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Journal of

Manufacturing and
Materials Processing

Review
Laser-Based Additive Manufacturing of Magnesium Alloys
for Bone Tissue Engineering Applications: From Chemistry
to Clinic
Mohammad Ghasemian Fard 1 , Fariborz Sharifianjazi 2 , Sanam Sadat Kazemi 3 , Hosein Rostamani 4,5
and Masoud Soroush Bathaei 5,6, *

1 Department of Mechanical Engineering, Babol Noshirvani University of Technology, Babol, Iran


2 School of Science and Technology, The University of Georgia, Tbilisi, Georgia
3 Biomedical Engineering (BME) Department, Nikan Hospital, Tehran, Iran
4 Department of Biomedical Engineering-Biomaterials, Faculty of Engineering, Islamic Azad University,
Mashhad, Iran
5 Department of Materials Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran
6 Department of Mining and Materials Engineering, McGill University, Montréal, QC, Canada
* Correspondence: ms.bathaei@gmail.com or masoud.bathaei@mail.mcgill.ca

Abstract: Metallic biomedical implants are made from materials such as stainless steel, titanium,
magnesium, and cobalt-based alloys. As a degradable biometal, magnesium (Mg) and its alloys are
becoming more popular for applications in bone tissue engineering. Mg-based alloys have been found
to be biocompatible, bioabsorbable, and bioactive, allowing them to be used as orthopedic implants
with a low Young’s modulus. Computer-aided design can be used to design scaffolds with intricate
porous structures based on patient-specific anatomical data. These models can be materialized rapidly
Citation: Fard, M.G.; Sharifianjazi, F.;
and with reasonably acceptable dimensional accuracy by additive manufacturing (AM) techniques.
Kazemi, S.S.; Rostamani, H.; Bathaei, It is known that lasers are the most widely investigated energy source for AM’ed Mg, as they offer
M.S. Laser-Based Additive some distinct advantages over other forms of energy. Recent studies have focused on developing
Manufacturing of Magnesium Alloys biodegradable Mg scaffolds by using laser-based AM techniques. In this paper, we aim to review the
for Bone Tissue Engineering recent progress of laser-based AM for Mg alloys and survey challenges in the research and future
Applications: From Chemistry to development of AM’ed Mg scaffolds for clinical applications.
Clinic. J. Manuf. Mater. Process. 2022,
6, 158. https://doi.org/10.3390/ Keywords: magnesium; laser; additive manufacturing; implant; tissue scaffold; bioactivity
jmmp6060158

Academic Editors: Siavash


H. Khajavi and Mika Salmi
1. Introduction
Received: 1 November 2022
Accepted: 6 December 2022
It has been proven that magnesium (Mg) alloys are a viable degradable biomaterial
Published: 10 December 2022
that can be used in orthopedic surgery, respirology, cardiology, and urology [1–3]. Mg
has the advantage of minimizing or avoiding long-term complications due to the fact
Publisher’s Note: MDPI stays neutral
that it completely absorbs away over time in the human body [4]. About 65% of the Mg
with regard to jurisdictional claims in
element in the body is found in bones, making it a crucial nutrient for the human body [5].
published maps and institutional affil-
Additionally, Mg’s modulus is more similar to bone compared to the conventional metallic
iations.
implants such as stainless steel, CoCrMo alloy, and titanium alloys, which minimizes
stress shielding effects in orthopedics [6]. Table 1 compares the mechanical properties of
Mg implants with those of typical metallic and polymeric biomaterials [7,8]. Generally,
Copyright: © 2022 by the authors.
Mg-based alloys are produced by pressure die casting, and wrought Mg-based materials
Licensee MDPI, Basel, Switzerland. have limited engineering applications, particularly because they cannot be formed and
This article is an open access article processed at room temperature [9]. Moreover, conventional production methods of Mg
distributed under the terms and alloys for bone tissue engineering applications are challenging, since they cannot generate
conditions of the Creative Commons well-connected pore structures and customized geometric forms, which are the required
Attribution (CC BY) license (https:// parameters of novel implants and the personalized medicine field [9,10]. Nowadays, the
creativecommons.org/licenses/by/ biomedical industry continues to face many challenges due to the time-consuming and
4.0/). energy-intensive nature of conventional production processes such as casting, forging, and

J. Manuf. Mater. Process. 2022, 6, 158. https://doi.org/10.3390/jmmp6060158 https://www.mdpi.com/journal/jmmp


J. Manuf. Mater. Process. 2022, 6, 158 2 of 18

powder metallurgy, especially in the manufacturing of complicated Mg-based implants of


high quality [11,12].

Table 1. Comparison of Mg implant properties with other biomaterials [7–10].

Young’s Modulus Compression Strength Tensile Strength


Tissue/Material Yield Strength (MPa)
(GPa) (MPa) (MPa)
Cortical bone 7–30 - 100–230 164–240
Cancellous bone 0.01–3.0 - 2–12 -
Ti-6Al-4V (casted) 114 760–880 - 895–930
Ti-6Al-4V (wrought) 114 827–1103 896–1172 860–965
Stainless steel 316 L 193 170–310 480–620 540–1000
CoCrMo Alloy 240 500–1500 - 900–1540
Mg (99.9%, casted) 41 21 40 87
Mg (99.9%, wrought) 41 100 100–140 180

The additive manufacturing (AM) of Mg implants is of increasing interest within the


biomedical engineering community due to the capabilities of this form of manufacturing,
which are not achievable with conventional manufacturing processes, as well as the pos-
sibility to design novel biomaterials [13,14]. In addition to the freedom to design (and to
optimize topology), additive manufacturing reduces energy consumption and waste by
reducing waste materials [15–18]. It also overcomes the limitations associated with conven-
tional fabricating methods (formative or subtractive) [14]. Through topology optimization
and the use of free space as a design variable, the lightest engineering metal can be made
even lighter [19]. It is also recommended that components that have a large surface area be
used as biomaterials in order to enhance the development of cells, proliferation, and bone
regeneration; or as electrodes for Mg in order to provide significant reaction areas [20]. As
shown by Equation (3), Mg hydroxide and hydrogen gas are the primary products of the
degradation of Mg in water. The following reactions demonstrate the anodic (for Mg) and
cathodic (for H2 O) nature of this reaction [21]:

