Acta Materialia 165 (2019) 294e306

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Acta Materialia
journal homepage: www.elsevier.com/locate/actamat

Full length article

A paradigm shift towards compositionally zero-sum binderless 3D

printing of magnesium alloys via capillary-mediated bridging
Mojtaba Salehi a, Saeed Maleksaeedi b, Sharon Mui Ling Nai b, **,
Ganesh Kumar Meenashisundaram b, Min Hao Goh b, Manoj Gupta a, *
a
Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore, 117576, Singapore
b
Singapore Institute of Manufacturing Technology, 73 Nanyang Drive, 637662, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: Several metallurgical issues arise during melting and solidification-based additive manufacturing (AM)
Received 10 October 2018 methods which limit their use to only a few alloys. This study shows how capillarity-driven bridging can
Received in revised form serve as a new and rapid tool of assembling powder particles into 3D structures providing the least
1 November 2018
metallurgical complexity. According to the established conceptual framework, in-situ binding agent can
Accepted 30 November 2018
be derived autogenously from selective interactions of a liquid solvent with superficial layer of powder
Available online 3 December 2018
particles to form in-situ solid interparticle bridges which enables AM at ambient conditions. Magnesium
(Mg) is the most difficult engineering metal to handle in all 3D AM processes in view of its intrinsic
Keywords:
Additive manufacturing
properties. Supported by transmission and scanning electron microscopies together with Fourier
3D printing transform infrared and Raman spectroscopy, the introduced 3D printing concept is readily accomplished
Magnesium alloy for Mg alloys by conversion of MgO film, inevitably existing on the outermost layer of Mg powder, into
Inkjet technology interparticle bridges. In the absence of pyrolysis-adapted sintering profile, these bridges fully decompose
Capillary bridging during the following sintering step which result in functional Mg parts with chemical composition same
as the starting Mg powder with zero contamination, according to chemical and thermal analysis results.
The introduced capillary-mediated binding of particles is simple and generic that could be extended to
additively manufacture other metals, ceramics and found applications in other traditional ex-situ binder-
based processes.
© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction techniques since all microstructural transformations occur during

Additive manufacturing (AM) has been developing very rapidly
into a game changer technology owing to its capability to fabricate
complex structures [1e5]. Binder jet 3D printing is an AM process
that works in accordance with inkjet technology in which ex-situ
polymeric binder materials selectively glues powder particles
together forming a 3D object. Then, the as-printed object is trans-
formed into end part by debinding (i.e. a binder removal treatment
involving solvent washing and/or thermal decomposition pro-
cesses) followed by sintering process. From metallurgical
perspective, material innovations through binder jet 3D printing
are far less complex than laser or electron beam-based AM
* Corresponding author.
** Corresponding author.
E-mail addresses: mlnai@simtech.a-star.edu.sg (S.M.L. Nai), mpegm@nus.edu.sg
(M. Gupta).
sintering of 3D printed objects provided challenges of the need for
ex-situ polymeric binder and the debinding that leaves behind
residue are resolved. The adhesive-based binding used in binder jet
3D printing adversely affects its reliability and sustainability due to
the need for debinding process. The debinding process is lengthy
and messy, and there are concerns about its residue that serves as
contamination and adversely affects the sintering process.
Furthermore, by-products of binders during the debinding process
may react with the powder particles. Moreover, printed parts may
distort or slump during debinding and before sintering. Binder is
the backbone of inkjet-based 3D printing technology while the
debinding step is the main formidable challenge to make this
technology more environmentally sustainable with shorter lead
time. Overcoming this obstacle to create a breakthrough innovation
begs the question: How do we eliminate the debinding step for any
given powder feedstock that neither disrupt the built cycle nor
degrade the chemical composition of end products?

