaction laser cladding technique.

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In Chung’s report, selective laser sintering technique was investigated on blends of Nylon-11 with
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different volume fractions of silica nanoparticles (2%-10%). Finally, two component designs
exhibiting a one-dimensional polymer nanocomposite material gradient were fabricated (Fig. 36)[165].
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2.11 Biomaterials
SLM allows production complex 3D component directly from CAD data by selectively melting
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successive layers of metal powder on top of the previous one, using thermal energy supplied by a laser
beam [166, 167], and this technology could be very suitable for biomedical applications due to its ability
to fabricate complex shapes of custom-designed functional implants or prostheses made from
biocompatible metals[168, 169].
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The as-built Ti-6Al-7Nb (wt%) alloy by SLM has layered microstructure with thin plates of α’
martensite hardened by evenly distributed dispersive phase, likely β-AlNbTi2, which results in higher
tensile and compressive strengths, but lower ducility in comparison to those of an alloy manufactured
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by conventional methods[170]. Furthermore, the layered microstructure of the material gives it a

significant anisotropy of Young’s modulus, moderate anisotropy of mechanical properties, but strong
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anisotropy of sensitivity to the build porosity.

Zhang et al.[171] manufactured components using SLM from a novel biomedical beta Ti-24Nb-
4Zr-8Sn alloy[172, 173]. Near full density parts (>99%) have been obtained at a laser power of 200W
and with a scan speed range of 300-600 mm s-1. Compared with material prepared by conventional
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processing routes, SLM processing produces samples with similar mechanical properties but without
pronounced super elastic deformation due to the high oxygen of the starting powder. For the near fully
dense sample at 550 mms-1 the powders have completely melted/resolidified and there is no apparent
porosity in the microstructure (Fig. 37 (a)), and elongated dimple features are clearly visible on the
fracture surface (Fig. 37 (b)). Furthermore, an example of an acetabular hip cup complete with complex
outer scaffold has been manufactured (Fig. 37 (c)).

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 Porous titanium scaffolds for biomedical application could be fabricated with TiH2-Ti blended
powder system by SLM. It is believed that, porous Ti scaffolds could circumvent the issue of
mechanical mismatch between the bulk titanium implants (especially, stiffness and elastic modulus)
and natural bones, and the pores could offer a preferable environment for bone ingrowth and thus
achieve a tight fixation between the implant and surrounding bone[174-176]. A high porosity of ~70%
with pore size in a range from 200 μm to 500 μm was obtained at a laser power of 1000W and a scan
speed of 0.02 m/s with 40 wt% Ti [177]. Furthermore, the strong diffraction peaks of Ti and weak
diffraction peaks of TiO2 were detected in the XRD spectrum of the porous structure. The generation
of TiO2 result from oxidation of a minority of Ti[177]. However, the TiH2 peaks were absent, indicating
that TiH2 had been completely decomposed.

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Some attempts have also been made for the AM of Co-Cr-Mo biomaterials[178-181], for example,
Sun et al.[178] studied the phase and grain size inhomogeneity and their influence on creep behavior of

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Co-Cr-Mo alloy manufactured by EBM. The results showed that although constituent phase varied
along the build direction in the as-EBM-built rod (Fig. 38), from a single ε-hcp phase in the bottom to
a single γ-fcc phase in the top, the γ-fcc phase could be obtained in a wide range of build height, i.e.

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~40 mm from the top finishing plane. In the as-EBM-built rod, the ε-hcp phase in the bottom (i.e.

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early-built part) exhibited weak texture, while that in the latter-built part (far from bottom of the rod)
tended to exhibit random orientation. This can be attributed to the increase of post-build heating
temperature along the build height.