Mg → Mg2+ + 2e− Anodic reaction (1)

2H2 O + 2e− → H2 + 2(OH− ) Cathodic reaction (2)


Mg + 2H2 O → Mg(OH)2 + H2 Net reaction (3)
There are a number of challenging problems associated with Mg implants, including
their high corrosion rate and low bioactivity. These issues should be addressed before they
are used in clinical applications. It is highly desirable to modify the surface of implants
containing Mg alloys, so that the corrosion rate is reduced and the bioactivity is enhanced,
thus improving their biocompatibility [22].
Using AM technologies, it should be possible to manufacture patient-specific and
topologically optimized biodegradable Mg-based implants for bone tissue engineering
applications [23]. Up to now, the various AM techniques involved in the fabrication of
Mg implants include powder bed fusion, wire arc additive manufacturing, paste extrusion
deposition, friction stir additive manufacturing, and jetting technologies. These techniques
are shown in Figure 1 schematically [23–27].
Despite the mentioned advantages, there has been limited research in the field of
AM’ed Mg implants [25]. The main challenge is that the Mg powder may be subject to
oxidation, evaporation, and handling issues as a result of its reactive nature (in atmospheric
conditions) [25,26].
Figure 2 shows porous WE43 Mg alloy cubes in three different sizes developed by the
authors using the LPBF technique. This work reviews the recent progress on the LPBF of
Mg alloys for the construction of bone scaffolds and compares their mechanical corrosion
and bio-compatibility. The risk controls employed during laser-based AM techniques
have demonstrated excellent success in facilitating the routine and reproducible use of
Figure 2 shows porous WE43 Mg alloy cubes in three different sizes developed by
the authors using the LPBF technique. This work reviews the recent progress on the LPBF
of Mg alloys for the construction of bone scaffolds and compares their mechanical corro‐
J. Manuf. Mater. Process. 2022, 6, 158 sion and bio‐compatibility. The risk controls employed during laser‐based AM tech‐ 3 of 18
niques have demonstrated excellent success in facilitating the routine and reproducible
use of Mg powder additive methods for the manufacture of Mg implants of a wide range
of compositions [28,29]. As one of the most powerful and efficient processes in the mod‐
Mg powder additive methods for the manufacture of Mg implants of a wide range of
ern AM field, laser powder‐bed fusion (LPBF) has recently been recognized as an efficient
compositions [28,29]. As one of the most powerful and efficient processes in the modern
and powerful way of fabricating complex 3D objects with a high level of accuracy and
AM field, laser powder-bed fusion (LPBF) has recently been recognized as an efficient
reproducibility,
and powerful way as well as superior
of fabricating metallurgical
complex and with
3D objects mechanical
a high properties [29]. Cur‐
level of accuracy and
rently, the most commonly used Mg compositions in the LPBF method are
reproducibility, as well as superior metallurgical and mechanical properties [29].pure Mg,
Currently,
Mg‐Al,
the mostMg‐RE (rare used
commonly earth),
Mgand Mg‐Zn alloys,
compositions in theprimarily for their
LPBF method comparatively
are pure Mg, Mg-Al,higher
Mg-RE
market demand, better printability, and properties for use in structural and biomedical
(rare earth), and Mg-Zn alloys, primarily for their comparatively higher market demand,
applications.
better printability, and properties for use in structural and biomedical applications.

J. Manuf. Mater. Process. 2022, 6, 158 4 of 19


Figure
Figure1. Schematic of (a)
1. Schematic (a) powder
powderbed bedfusion
fusion[23], (b)(b)
[23], wire arc arc
wire additive manufacturing
additive manufacturing[24], [24],
(c) paste
(c)
paste extrusion
extrusion deposition
deposition [25],
[25], (d) (d) friction
friction stir additive
stir additive manufacturing
manufacturing [26],
[26], and (e) and technologies
jetting (e) jetting tech‐
[27].
nologies [27].

Figure
Figure 2. 2.
TheThe WE43Mg
WE43 Mgalloy
alloy cubes
cubes in
inthree
threedifferent
differentsizes developed
sizes by Dr.
developed by M.
Dr.S.M.
Bathaei’s groupgroup
S. Bathaei’s
using the LPBF technique for bone tissue engineering applications.
using the LPBF technique for bone tissue engineering applications.

2. AM of Mg for Bone Tissue Engineering


Adult humans are made up of 206 to 213 bones that make up the skeleton as a dy‐
namic support structure [30]. The human body is reinforced structurally through the
bone, which allows the body to move, facilitates the process of respiration, allows for
adequate breathing, and protects the vital organs within the body [31,32]. Bones also
Figure 2. The WE43 Mg alloy cubes in three different sizes developed by Dr. M. S. Bathaei’s group
using the LPBF technique for bone tissue engineering applications.
J. Manuf. Mater. Process. 2022, 6, 158 4 of 18

2. AM of Mg for Bone Tissue Engineering


Adult humans are made up of 206 to 213 bones that make up the skeleton as a dy‐
2. AM of Mg for Bone Tissue Engineering
namic support structure [30]. The human body is reinforced structurally through the
Adult humans are made up of 206 to 213 bones that make up the skeleton as a dynamic
bone, which allows the body to move, facilitates the process of respiration, allows for
support structure [30]. The human body is reinforced structurally through the bone, which
adequate breathing,
allows the and protects
body to move,the vital organs
facilitates within
the process the bodyallows
of respiration, [31,32]. Bones also
for adequate breathing,
store magnesium, calcium, and phosphorus and produce white and red blood
and protects the vital organs within the body [31,32]. Bones also store magnesium, cells as
calcium,
well as platelets
and [33]. As people
phosphorus age, their
and produce bones
white undergo
and red constant
blood cells as wellreshaping
as plateletsand
[33].bio‐
As people
logical remodeling [34].bones
age, their The undergo
structure is pulled
constant by involuntary
reshaping muscles
and biological that contract
remodeling [34]. Theand
structure
is pulled by involuntary muscles that contract and relax in response
relax in response to the movement of the involuntary muscles [35]. The structural bones to the movement of
can be dividedthe involuntary
into three main muscles
parts [35]. The structural
including bones
the macro‐, can beand
micro‐, divided into three
nano‐scale main parts
levels,
including the macro-, micro-, and nano-scale levels, as shown in Figure 3. Bones can
as shown in Figure 3. Bones can be classified as trabecular or cortical, based on their
be classified as trabecular or cortical, based on their structure and density [30]. Based
structure and on
density [30]. Based on location and age, trabecular and cortical bones have
location and age, trabecular and cortical bones have a porosity of 50–90% and 3–5%,
a porosity of 50–90% and 3–5%, respectively [36].
respectively [36].