https://doi.org/10.1016/j.actamat.2018.11.061
1359-6454/© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
Capillary force can bind particles to shape 3D structures.
Building sandcastles is a well-known example of binding particles
through the formation of capillary bridges in which water is drawn
by capillary force to the gap between wet sand particles and hold
them together into 3D networks [6]. Similarly, capillarity was used
as a powerful tool to form assemblies of particles targeting a variety
of applications [7e10].
Magnesium (Mg) has potential applications in both structural
and biomedical sectors [11e15]. Previously, several attempts were
made to additively manufacture Mg alloys especially with selective
laser melting (SLM). In view of intrinsic properties of Mg, several
challenges such as safety concerns, oxidation during SLM process,
and recycling of used Mg powder after SLM are raised, which have
not been totally addressed [15e19]. For example, MgO film, inevi-
tably existing on the outermost layer of Mg powder due to its high
affinity to oxygen, disrupts AM processability. As another example,
fine Mg powder used for SLM can oxidize significantly under pro-
tective atmosphere of argon gas due to presence of very minimal
oxygen impurity in the streaming gas [16]. Furthermore, evapora-
tion of Mg and some alloying elements such as zinc during laser
scanning leads to undesirable compositional variation in SLM
fabricated parts [20,21]. In view of very high vapor pressure of Mg,
electron beam melting process is not able to handle Mg alloys. To
the best of our knowledge, there is no report on inkjet-based 3DP of
Mg alloys as well. These results of literature search signify that
employing AM techniques for Mg alloys is in preliminary stages of
developments, as against for other standard materials such as
steels, titanium, aluminum, and nickel base super alloys where AM
processes have been commercialized.
Here, we demonstrate that capillary bridging concept can be
used as a rapid, facile, and extensible approach to additively
manufacture a 3D object with no ex-situ binder material and totally
eliminate the debinding step. Firstly, the concept is established to
relate the physical properties of a powder feedstock to the amount
of liquid required for formation of capillary-driven bridges. Sec-
ondly, Mg alloys, which are the most difficult materials to handle in
all the 3D AM processes, are used as a demonstration platform to
implement the concept. We show that a judiciously formulated
solvent allows 3D objects to be made of Mg powder by in-situ
formed binding agents. Transmission and scanning electron mi-
croscopies are carried out to characterize superficial interactions
between the solvent and Mg powder. Then, chemical and thermal
analysis results are used to validate that the chemical composition
of starting powder remained intact after sintering of as-printed
parts in the absence of debinding step. Finally, the extension of
this approach is further demonstrated by developing a second Mg
alloy made of Mg-Zn-Zr, providing comparable properties with
various bone types.
2. Materials and methods
2.1. Materials
The centrifugally atomized 99 þ% pure Mg (D50 ¼ 30.3 mm) and
Mg-5.9wt.% Zn- 0.13wt.% Zr alloy (60e70 mm) with spherical par-
ticle shape (International Laboratory, USA) were used as powder
feedstock materials. Apparent and tapped density of the powder
was measured according to ASTM standards B212 e 13 and B527 
15.
2.2. 3D printing process
An inhouse-modified 3D printer that utilizes a drop on demand
print head to generate ink with droplets of size 40 mm was used as a
3D printing apparatus. The selection of ink materials (binders or
295
solvents) for powder bed inkjet 3D printing is a critical task since it
affects the built cycle as well as the post-printing steps, including
post-printing bed manipulation, depowdering, debinding, and
sintering. In addition to formulating composition, ink formulation
processing steps include adjusting ink rheology to have reliable
jettability by a print head and testing ink compatibility to effec-
tively interact with powder within the powder bed. For example,
furan, phenolic, silicate, and aqueous-based binder materials are
used in commercial binder jetting systems. More detailed de-
scriptions of binder materials classes and process development
stages for inkjet-based 3D printing of metals or a new material
system are provided in Refs. [22,23]. In this study, the ink was a
single-phase solvent with no binder or solute formulated based on
chemistry of Mg alloys. The layer thickness was set to 100 mm, and
the build process was carried out under ambient conditions. After
the end of build cycle, the entire powder bed was maintained under
temperature ranging from 35  C to 45  C for an hour so that the as-
printed samples could be successfully removed from the sur-
rounding loose powder in the powder bed. The as-printed samples
were sintered in a tube furnace under protecting atmosphere of
argon gas. For as-printed parts made of the pure Mg powder, the
sintering profile comprised of heating ramp rate of 10  C/min from
room temperature to 650  C, holding for 1 h, and furnace cooling
until room temperature. For as-printed parts made of the Mg-Zn-Zr
powder, the sintering profile consisted of heating ramp rate of
10  C/min from room temperature to 576  C and holding isother-
mally for two different periods of 40 h and 100 h followed by
furnace cooling until room temperature.
2.3. Characterization methods
Specimens in the as-printed and as-sintered conditions were
examined under a Hitachi S-4300 field emission scanning electron
microscope (FESEM). Samples were cross-sectioned for observation
under the microscopes. Specimens for transmission electron mi-
croscope (TEM) were prepared by using focused-ion beam (FIB)
milling technique (Helios NanoLab™ 600i). As-printed sample
made of pure Mg was initially examined using FESEM to find a
proper pair of particles for cutting (Fig. 1a). A layer of 5 mm thick
platinum (Pt) was coated on the top surface of particles to protect
the surface films as well as interparticle bridge from spurious