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Additionally, it was reported that microscale poly (ε-caprolactone) (PCL) and hydroxyapatite
nanoparticles (nHA) composite scaffolds were even fabricated with the average fiber diameter of 8.85
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μm by melt electrohydrodynamic printing to mimic collagen fibers and HA crystals in natural bone[182].
The microscale composite scaffolds exhibited good biocompatibility and facilitated cellular
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proliferation and alignment in vitro.
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2.12 High entropy alloys

High entropy alloys (HEAs) were first reported by Yeh et al.[183]. HEAs are defined as alloys that
have at least five principal elements in equimolar/equiatomic or near equimolar/equiatomic
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compositions and the concentration of each element is between 5% and 35%. Due to the unique alloy
design, the formation of intermetallics or ordered phases is suppressed and solid solution phases are
easily obtained[184-186]. HEAs have superior properties such as high strength, excellent high-
temperature strength, good corrosion resistance and good wear resistance. However, it is difficult to
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overcome the inherent complexity and high levels of control required to produce homogeneous bulk
alloys industrially using a conventional casting method. AM which facilitates a high level of local
process control, generates rapid solidification cooling rates, and enables the production of complex
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geometries, may be a suitable way of utilizing HEAs as engineering materials[187]. The study on AM
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of HEAs just began several years ago.

Fujieda et al.[187] first demonstrated the feasibility to process HEAs by SEBM. Cube-shaped
SEBM specimens (20 mm × 20 mm × 16 mm) were manufactured from gas-atomized AlCoCrFeNi
powders. The SEBM specimens exhibit superior ductility and lower yield strength than the as-cast
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specimens, as shown in Table 2.

Further, IPF maps and phase maps of the cast and the SEBM specimens indicated that the cast
specimens showed almost exclusively B2/BCC phases and nearly no FCC phase (Fig. 39). However
the SEBM specimens exhibited the FCC phase precipitation at grain boundaries of the B2/BCC grains.
The average grain sizes of the B2/BCC phases of the cast and SEBM specimens are approximately
300 µm and 10 µm, respectively. The grain refinement by SEBM is assumed to be related to the rapid
solidification cooling rates during the SEBM process. The fraction of the FCC phase in the bottom part
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(29.7%) is significantly higher than that of the top part (7.1%). The bottom part of the SEBM
specimens was maintained at 950 °C for about 13 h during fabrication which promoted the formation
of the precipitation of the FCC phase at grain boundaries. The hardness of the FCC phase is much
lower than that of the B2/BCC mixture. The finer grains and larger amount of FCC phases of the
SEBM specimens contribute to the better ductility and lower yield strength compared to the cast
specimens[188].

Ocelik et al. concentrate on the possibilities of AM of high-entropy clad layers by laser

processing[189]. The specimens were designed with the chemical compositions of AlxCoCrFeNi (x
values in molar ratios, x=0.4, 0.7, and 1.0). In Fig. 40, there are different amounts of fcc and bcc phase
present in arc-melted samples. Al-0.4 contains 99.9%, Al-0.7 97.0%, and Al-1.0 65.3% of fcc phase,

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respectively. The grain size for Al0.4CoCrFeNi is larger than 500 μm in diameter, while in
Al0.7CoCrFeNi small equiaxed grains of bcc appear surrounded by much bigger equiaxed fcc grains

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(Fig. 39(d)). The hardness is almost doubled going from Al-0.4 (148 HV) to Al-1.0 (278 HV), which
is due to the increase of the fraction of bcc phase in the alloy.

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Besides, Chao et al. produced AlxCoCrFeNi (x=0.3, 0.6 and 0.85) HEA claddings by coaxial
direct laser deposition (DLD) on a 253MA austenitic steel substrate using a mixture of blended
elemental powders[190]. The variation of Al content (i.e. x= 0.3, 0.6 and 0.85) resulted in different phase
constitutions in the HEA claddings, principally FCC phase for x= 0.3, mixed FCC + BCC phases for x
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=0.6 and BCC phase for x= 0.85. The cladding cross-section was composed of coarse columnar grains,
mostly enclosed by high angle grain boundaries (HAGBs), and the mean grain size was ~40.9 ± 3.7,
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38.2 ± 3.1 (FCC grain size) and 32.5 ± 1.5 μm for the Al0.3, Al0.6 and Al0.85 HEA claddings,
respectively[190]. Shon et al. also fabricated HEA coatings on aluminum substrate for the improvement
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in corrosion resistance by laser additive manufacturing[191], using Al, Fe, Co, Cr, and Ni elemental
powders.
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Furthermore, Joseph et al. deeply studied the HEA[192]. This alloy was fabricated by direct laser
fabrication and it exhibited significant tension/compression asymmetry in its work hardening rate and
ductility. The exceptionally high work hardening in compression was attributed to profuse mechanical
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twinning, which had been exacerbated by a strong texture in the as-cast material. The crystallographic
texture in the build direction shows a strong <001> alignment .
Fujieda et al.[193] fabricated Co1.5CrFeNi1.5Ti0.5Mo0.1 HEA specimens and studied the effect
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of solution treatment (ST) on the tensile properties and corrosion resistance (Fig. 41). The SEBM
specimens exhibited superior tensile properties to those of the corresponding casting specimen. The
solution-treated SEBM specimens exhibited both high strength and high pitting potential, which in
combination were superior to the conventional alloys used in severe corrosion environments. The
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strength of the SEBM specimens air-cooled (A.C.) by ST was higher than that of the SEBM specimens
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water-quenched (W.Q.) by ST. On the other hand, the elongation was lower than that of the SEBM
specimens W.Q. by ST. It was believed that the finer (10 nm in diameter) ordering phase (Ni3Ti) of
W.Q. specimen acted as a weaker obstacle to dislocation motion and stronger resistance to pitting
corrosion.
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3. Outlook