Figure 3. Hierarchical macro‐


Figure 3. to nanostructures
Hierarchical of natural human
macro- to nanostructures bone
of natural [37].bone [37].
human

Bone regeneration
Bone regeneration at the site ofatdamage
the site of damage
should beshould be promoted
promoted by successful
by successful implantsimplants
that restore the physical function of bone [30]. In general, they should
that restore the physical function of bone [30]. In general, they should possess character‐ possess characteristics
that are to
istics that are similar similar
thosetoofthose
nativeofbone.
nativeThese
bone. properties
These properties
include: include: (i) the mechanical
(i) the mechanical
properties should be matched to support loading and reduce/minimize the level of stress-
properties should be matched to support loading and reduce/minimize the level of
shielding effect; (ii) biocompatibility, suited for cell adhesion/spreading, and does not
stress‐shielding effect; (ii) biocompatibility, suited for cell adhesion/spreading, and does
release toxic ions to extracellular medium; (iii) an extremely porous structure that facilitates
bone ingrowth and enables robust biological fixation of the implant to the bone [33]. The
natural degradability, biocompatibility, and osteoporotic nature of Mg and its alloys has
led to their rapid development as revolutionary metallic biomaterials in the field of bone
tissue engineering [3–5]. Mg and its alloys have a relatively similar mechanical strength to
that of human bones, as seen in Table 1. Mg and it alloys have high biocompatibility and
similar mechanical properties with natural bone properties that meet two requirements of
implant design intrinsically [7–10]. Moreover, the permeability of the porous metal used
in bone implants is also an important characteristic as a third requirement, since blood
must travel through them in order to transport cells [36]. By utilizing the AM technique
as a new technology, porous Mg-based scaffolds that are tailored to the anatomical needs
of a patient can be manufactured layer-wise using well-developed architectures derived
from computer-aided design (CAD) models in accordance with the patient’s anatomical
requirements [38]. Unique abilities that could not be reached in any way in traditional
Mg production methods can be used, such as die cast [39]. It is also possible in AM
to adjust the modulus of the implant or porous mesh by varying the porosity and strut
size [40]. Among the types of patients who would benefit from AM strategies are those
J. Manuf. Mater. Process. 2022, 6, 158 5 of 18

who require a resection of bone tumors, treatment following fractures, and other types of
bone loss, whether regular or irregular. It has been established that LPBF, formerly known
as selective laser melting (SLM), is the most widely explored method for the AM of Mg and
its alloys [13,14,25], with very few attempts to use direct laser deposition (DLD). Therefore,
DLD was excluded from the main body of the present review.

3. Laser Powder-Bed Fusion (LPBF)


Using CAD design, laser processing, and computer numerical control, PBF creates
metallic components with enhanced properties [41–43]. Figure 4 illustrates the typical
LPBF manufacturing process: (i) the computer obtains the model slice data from the 3D
model by converting it to an STL file; (ii) the forming cylinder is covered with a layer of
Mg powder that is evenly distributed; (iii) as a result of the computer’s control of the laser
beam based on the model slice data, the powder layer is imaged selectively with the laser
beam, which receives heat and starts to melt/solidify, resulting in a single layer of material;
(iv) a new layer of powder is paved by the roller after the molding cylinder is lowered by a
layer. After the first layer has been constructed, the second layer will be applied on top of
it, until the final part has been formed [44,45]. In LPBF, Mg powders varying from 15 µm
to 160 µm are used, with the majority of powder being on the lower end of the mentioned
range [46,47]. Moreover, the chemical composition, mechanical properties, and geometry
J. Manuf. Mater. Process. 2022, 6, 158 of manufactured Mg implants can vary due to LPBF’s wide range of parameters. Laser 6 of 19
power, scanning speed, and layer thickness are the most important parameters in the LPBF
process [48–50].

Figure 4. Mg‐based bone implant manufacture using a typical LPBF technique that uses laser‐based
Figure 4. Mg-based bone implant manufacture using a typical LPBF technique that uses laser-based
AM principle [44].
AM principle [44].

Most
Mostofof the experiments
the experiments onon
thethe
PBFPBFof Mgof alloys
Mg alloys haveconducted
have been been conducted using
using lasers lasers
[50–52].
[50–52]. Theconcentrate
The lasers lasers concentrate high concentrations
high concentrations of heat overofa limited
heat over
areaaoflimited area bed,
the powder of the
powder
meltingbed,
the melting the powder
powder over a limitedover a limited
timeframe timeframe
[53]. [53].solidification
Then, rapid Then, rapid occurs
solidification
as a
result of this short-timed heat flux. It is possible to carry heavier loads due
occurs as a result of this short‐timed heat flux. It is possible to carry heavier loads due to to this rapid
solidification,
this which refines
rapid solidification, the grain
which compared
refines to conventional
the grain compared production methods
to conventional [54,55].
production
The vaporization
methods of some
[54,55]. The elements ofofMg-based
vaporization powderof
some elements occurs when the
Mg‐based powder
powder is heated
occurs when
to a high temperature [56]. In the melt pool, powder vaporization builds
the powder is heated to a high temperature [56]. In the melt pool, powder vaporization up vapor pressure
locallyup
builds [57]. In apressure
vapor melt pool, molten
locally material
[57]. is spattered
In a melt outward
pool, molten by pressure,
material forming
is spattered out‐
low-density structures that may reduce the stress-shielding effect [57,58]. In addition to
ward by pressure, forming low‐density structures that may reduce the stress‐shielding
variations in the chemical composition, this also leads to variations in particle size [59]. For
effect [57,58]. In addition to variations in the chemical composition, this also leads to
printed components to perform well under corrosion conditions, alloying elements must
variations in particle size [59]. For printed components to perform well under corrosion
have good solubility during AM and create corrosion resistance intermetallic phases [59].
conditions, alloying
PBF is influenced in elements must
a significant wayhave
by thegood
power solubility during
of the laser and AM and create
scanning speed incorrosion
order
resistance intermetallic phases [59]. PBF is influenced in a significant way by the power of
the laser and scanning speed in order to determine the melt pool, vaporization, and the
deposition results [60]. There are many factors that affect the quality of depositions, in‐
cluding laser power and scanning speed [61]. However, the effects of each factor on the
J. Manuf. Mater. Process. 2022, 6, 158 6 of 18

to determine the melt pool, vaporization, and the deposition results [60]. There are many
factors that affect the quality of depositions, including laser power and scanning speed [61].
However, the effects of each factor on the other are difficult to describe on their own [60].
J. Manuf. Mater. Process. 2022, 6, 158 In combination, they are essential for determining how much energy is transferred 7 to
of Mg
19
powder via the laser [60]. It has been reported that spherical Mg powder particles with a
purity of 99.9% and a mean size of 24 µm were used with 155.56 J/mm3 energy density
to achieveenergy
decreasing 97.5% density
density[62].
[69].Moreover, researchers
A porous scaffold found that
composed in response
of diamond unittocells
an increase
could
or decrease in energy density, the material’s relative density and
also be constructed with a WE43 alloy. Unit cells with a low energy density of 100 J/mm3 mechanical strength
deteriorated
were [63]. In strut
able to achieve the case of of
sizes Mg400alloy
μmpowders, it was found
[60]. In another study,that
theMg and
laser zinc elements
power was 15
within ZK60 powder were heavily vaporized when subjected to 1250 J/mm 3 of energy
W, and the scanning speed was 20 mm/s, which allowed the Mg‐Al alloy to melt com‐
density
pletely [56]. The
(Figure 5b) melt
[70]. pool
This stabilized
is equivalentandto the vapor
187.5 pressure
J/mm wasenergy.
3 of laser reduced Theafter the laser
Mg–9%Al
density
alloy maywas
havereduced
a rangeto of250 J/mm3 [64].
acceptable energy A poor relative
density regions density
basedof on82.25%
a studywas thesame
of the result
of the incomplete fusion of powder particles. With an energy density of 416.67 J/mm 3,
material at an energy density of 155.6 J/mm3. In addition to powder quality and layer
a maximum relative density of 94.05% could be achieved, as seen in Figure 5a [65]. In
thickness, several parameters affect this range of energy density [71].
another case, with an energy density of 238 J/mm3 , WE43 was printed at a relative density
LPBF of metallic materials must also take porosity into account, which is a common
of 99.4%. WE43 is an alloy of Mg that contains the primary alloying elements yttrium
problem [72]. An analysis of how processing parameters affect the porosity of Mg spe‐
and neodymium [66]. There is evidence suggesting that optimal printing parameters are
cifically has been presented in the following Table 2. Changing any one of the listed pa‐
generally found when the energy density of the melt pool is low, resulting in a high part
rameters will result in a different porosity, so it is difficult to extract a trend based on the
density and low vaporization of the alloying elements inside the melt pool [67]. In addition,
effect of any individual processing parameter [72]. In order to achieve high density and
porosity increases with increasing energy density. The porosity increased from 0.4% to 17%
low porosity, alloy composition dictates the ‘printability’ of the alloy during the opti‐
when the laser power was decreased from 195 W to 135W, and the scanning speed increased
mum processing windows [73]. It is inevitable that porous materials will tear and crack;
from 800 mm/s to 1200 mm/s [68]. In split Hopkinson pressure bar tests, the dynamic
however, it is necessary to avoid hot tearing or cracking while porous materials are pre‐
strength decreased with decreasing energy density [69]. A porous scaffold composed of
sent [74]. Aunit
diamond LPBF component’s
cells could also quality is deteriorated
be constructed with a most
WE43severely
alloy. Unit by hot tearing
cells with aand low
cracking. When the temperature3 gradient remains high, even when
energy density of 100 J/mm were able to achieve strut sizes of 400 µm [60]. In another the constitutional
super‐cooling is lower,
study, the laser power wascolumnar
15 W, grains
and theare more susceptible
scanning speed was to 20 hot
mm/s, tearing
which[75]. Cavities
allowed the
and
Mg-Al alloy to melt completely (Figure 5b) [70]. This is equivalent to 187.5 J/mmtemper‐
hot‐tearing cracks can occur across the full length of columnar grains when 3 of laser
ature andThe
energy. liquid volumealloy
Mg–9%Al fraction
may decrease.
have a rangeSinceof there has been
acceptable limited
energy research
density regions onbased
the
impacts of alloying
on a study of the sameandmaterial
processing
at anparameters
energy densityon hot tearing
of 155.6 J/mmduring LPBF in to
3 . In addition Mg, it is
powder
unclear what effect they have [76].
quality and layer thickness, several parameters affect this range of energy density [71].

Figure 5. (a) Influence of laser scanning speed on relative density of ZK60 [65] and (b) grain size
Figure 5. (a) Influence of laser scanning speed on relative density of ZK60 [65] and (b) grain size
variation of Mg–9%Al powder as a function of laser power and scan speed [70].
variation of Mg–9%Al powder as a function of laser power and scan speed [70].
4. TheLPBF
Advantages of LPBF
of metallic over must
materials Otheralso
AMtake
Processes
porosity into account, which is a common
It is worth
problem [72]. Annoting thatofLPBF
analysis has the added
how processing advantage
parameters affectofthe
being able of
porosity toMgproduce
specifi-
highly porous
cally has been and fine structures
presented as well
in the following as accommodate
Table 2. Changing any many
one offorms, not only
the listed pris‐
parameters
matic ones [72].
will result Thus, it isporosity,
in a different widely soused
it istodifficult
manufacture metallic
to extract scaffolds
a trend based onandtheimplants. In
effect of any
addition,
individualosseointegration studies have
processing parameter [72]. In shown
orderthat implants
to achieve candensity
high be designed
and low with pref‐
porosity,
erentially porous layers
alloy composition to enhance
dictates adhesion of
the ‘printability’ between theduring
the alloy bone tissues and implant
the optimum ma‐
processing
terial [75]. A human bone consists of three distinct anatomical cavities: haversian canals,
osteocytic lacunae, and canaliculi [66–69]. A bone’s mechanical characteristics and pro‐
cesses are remodeled in these three cavities. Living tissues can flourish in porous struc‐
tures, as nutrients can be transported [49–54]. It is possible to design components with a
modulus similar to the bone’s, which reduces stress‐shielding problems in metallic or‐
J. Manuf. Mater. Process. 2022, 6, 158 7 of 18