(1) Significance of the particles size and size distribution of powders

A wide range of materials and alloys are considered as “processable” for AM[194-196]. The term
“processability”, however, contains several parameters, which affect the additive build processes, and
the final product properties. Scanning speed, laser power, powder feed rate are the major parameters
used for laser cladded coating technique, but there are some other parameters which will affect the
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quality of clad, i.e. clad direction, preheating, laser spot dimension, injection angle nozzle distance and
percentage of clad overlap[197-199].
As a powder-bed AM process, the shape and size of particles are two crucial factors for the
printing process and performance of the resulting 3DP part[200]. According to Yang et al.[201], irregular
morphology and large particle size range may significantly reduce the powder’s flowability during the
3D printing process. Sometimes, finer powders are required to achieve finer microscale features, better
surface finishes, thinner layers and to promote printability, especially for powder bed printing.
However, fine powders may exhibit a significant aggregation which is principally determined by van
der Waals forces. In a recent review by Vorndran et al.[202], it was found that the smaller-sized particles
of ceramic powders, with dimensions smaller than 5 m, are prone to agglomerate, thus forming
defects and craters on the surface of the powder during layer preparation. However, large particles

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(>90 m) reduce the maximum layer packing density available in SLM. Furthermore, it has been
realized that the particle size distribution of the powders has an important effect on their flowability

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and thermal behavior as well as the mechanical properties of the manufactured product [197, 200].
Therefore the forming quality in AM can be determined by particle size, size distribution, surface

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roughness, and shape[203]. For example, in the reference[204] particle size gradation was optimized to
obtain both acceptable flowability of the powder material and high-strength 3D-printed glass-ceramic

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products, that is, the powder mixed by 60 wt%, 45-100 μm and 40 wt%, 0-25 μm particles presented
the satisfactory effect. The flowability decreased with an increasing proportion of fine particles.
Additionally, irregular shapes of single and agglomerated particles naturally induce poor flowability[205,
206]
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(2) Approaches for producing fine microstructures
Generally, the laser 3-D printing often produces fine microstructures in the laser cladded layer
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due to the high solidification rate. In the meantime it has been realized that in situ reaction during the
laser cladding process[207], addition of refractory particles and addition of rare earth elements into the
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raw materials are three important factors for favoring the formation of finer microstructures in the
resulted parts. In the work of Gu et al.[208], the mixed titanium and SiC powder particles were also used
as raw materials for SLM, and the as-milled powder also favored the in situ formation of TiC/Ti5Si3
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composites. Furthermore, the low energy from 75W to 120W in the SLM process caused the formation
of TiC particles with the size of 500 nm. Additionally, as described previously, when titanium and
graphite particles with the average size of 2-4 μm were mixed with Ni alloy powder, with the
processing parameters of 4-15 mms-1 beam scanning speed, 3 mm beam diameter and 2kW laser power,
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Ni alloy composite coating was produced on a 5CrMnMo steel substrate, in which TiC particles with
nanometer size was formed by in situ reaction as the reinforcement[98].
Another research result is noticeable concerning the fabrication of TiNi/Ti 2Ni matrix composite
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coatings on Ti6Al4V by laser cladding the mixtures of NiCrBSi and different contents of TaC (0-40
wt%)[209]. The coating without TaC addition was mainly composed of TiNi/Ti2Ni as the matrix and
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TiC/TiB2/TiB as the reinforcement. The added TaC particles with the uniform size of about 0.5 μm
was dissolved completely during laser cladding due to the very high processing temperature, and TaC
was in situ systhesized again during the subsequent solidification. TaC nucleated first in the molten
pool due to its very higher melting point of about 3880 °C than those of the three reinforcements. Then
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TiC, TiB2 and TiB preferentially nucleated and grew on the surfaces of TaC particles. In this way, the
microstructures of the coatings were refined[209].
Incorporation of an appropriate amount of rare earth (RE) in laser claddings can remarkably
prevent those defects of cracks, pores and inclusions within the coatings by traditional coating
techniques, and the presence of rare earth in laser claddings can notably enhance tribo-mechanical
properties[210-213]. Furthermore, RE atoms with the surface activity, tend to distribute at grain
boundaries and cause a dragging effect on the movement of the grain boundaries. Besides, the
unmelted RE oxides will act as nuclei and promote the nucleation rate[122, 214].
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 It should be pointed out that the application of electromagnetic field and vibration in different
material preparation process, such as casting of different metals or alloys, is effective in reforming the
fabricating process and refining the microstructure[215-217]. Besides, there have been some references
about applications of electromagnetic field and vibration in laser treatment of different materials[218-
223]
. In general, the external electromagnetic field, vibration or the two together have an agitation effect
on the materials of molten state so that the diffusion and other physical and chemical reactions will be
abundant. Moreover, the electromagnetic field can also act as a heat producer (i.e. induction heating),
which is demonstrated beneficial to the wettability between liquid titanium and calcia-stabilized
zirconia ceramic[224]. Vibration is valid in the modification of solidification structure, since when
vibration is applied, heat flow is disturbed and the alignment of grains is randomized. In addition,
growing dendrites may break up, and the pieces serve as seeds for new grains[225].

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Then, incorporating electromagnetic field, vibration or other assisted measures into laser cladding
process should have a high potential for the improvement in microstructures and properties.

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Therefore, some great and even amazing results are expectant if several factors previously
mentioned are together taken into account in the AM process, and this may directly develop some new

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materials with outstanding properties and performance.

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(3) Opportunities for creating new materials by additive manufacturing
The design of the coatings for metal substrate is important for different working environment,
including high-temperature oxidation [146], wear condition, marine environment[226, 227], medical
implant[228], etc. On one hand, undoubtedly, the investigation of new cladding materials is still highly
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needed; on the other hand, it is important to notice that by using gradient coatings, a compositionally
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graded interface can be obtained with a gradual change in microstructure instead of sudden change,
which is beneficial to the combination between the coatings and substrate and reduces the residual
stress to some extent due to the buffer effect of the multiple layers[122]. Additionally, up to date, only
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several examples of gradient materials as structural component by AM have appeared[158, 159, 162].
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Therefore, in future not only functional materials but also structural ones are important developing
direction in the field of FGM AM.
Cooper et al. studied the additive layer manufacture of Inconel 625 metal matrix composites and
demonstrated that TiC was the most promising reinforcement particulate among Al2O3, SiC and TiC
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ceramics. On this basis the possibility of producing “nano reinforced composite” using micro-sized
TiC particulates as the reinforcement material was proposed, that, is, under the suitable processing
parameters the ceramic constituents would be completely dissolved and during the cooling process
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they would re-precipitate at a smaller scale[229]. Furthermore, if particulate reinforcements on such a

sufficiently small scale can be achieved, on the one hand, the interface cracking will be substantially
restricted, and more important, the strengthening effect will be more significant, because Orowan
strengthening should be remarkably enhanced, and this may be beneficial to the material properties[230].
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In short, the study and development of ceramic-reinforced metal matrix composites should be an
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attractive research direction in future.

In fact, due to the requirement of high-performance ceramic components with complex structure,
and the fact that the main difficulty in the laser fabrication of ceramic parts is the intrinsic brittleness
of ceramic during the process, the study on the laser fabrication of ceramics especially the ultra-high-
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temperature ceramics or ceramic matrix composites is also highly needed in future.