windows [73]. It is inevitable that porous materials will tear and crack; however, it is
necessary to avoid hot tearing or cracking while porous materials are present [74]. A LPBF
component’s quality is deteriorated most severely by hot tearing and cracking. When the
temperature gradient remains high, even when the constitutional super-cooling is lower,
columnar grains are more susceptible to hot tearing [75]. Cavities and hot-tearing cracks
can occur across the full length of columnar grains when temperature and liquid volume
fraction decrease. Since there has been limited research on the impacts of alloying and
processing parameters on hot tearing during LPBF in Mg, it is unclear what effect they
have [76].

Table 2. Processing-relative densities of LPBF’ed Mg and its alloys for bone tissue engineering applications.

Parameters
Powder Size and Input Energy Relative
Alloys Spot Size Speed Thickness Hatch Ref.
Shape (µm) Power (W) Density (J/mm3 ) Density (%)
(µm) (mm/s) (µm) Spacing (µm)
90 100 300 96.1
Mg Pre-alloyed 43, s 1 90 100 100 30 100 >300 Evaporated
[77]
Mg Pre-alloyed 24, s 70 80 500 30 30 156 97.5 [78]
1250 63 88.2 [79]
195 800 200 41 99.7
195 800 250 33 98.3
WE43 25–63, s 195 100 1200 30 200 27 96.6 [67]
135 1200 200 19 87.6
WE43 25–63, s 200 125 700 30 40 238 99.9 [28]
WE43 25–63, s 200 70 1100 40 130 35 99.7 [80]
WE43 25–63, s 200 90 700 30 40 238 99.8 [81]
120 960 30 104 98.6
WE43 30, p 45, 63, s 150 90 1200 40 104 99.0 [82]
300 1200 208 99.5
GZ151K 25–65, s 200 – 700 30 70 136 97.9 [83]
100 267 98.7
300 89 99.9
500 53 99.7
700 100 38 99.8
GZ112K 31–44, s 80 100 1000 30 27 96.9 [65]
1500 18 71.8
500 50 107 99.5
500 150 36 96.5
G10K 63, s 80 – 200 30 100 133 99.2 [84]
Mg-1Zn Blended Mg-5.5 99.4
Mg-2Zn Zn (36, s), Mg 98.2
Mg-6Zn 180 150 700 20 70 183 94.7 [47]
(31, s) and Zn
Mg-12Zn (19, s) 98.9
6.7 750 94.5
8.3 600 97.4
ZK60 30, s 50 150 10 100 100 500 88.6 [85]
11.7 420 72.8
300 417 94
500 250 93
ZK60 30, s 200 150 700 20 80 179 88 [86]
900 139 84
1 Spherical shape.

4. The Advantages of LPBF over Other AM Processes


It is worth noting that LPBF has the added advantage of being able to produce highly
porous and fine structures as well as accommodate many forms, not only prismatic ones [72].
Thus, it is widely used to manufacture metallic scaffolds and implants. In addition, osseoin-
tegration studies have shown that implants can be designed with preferentially porous
layers to enhance adhesion between the bone tissues and implant material [75]. A human
bone consists of three distinct anatomical cavities: haversian canals, osteocytic lacunae,
and canaliculi [66–69]. A bone’s mechanical characteristics and processes are remodeled
in these three cavities. Living tissues can flourish in porous structures, as nutrients can
be transported [49–54]. It is possible to design components with a modulus similar to
the bone’s, which reduces stress-shielding problems in metallic orthopedic materials by
adjusting porosity levels. Based on the geometries of metallic cellular structures, non-
stochastic and stochastic structures are distinguished [77]. An arbitrary number of closed
or open voids characterize stochastic metal porous structures. The non-stochastic structure
of metal shows homogeneous patterns that repeat over many units cells, as opposed to
the stochastic structure [78]. Because metal cellular/porous structures are lightweight and
have better power absorption properties and excellent acoustic and thermal properties,
they are commonly used in the automotive, aerospace, and chemical industries [79]. A
J. Manuf. Mater. Process. 2022, 6, 158 8 of 18

structure with such complex external shapes and intricate internal structures is difficult
to fabricate using traditional casting and powder metallurgy techniques. Changing the
specifications of these production techniques may alter the dimensions of the pores, but
it will only produce a porous structure that is arbitrarily arranged [80]. Using LPBF, on
the other hand, can create porous metals with a predefined external form and an inter-
nal structure that complements the rigidity of bone and reduces or diminishes the need
for stress shields during manufacturing [81]. Compared with directed energy deposition
(DED), which is also widely used for the fabrication of metals, PBF has a smaller beam
spot, finer powder, and a thinner layer, which provide better dimensional accuracy [10]. In
addition, the LPBF process is characterized by its high energy density and the absence of
sacrificial binders, which allows for nearly complete densification of metal parts, which is
an advantage over other metal additive manufacturing technologies such as binder jetting.
Laser and electron beam spot sizes are currently between 50 and 100 microns, powder
sizes are between 20 and 50 microns, and the thickness of each powder layer is between
20 and 80 microns for LPBF and electron beam powder bed fusion (EBPBF), respectively.
Therefore, the dimensional deviation between the as-built geometry and the designed
geometry is decreased as a result of the higher forming accuracy of LPBF when compared
to EBPBF [13]. Its high dimensional accuracy, high performance, geometric freedom, and
geometric freedom without rigid support make LPBF suitable for metal implants. There are
many disadvantages to the wire arc additive manufacturing (WAAM) of Mg in comparison
with LBPF, including the possibility of scaffold structures that might be too coarse to be
used in medical applications, the availability of wire (no custom alloys), and the high level
of processing required. Moreover, compared to LPBF, WAAM produces components with
a high deposition rate and surface roughness, resulting in a higher degradation rate of
WAAM’ed Mg implants in physiochemical solutions [14].