Besides, as we know, high entropy alloys have superior properties such as high strength, excellent
high-temperature strength, good corrosion resistance and good wear resistance. Therfore it is also
necessary to deeply study such kind of materials in near future[231].
As pointed out by Murr, the concept of AM could be expanded for fabricating a variety of
functional material systems and components[232]. Such systems may require several more decades to
fully develop and optimize, but the outcomes could be truly revolutionary in a manufacturing contex.
AM opens completely new possibilities to design novel classes of materials (architectured materials,
24
metamaterials) with designed or novel properties and which cannot be realised with conventional
processes[233].

(4) Further study and wide applications in reconditioning of damaged components

AM technology can be applied to not only the production of the material blocks but also the
reconditioning of worn components[234]. The reconditioning of expensive or complicated components
is relatively time-consuming and if the reconditioning components are selected taking into account
their price, specific features of service environment and also specific features of reconditioning
technology, it is often possible to obtain significant gains in time and cost and also the quality of the
bond[235-237].
So far, it has been recognized that laser cladding should have a great potential for the repair of

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damaged components with a number of materials and thus, meet a great market including airplane and
submarine components, aircraft engines, equipment components in oil and gas industry, and even for

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medicine and health care[19, 238, 239]. For example, it is assumed that laser cladding is a highly promising
technology for the reconditioning of damaged blades of titanium turbines. Qin et al. have fabricated

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high Co-Ni secondary hardening steel coating on the low alloy hardened steel by laser deposition
method for the repair of locating pins in airplane[113]. Reconditioning of damaged high-strength steel

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landing gear actuators for aircraft and Ni-based superalloy cases for aero-engine has been conducted
by laser deposition method. The application of AM in reconditioning of damaged components will be
expanded in future.

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The epitaxial growth of single crystal microstructure (CMSX-4) by laser cladding is undoubtedly
an encouraging result[48], and once again, this should be of great significance for turbine hot section
repair[240]. Furthermore, as described previously, the laser cladding of SiC particles reinforced Si
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composite was successfully carried out on the silicon-infiltrated SiC ceramics without substrate
damage[153], inferring the great potential of repairing ceramic components in future. But, on the one
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hand, how to repair large-area defects is still a great challenge. On the other hand, to a certain ceramic
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or ceramic composite component to be repaired, it is not easy to design and fabricated suitable ceramic
constituents at the surface to ensure good metallurgical bonding with the original ceramic substrate[153,
241-247]
and better service performance during the second life period.
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(5) Challenges for deep understanding and applications of the AMed new materials
The main challenges for material AM in future include the design of raw materials in order to
obtain the desired properties for the AMed components, the control of the stresses and distortion during
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the forming process, the deep understanding of the forming process and synthesis principle, the
reproducibility of the microstructures and properties of the manufactured materials, the need for
decreasing the anisotropy extent[23, 24, 26, 170, 248], the prevention of the defects within the manufactured
components as well as the non-destructive testing for the components and the standard establishment
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for the preparation of the AMed materials or the relevant AMed components. In particular, in the case
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of non-destructive testing for the AMed components, in-situ sensors to provide non-destructive
evaluation during the AM process and thus allow for early detection of flaws/defects, need to be deeply
explored.
Considering the possibility of some abnormal phenomena in metallurgical reactions and the
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resulted micro-scale and even nano-scale phase constituents in the AMed new materials using raw
multi-component particles, the computer simulation and precise prediction of the particle size of the
reaction products and the detailed phase constituents, will become very difficult but extremely
necessary. Maybe it will cost long time to solve this complex problem. But, once this difficulty is
overcome gradually, it will in turn greatly promote the advance of the design science of AMed
materials and even new science in the materials field.
Finally, with the continuous development and increasing applications of AMed materials, the
database of comprehensive mechanical properties of the AMed materials should be built[106, 110, 113, 249],
25
and the failure analysis and prediction of lifecycles for the AMed components will become extremely
important. In conclusion, a series of scientific, technological and engineering problems remain to be
solved in future.

Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (Grant
Nos. 51775525, 51605456 and 51701198).

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Fig. 1 Additive manufacturing of 7075 Al alloy via selective laser. (a) Al7075 powder functionalized with

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nanoparticles. (b) equiaxed grain growth. (c) Functionalizing the powder feedstock with nanoparticles produces fine
equiaxed grain growth and eliminates hot cracking[13]

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Fig. 2 SEM images of microstructure. (a) cast AZ31 alloy. (b) Phase microstructure analysis of AZ31 alloy processed
with SLM[14]
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Fig. 3 IPF maps of the α-phase and calculated prior-β phase (X _ dir. ‖ ND) captured from the “cross-section” YZ
plane (a), (b), respectively, and section of a [-110]-oriented stereographic projection with relevant planes/directions
identified (c)[21]

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Fig. 4 Microstructure of electron beam deposited Ti-8Al-1Er (a) and Ti-6Al-4V (b), normal to build direction[27]

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Fig. 5 3D-optical micrograph composite section view for 17-4PH stainless steel fabricated by SLM. The build
direction is shown by arrow at lower right[3]
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Fig. 6 (a) 3D-optical microscopy image composite section view for alloy 625 component fabricated by EBM. The
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build direction is noted by the arrow (lower right). (b) TEM bright-field image showing Ni3Nb bct precipitate plates
coincident with NiCr fcc {111} planes noted. The vertical reference plane view corresponds to (a)[3, 37]

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Fig. 7 Optical micrograph of the lengthwise section of the first half of a CMSX-4 sample with the starting edge on
the left side of the image[48]

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Fig. 8 Microstructure of the as-deposited Ti-40Al-2Cr (a, b) and Ti-47Al-2.5V-1Cr (c, d) alloy[63, 64]
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Fig. 9 Microstructure of the the SLM-processed Ti-45Al-2Cr-5Nb alloy[66]

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Fig. 10 Microstructure of the vertical cross-section of at θ= 0° (a), 45° (b), and 90° (c), at high magnification[73]

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Fig. 11 BSE images of the as-deposited alloy (a), and the alloy annealed at 1500 °C for 24h in flowing argon (b).
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Processing parameters: laser power = 432W, powder feed rate = 18.1 g/min, scan speed = 400 mm/min[82]
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Fig. 12 Schematics of LMD with dual powder feeding method[83]

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 (a) (b)

Nb3Si
Ti-rich NbSS
2m 2m

5m 5m

(c) (d)

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NbSS
2m 2m

Ti-rich NbSS

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10m 10m

Fig. 13 BSE images of the as-deposited Nb-17Si-23Ti alloys fabricated by LMD with the laser power of 1 kW (a)

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and 2 kW (b), and BSE images of longitudinal sections (c) and transversal sections (d) for the as-deposited Nb-17Si-
23Ti alloys with DS microstructure. Inserts are enlarged images, and arrows indicate the build direction[83]
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Fig. 14 Schematic reaction process that takes place in Al12Si20Ti/SiC coating. (a) an SiC particle in a molten Al-Ti
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matrix. (b) reaction between SiC particle and molten Al. (c) reaction between molten Ti with Al4C3 and Si. (d) Al and
TiC ring formation[90]
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Fig. 15 EBSD maps of AA6061/TiC in situ composite containing TiC. (a) 0; (b) 2.5%; (c) 5%[91]

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Fig. 16 Evolution mechanism of SLM-processed B4C/Ti composite parts at variable laser power: (a) 125 W, 800
mm/s, (b) 200 W, 800 mm/s[93]
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Fig. 17 Bright-field TEM micrograph of micro-morphology of TiC in eutectic austenite (a) and HREM image of TiC-
γ-Ni interface (b)[98]
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Fig. 18 Gradient distribution of TiC particles and Microhardness variation with the coating depth[98]
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Fig. 19 Microstructure of Inconel 690/TiC samples. (a) Equiaxed grains found in 8.7 vol.% TiC. (b) Groups of
columnar dendrites in 15.3 vol.% TiC layer. (c) Dendritic TiC phase (43 vol.% TiC)[99]

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Fig. 20 Transmission electron microscopic images of TiC particles in primary dendrites of γ-Ni (a) and dislocation
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Fig. 21 Microstructure of as-fabricated WCp/NiBSi MMC (a) and higher magnification (b)[106]
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Fig. 22 Diagram illustration for the action mechanism of Ti on the microstructure of VN alloy/Co-based composite

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coatings[112]