5. Properties of LPBF’ed Mg Implants


5.1. Mechanical Properties
Mg components processed using LPBF have a significantly improved mechanical
performance due to the thin continuous refined microstructure formed [10]. The ideal
powder particle size should be between small and large: finer particles can be melted
easily and are beneficial to model quality surface finishes, and larger particles are beneficial
for ductility, hardness, mechanical strength, and toughness [13]. Further, components
produced by LPBF typically exhibit anisotropic microstructures at a variety of length scales.
A rapid solidification process forms an anisotropic microstructure in the heat dissipation
direction through conduction, convection, and radiation. It is important to consider the
type of scanning strategy used, the base plate temperature, and the direction in which the
build takes place when determining anisotropy. A component built in a different direction
to the substrate such as perpendicular (e.g., vertical) or parallel (e.g., horizontal) has a
different thermal history [13,14]. This creates an anisotropic mechanical property as well
as a different surface texture (finish). Selecting the right combination of parameters is
crucial to the quality of LPBF’ed Mg implants. As a result of non-optimized LPBF process
parameters such as laser energy density, metallurgical defects, cracks, and pores are formed,
resulting in poor mechanical properties. The tensile properties of LPBF’ed Mg and its alloys
are listed in Table 3. The yield strength of LPBF’ed Mg alloys compared with cast and
wrought (rolled and extruded) alloys is shown in Figure 6. Typical alloy yield strength for
most structural applications is greater than 200 MPa, with some alloys reaching 350 MPa.
A majority of LPBF’ed Mg alloys have less than 5% ductility, and some alloys may not even
have ductility. Compression or hardness tests are required to measure their mechanical
properties. The low ductility of such a material makes it unsuitable as an engineering
material. Several alloys are characterized as having fine grains, weak textures, and low
porosities, yet ductility is still poor [87]. Here are some reasons for the change. Because
the as-LPBF solidifies rapidly, it has a high residual stress, which reduces its ductility.
There is a high concentration of intermetallic elements along the grain boundaries of alloys
J. Manuf. Mater. Process. 2022, 6, 158 9 of 18

such as the AZ91, WE43, and Mg-Gd alloys studied [70]. Thereafter, the grain boundary
becomes brittle and responsible for local failures (e.g., slip and twin transmission across
grain boundaries, grain boundary sliding, etc.). Once this happens, they do not have the
ability to accommodate plastic deformation. It would also be possible for the sputtering
powder or vapor to re-deposit on the surface of the sample, which would result in the part
being poorly consolidated or with a weak bond to the sample [13].

Table 3. Input energy density, grain size, tensile, and electrochemical properties of LPBF’ed Mg and
its alloys.

Mechanical Properties Electrochemical Properties


Energy Density Grain Size
Alloys H1 YS 2 UTS 3 EL 4 icorr Mass Loss Ref.
(J/mm3 ) (µm) Solution
(HV) (MPa) (MPa) (%) (µA/cm2 ) (mm/year)

Mg 97.5 1–5 – – – – 74 3
88.2 – 177 32 [77]
Mg 300 – 52.4 – – – – – [70]
Mg-9Al 250 10–20 70 – – – – – [88]
Mg-9Al 156 1–3 – 274 1 Hank’s solution – – [89]
139 1.6 219 273 3.3
156 1.8 – 233 287 3.1 – –
AZ61 179 2.1 225 261 2.8 [90]
208 2.5 216 239 2.1
120 4.5 70 2.7
140 8 80 – – – – 2.4
AZ61 160 10 93 12 [91]
180 13 90 1.5
AZ91 167 274 296 1.2 – –
83 1–2.9 85–100 237 254 1.8 – – [92]
SBF solution
AZ91 68.6 1–10 115 – – – – – [47]
AZ91 104 1–1.5 – 265 328 3.8 – – [93]
AZ91 278 3.3 – 308 345 1 – – [79]
AZ91-SiC 278 1.1 – 260 300 2 – – [67]
AZ91–2Ca – – – 235 332 3.2 – – [29]
120 34 5.1
WE43 150 27 - - - - 5.0 6–7.2 [28]
300 18 4.4
WE43 238 1 – 296 308 12.2 – – [80]
WE43 35 1–3 – 214 251 2.6 – – [82]
WE43 238 20.4 – – – – – – [82]
G10K 133 27 80 180 228 2.2 0.1 M NaCl – – [83]
J. Manuf. Mater.
GZ151K Process.
136 2022, 6, 158 2 368 3 – – [94] 10 of 1
Mg-1Zn 50 145 11
Mg-2Zn – 46 345 70 2.5 – –
Mg-6Zn 183 65 50 1.5 [95]
Mg-12Zn 83 75 3.2
ZK30 – 80 – – – 17.8 1.23
2000 [96]
ZK30-Cu the sample,
98 which would result in the partSBFbeing solution
poorly47.8
consolidated
2.12 or with a wea
1 Hardness; 2 yield strength; 3 ultimate tensile strength; 4 elongation.
bond to the sample [13].

Figure6.6.Comparison
Figure Comparison of tensile
of tensile properties
properties of Mgofalloys
Mg alloys developed
developed by LPBFby LPBF
and otherand other conventiona
conventional
production techniques
production techniques [87].[87].

Table 3. Input energy density, grain size, tensile, and electrochemical properties of LPBF’ed M
and its alloys.

Grain Mechanical Properties Electrochemical Properties


Energy Densi‐
Alloys 3
Size H1 YS 2 UTS 3 EL 4 icorr Mass Loss Ref.
J. Manuf. Mater. Process. 2022, 6, 158 10 of 18