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Fig.23 Laser cladding high Co-Ni steel coating on 18Cr2Ni4WA steel: (a) cross-section morphology of coating and
substrate; (b) and (c) SEM micrograph of coating and substrate, 1- martensite, 2- retained austenite, 3- M3C cementite,
4- M2C carbides; (d) locating pins in airplane repaired using laser cladding technology[113]

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Fig. 24. Typical SEM view of (a) SS/HA and (b) 316L SS microstructure[114]

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Fig. 25 SEM images of the microstructure of (a) 316L alloy and composites reinforced with (b) 3 wt% PCS. (c) 7
wt% PCS[115]
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Fig. 26 Scheme of the printing process for carbon fiber reinforced PLA composites[135, 136]

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Fig. 27 Chain-mail structure consisting of joint rings hanging on supporting walls, showing possibility to fabricate
flexible scaffolds[138]

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Fig. 28 (a) FESEM image of the dry mixed alumina/zirconia powder. (b) Phase diagram of the alumina and zirconia
system[142]
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Fig. 29 SEM micrographs showing the dispersion of CaF2 spheres in the inter-plate regions of the laser clad Al2O3–
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30%CaF2 ceramic matrix composite coating[145]

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Fig. 30 BEIs of different gradient layers. (a) 40% SiC; (b) 60% SiC; (c) 70% SiC[146]

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Fig. 31 Microstructure of SiC+ Si laser clad coating. (a) Cross-section of a strip obtained by using SiC+ Si powder
mixture as raw material. (b) Detail of the SiC/Si composite coating (the circle is a SiC grain)[153]

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Fig. 32 Optical micrograph of the compositionally Ti-Co system graded interface[157]

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Fig. 33 Macro-surface of the LMD Ti/TiAl SGM component (a). Microstructure of the as-deposited Ti-43Al-1.8V-
0.8Cr (b). TEM BF of Ti-43Al-1.8V-0.8Cr (c). Ti-30Al-1.4V-0.5Cr (d). Ti-17Al-V-1.8Zr-Mo (e), and Ti-6.5Al-V-
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2Zr-Mo (f)[159]
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Fig. 34 Gradient composite coating of cross section (a). Morphology of WC particles in wear-resisting layer (b), and
interlayer II (c) [160]
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Fig. 35 Cross-section gradient microstructure of Ti/SiC bulk FGM sample[146]

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Fig. 36 Schematic description, and fabricated part of rotator cuff scaffold[165]

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Fig. 37 (a) Microstructures of the parts manufactured at laser scan speeds of 550 mm s-1. (b) The fracture surface of
the samples. (c) An example of precise acetabular cup produced by SLM[171]
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Fig. 38 EBSD phase maps (a, c, e) and IPF maps (b, d, f) on longitudinal cross-section of different height of as-EBM-
built rod. (a, b) top part. (c, d) center part and (e, f) bottom part[178]
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Fig. 39 IPF maps and phase maps of the cast and the SEBM specimens of the equiatomic AlCoCrFeNi HEA obtained
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Fig. 40 EBSD phase map of (a) Al-0.4. (b) Al-0.7, and (c) Al-1.0 arc-melted samples showing fcc (red) and bcc
(green) phases. (d) Grain size distributions of the fcc and bcc phases of the arc-melted samples[189]

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Fig. 41 Tensile strength and pitting potential of SEBM specimens under different conditions. (a) Tensile
engineering stress-engineering strain curves; (b) potentiodynamic polarization curves[193].
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 Table 1 Tensile YS and UTS in the (L-T) plane of the Inconel 718 EBF3 block in the AD and the HT conditions[41]
AD (measured) HT (measured)
Cast (literature) Wrought (literature)
Orientation Property
(MPa) (MPa) (MPa) (MPa)
YS 655 986 488 1182
L
UTS 978 1114 786 1369
YS 699 998 - 1208
T
UTS 936 1162 - 1374
YS 703 995 - -
45 deg
UTS 993 1171 - -

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 Table 2 Room temperature compressive properties of the equiatomic AlCoCrFeNi HEA produced by SEBM
and casting[187]
εf (%) σ0.2 (MPa) σmax (MPa)
Casting 5.6±1.9 1308.3±77.3 1425.0±127.5
SSEBM (0°) 26.4±6.7 1015.0±52.5 1668.3±71.5
SSEBM (90°) 14.5±5.3 944.0±55.4 1447.0±135.8

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