5.2. Corrosion Behavior


The corrosion of metallic implants develops rapidly in the human body as a result
of aggressive conditions. As a result of the chloride ions in biological media, corrosion
occurs, and H2 gas is produced, which slows down the healing process and causes necrosis
of the tissues in the surgical area [97]. Surface coatings can be applied to the surface of
Mg implants to inhibit the corrosion progress [98]. The LPBF’ed Mg alloys are currently
used most frequently in biodegradable scaffolds and implants. In the case of oral and
maxillofacial implants, for example, the Mg-based biomaterials should remain mechanically
intact for the initial month, before gradually decomposing and eventually dissolving. Due
to the poor corrosion resistance of Mg and its alloys in most aqueous environments, enough
electrochemical durability is needed. Table 2 illustrates the electrochemical corrosion
behavior of LPBF’ed Mg and its alloys in simulated biological solutions. It has been reported
that the corrosion current density (icorr ) of LPBF’ed pure Mg ranges from 74–177 µm/cm2
in Hank’s solution, which is higher than the casted pure Mg ingot measured under the
same condition (23.6 µm/cm2 ). Through the manipulation of print process parameters,
it is possible to alter the porosity of a 3D construct, which has a significant impact on
corrosion rates and the behavior of the cells. According to the processing parameters,
mass losses range from 3 mm to 32 mm per year. Pure Mg manufactured by LPBF has an
extremely high corrosion rate, about 144 mm/year when it is dissolved in a 3 wt.% NaCl
solution. Due to the loosely fused Mg clusters and sintered Mg powder, the corrosion
resistance is significantly reduced. This higher corrosion rate is closely related to the
defects generated during LPBF. Indeed, degradation rates are faster when there are more
defects. Furthermore, the corrosion resistance of the LPBF’ed WE43 alloy was much lower
than the casted alloy. In comparison with the interface and cast samples, the LPBF’ed
WE43 exhibits a significantly higher corrosion potential and significantly lower corrosion
current density. Accordingly, all samples exhibit localized corrosion morphologies with
differing severity, based on the observed active-like behavior. As a result of the absence of
a distinct Tafel region in the anodic polarization curves, the quantitative values deducted
from the polarization plots cannot be used individually, but can only be used in qualitative
comparative studies of the polarization response [99]. Based on 5% foetal bovine serum
in a revised simulated body fluid (r-SBF), corrosion current density ranges from 20 to
60 m/cm2 . Moreover, it loses mass 6 to 7.2 mm per year when it is dissolved in 0.1 M
NaCl solution, which is approximately six times greater than the mass loss rate of cast
WE43 alloy (0.8 to 1.2 mm per year). A high density of stable RE oxide particles and a
reactive Mg matrix results in a micro-galvanic reaction, resulting in a higher corrosion rate.
If plasma electrolytic oxidation is not performed on the scaffold surface of the LPBF’ed
WE43 scaffold after 21 days of immersion in SBF, its structural integrity is reported to be
lost after 21 days of immersion in SBF. Research in another study reported that the LPBF’ed
WE43 alloy retained structural integrity after 28 days in vitro without obvious particle
separation; however, it had a 41% loss in strength. Structural parameters, such as pore
size and strut diameter, seem to affect scaffold degradation more than bulk samples [95].
The corrosion resistance of the LPBF’ed Mg-Al alloy is similar to the cast alloy, however.
In the SBF state, the degradation rate for LPBF-AZ61 alloy was around 1.2–2.7 mm/year
as-immersed, and then it decreased. After 24 days of immersion in SBF, the corrosion rate
of cast AZ61 samples stabilizes at 1.299 mm/year, which is similar to the corrosion rate for
the cast AZ61 sample. Although the surface of the corroded sample seems to indicate a
more severe corrosion of LPBF’ed ZK60 than cast ZK60, the LPBF’ed ZK60 has marginally
better corrosion resistance in Mg-Zn systems than cast ZK60. By blending ZK powders
with Cu powders, Shuai et al. increased the antibacterial effect of Mg-Zn-Zr implants by
adding dilute Cu concentrations to LPBF ZK30 and ZK60 [100]. LPBF’ed ZK-Cu alloy
degradation is accelerated by Cu addition.
J. Manuf. Mater. Process. 2022, 6, 158 11 of 18

5.3. Biocompatibility
As AM’ed Mg alloys are the most promising materials for bone tissue implants, there
is a need to consider LPBF’ed Mg alloys’ biocompatibility. The human body requires Mg to
function properly. Due to its biodegradability, Mg is capable of gradually transferring a
load from the implant to the regenerated bone if the implant is biodegradable enough [101].
Mg has a degree of biocompatibility and bioactivity that allows it to promote the prolif-
eration and differentiation of cells even though it is biocompatible [102,103]. In addition
to stabilizing DNA and RNA, it promotes bone growth and healing. Biocompatible alloy-
ing elements are also needed when designing bioabsorbable biomaterials based on Mg
alloys [104]. However, a rapid breakdown of Mg scaffolds provides significant amounts of
hydroxides, Mg ions, and ions from alloying elements to be released in large quantities,
which have an adverse effect on the viability of cells and biocompatibility of the alloy. The
study of cell interactions with biomaterials can be performed by culturing cells [105–107].
LPBF’ed WE43 has been found to be biocompatible in vitro in numerous studies [108].
Four hours after immediate seeding, MG-63 cells in direct contact with WE43 appeared
to be dying as determined by live-dead staining, followed by dual-channel fluorescent
optical imaging (FOI) [109]. After seeding Ti-6Al-4V, on the other hand, no cell death can be
observed after 4 h. It was found that a substantial number of cells survived 24 h after direct
contact with WE43 scaffolds that had been pre-incubated in physiological serum-containing
culture medium for 48 h [110]. Using a similar methodology, it was reported that poor
cellular adherence to the scaffold was observed in a similarly designed study using indirect
extract-based assays (LDH, XTT, and BrdU). RE-based Mg alloys themselves appear to
possess no cytotoxic potential; however, the vast reaction on their bare metal surfaces causes
high levels of hydrogen gas to be evolved and pH shifts local to the surfaces, impairing
the metabolic efficiency of the cells [111]. LPBF’ed WE43 scaffold was found to contain
no viable cells, and only a few dead cells were visible by direct live/dead staining. There
is a possibility of resolving this problem if the surface of the substrate can be modified,
using plasma electrolytic oxidation, which seems to be a suitable niche for adhering cells
when the surface is passivated [112]. Additionally, this technique appears to have reduced
degradation byproduct releases, thus indicating that hardly any signs of cell impairment
were observed. Additionally, there are reports that LPBF scaffolds are manufactured on
pre-alloyed Mg-Nd-Zn-Zr (JDBM) materials, as shown in Figure 7a–i [113]. Similarly, in the
trial of cell adhesion to scaffolds coated with dicalcium phosphate dihydrate vs. scaffolds
left uncoated, more cells adhered to the scaffold coated with dicalcium phosphate dihydrate.
Neither the coated nor uncoated LPBF’ed JDBM scaffolds showed a significant difference in
terms of cytotoxicity in this study: both examples stimulated cell proliferation (Figure 7j–o).
The findings presented in this study and the verification of these findings require a fuller
study and verification, because it is highly unlikely that a direct cell response will not at
least be induced by uncoated AM’ed Mg scaffolds.
Moreover, the presence of bacteria in the implant may cause the implant to loosen or even
fail, demonstrating the importance of inhibiting infections caused by bacteria [114–118]. The
positively charged Cu ions released by the body are capable of attaching to the negatively
charged bacterial cell walls, impairing the permeability of the membranes and eventually
causing the bacterial cell to lyse and die. Additionally, Cu ions can also activate some en-
zymes by interacting with their thiol groups, resulting in bacterial death. Moreover, copper
functions as a cofactor in a wide range of metabolic enzymes in the human body [119].
LPBF’ed ZK60-Cu alloys prepared by Xu et al. exhibited strong antibacterial properties
when they contained Cu [95]. This study indicated that ionized Cu ions, combined with an
alkaline environment, could effectively kill bacteria by damaging the structure of cellular
membranes, causing enzymes to denaturate, inhibiting deoxyribonucleic acid replication
and destroying DNA.
Moreover, copper functions as a cofactor in a wide range of metabolic enzymes i
human body [119]. LPBF’ed ZK60‐Cu alloys prepared by Xu et al. exhibited strong
bacterial properties when they contained Cu [95]. This study indicated that ionize
ions, combined with an alkaline environment, could effectively kill bacteria by dam
J. Manuf. Mater. Process. 2022, 6, 158 12 of 18
the structure of cellular membranes, causing enzymes to denaturate, inhibiting deo
bonucleic acid replication and destroying DNA.

Figure
Figure7. (a–c) Micro-CT
7. (a–c) images,
Micro‐CT (d–f) SEM
images, (d–f)images,
SEM and (g–i) and
images, corresponding magnified images
(g–i) corresponding of
magnified ima
the as-polished B (a,d,g), D (b,e,h), and G (c,f,i) scaffolds. Cytocompatibility of (j–l) the G scaffolds
the as‐polished B (a,d,g), D (b,e,h), and G (c,f,i) scaffolds. Cytocompatibility of (j–l) the G sca
and (m–o) the G-DCPD scaffolds, where (j,m) show the results after 6 h, (k,n) show the results after
and (m–o) the G‐DCPD scaffolds, where (j,m) show the results after 6 h, (k,n) show the result
1 d, and (l,o) show the results after 3 d [113].
1 d, and (l,o) show the results after 3 d [113].
6. Conclusions, Challenges, and Future Perspectives
6. Conclusions, Challenges,
The biocompatibility and Future Perspectives
and biodegradability of Mg alloys make them ideal materials
for biomedical applications. Due to the manufacturing feasibility of complex-shaped
components, it would be possible to fabricate customized Mg components via additive
J. Manuf. Mater. Process. 2022, 6, 158 13 of 18

manufacturing techniques based on patient-specific anatomical data. The present review


article discusses the PBF-based AM process, which is used to fabricate Mg-based implants.
The reasons behind its selection over other AM techniques are compared and discussed in
detail. The following is a concise summary of the challenges and opportunities that emerge
in light of the review presented herein.

6.1. Bottlenecks
(1) Laser-based additive manufacturing presents a challenge in terms of producing pre-
alloyed powder. More research is needed in the area of blending magnesium powders
and building consistency.
(2) How the topology of scaffolds affects cell proliferation, new cell growth, and the
lattice structure of the fabricated Mg components that are fabricated using the additive
manufacturing process are still unexplored. This suggests that further studies should
be conducted using in vitro and in vivo methods for the Mg scaffolds manufactured
through LPBF.
(3) Mg implants are evaluated in vivo for their biodegradation performance out of both
processes. Therefore, the study of in vivo processes should be carried out in great
detail in order to succeed in clinical applications. For biomedical implants, LPBF of
Mg components has been shown to be an appropriate and promising alternative. An
alloy that is suitable for bio-implant application could be developed by evaluating
the Mg alloys used currently. An alloying element would be added according to the
strength considerations of the implant in question and its biocompatibility. This will
be considered in future work if a new Mg-based alloy is created.

6.2. Prospects
(1) As a result of the efficient infiltration and complete melting of Mg alloy, LPBF is
a suitable AM technology for the fabrication of Mg implants. This resulted in the
removal of voids and the creation of high-density components. The powder properties
that were used in the manufacturing process of the Mg scaffolds and implants, as well
as the printing parameters used in printing, play a major role in determining their
biological and mechanical properties.
(2) LPBF produces the Mg scaffold with a hierarchical porous structure that mimics the struc-
ture of the human bone in terms of micro- and macro-pores for personalized medicine.
(3) In comparison with other AM techniques, LPBF provides better dimensional accuracy,
because it has a smaller beam spot, finer powder, and a thinner layer. Additionally,
LPBF technology offers high-energy density, no sacrificial binder, and near-complete
densification of metal parts, which makes it superior to other metal additive manufac-
turing processes such as binder jetting and WAAM.
In conclusion, it is expected that future developments of the LPBF process of Mg,
particularly those for bone tissue engineering applications, will focus on a wide range of
properties, including mechanical properties, corrosion performance, biocompatibility, print-
ing properties, biomimetic properties, and biodegradation properties. It would be a reliable
method for building various organs and tissues with diverse mechanical requirements
whether the use of new types of steels as biomaterials with different compositions is being
developed. It would be a reliable way to achieve reprogrammed mechanical properties
and functions. The Mg-based alloys produced by LPBF will be used to make stents, screws,
plates, and scaffolds in the near future.

Author Contributions: M.G.F.—conceptualization, methodology, and writing (original draft prepa-


ration); F.S.—resources and writing (original draft preparation), supervision; S.S.K.—software,
writing (original draft preparation); H.R. writing (original draft preparation); M.S.B.—writing (re-
view and editing) and supervision. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
J. Manuf. Mater. Process. 2022, 6, 158 14 of 18

Data Availability Statement: Not applicable.


Conflicts of Interest: The authors declare no conflict of interest.

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