sputtering during the subsequent ion milling (Fig. 1b). Then, the
particles were milled using Ga-ion beam to 1 mm and the specimen
was directly mounted onto the TEM grid using in situ specimen lift-
out manipulator (Fig. 1c) followed by further thinning to be elec-
tron transparent for TEM examination. The thinned specimen was
analyzed in a FEI Tecnai G2 F20 field-emission gun TEM/STEM
operating at 200 KV accelerating voltage for imaging and micro-
analysis (EDS).
Chemical composition of the as-received Mg powder and
fabricated samples in the as-printed and as-sintered conditions
were analyzed by several techniques, consisting of:
1. Combustion-infrared absorbance using a Eltra CS 800 Carbon/
Sulfur Analyzer.
2. Inert gas fusion-infrared absorbance and inert gas fusion-
thermal conductivity by Eltra ONH 2000 Oxygen/Nitrogen/
Hydrogen Analyzers.
Thermal analysis of as-printed samples was carried out using a
Shimadzu DTG-60H Thermo-Gravimetric Analyzer capable of
recording Thermogravimetric analysis (TGA) and Differential ther-
mal analysis (DTA) curves simultaneously. Specimens were tested
under atmosphere of argon gas in the temperature range
30  Ce500  C at a heating rate of 15  C/min.
296 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
Fig. 1. Preparation of specimen for TEM studies using FIB technique, a) SEM image of selected pure Mg particles, b) platinum coating to assure the top surface of interest remained
intact during following FIB milling, and c) milled sample mounted onto the TEM grid.
Fourier transform-infrared (FTIR) and Raman spectroscopy are
powerful analytical techniques for analyzing trace levels of chem-
icals, amorphous and poorly crystalline materials. Hence, a portion
of as-printed samples was placed on the diamond attenuated total
reflection (ATR) crystal to obtain FTIR spectra using a Bruker Vertex
80v vacuum spectrometer. 32 scans between 400 and 4000 cm1 at
a spectral resolution of 4 cm1 were performed for each sample.
Raman spectra were acquired on Renishaw InVia Raman Micro-
scope equipped with 50X objective lens (working dis-
tance ~ 8.2 mm). Argon ion laser beam (l ¼ 514 nm) was excited
specimens and 2400 lines/mm grating was used for the spectra to
be collected over the Raman shift range 115e4000 cm1 at
1.12 cm1 resolution.
Non-destructive measurement of the dynamic Young's modulus
was made on cylindrical rods with dimension of F10  60 mm
made of the Mg-Zn-Zr alloy in the as-sintered condition by reso-
nant ultrasonic spectroscopy (RFDA; IMCE, Belgium), according to
ASTM E1876-15. In accordance with ASTM E9 e 09, the compressive
properties of as-sintered Mg-Zn-Zr alloy were determined using
MTS-810 testing machine on the test specimen of 10 mm in
diameter and 11 mm in length. Using the same testing machine, the
sub-size round tensile test specimens according to ASTM E8, were
used to determine tensile properties of as-sintered Mg-Zn-Zr alloy.
3. Results
3.1. The concept of capillary-mediated binderless 3D printing
Hysteretic nature of the capillary-driven bridges provides a basis
for 3D printing purpose (for more details about capillary bridges
see section A.1, Appendix A). This hysteretic phenomenon implies
that the adhering liquid layer of particles must come into contact to
form a bridge, but a certain critical separation between two
particles must be reached to rupture the liquid bridge. The amount
of liquid required for a given powder feedstock can be correlated to
its physical property. Consider a stationary layer of powder feed-
stock within the powder bed as a pile of monodispersed spheres
where each individual sphere just has sufficient contacts to hold its
position in the layer. The distance from the uttermost surface of one
sphere to that of the another is defined as interparticle spacing. The
interparticle spacing is equal to zero when the packing of equally
sized spheres is maximum in which the neighboring spheres share
contact points. Several equations on the basis of theory or empirical
evidence can be used to estimate interparticle spacing [24e27]. As
per detailed descriptions of a cell model based on first principles
[24,25], the following equation correlates interparticle spacing, L,
for powder bed with a particle packing fraction of r containing
equally sized spheres with radius R:
" 1=3 #
rm
L ¼ 2R 1 ðr  r m Þ (1)
r
where, rm is the maximum particle packing fraction.
Consider a wet spherical particle having a layer of liquid with an
average thickness of H on its surface. A dimensionless quantity of
the liquid content, W, is defined as the ratio between the volume of
added liquid to the total volume of a wet granule. The average
thickness, H, is related to liquid content and particle packing frac-
tion by the following equation [28]:
WR
H¼ (2)
3r
To fulfil the necessary condition for formation of liquid bridges
in terms of the hysteretic nature, the total thicknesses of the liquid
layer on the surface of each adjacent sphere should be equal to the
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306 297

interparticle spacing from Eq. (1). Substituting Eq. (2) into Eq. (1) should be noted that dense random packing, equal to 0.63 [32], is
and rearranging yields: assumed for rm to plot these curves. A greater amount of solvent is
" # required for powder with looser packing density, and therefore a
1=3
rm larger amount of solvent-powder interaction products, in volu-
W ¼ 3r 1 (3)
r metric percentage, forms in the interparticle necks. Two main
transformations occur when the amount of liquid content increases
Eq. (3) does not meet the necessary condition of liquid bridge in the powder. Firstly, the mutual attractive force acting on particles
formation while the particle packing fraction is maximum. To approximately remains constant which results in a negligible dif-
satisfy this condition, a minimal liquid content, W0, needs to be ference in packing density of the solid portion of wet granule [6].
added to Eq. (3) as in Eq. (4). Secondly, the bridge volume augments mainly due to the bridge
" # angle increment. This augmentation results in an increase in the
1=3
rm critical separation distance and therefore the work done to separate
W ¼ 3r  1 þ W0 ðr  rm Þ (4)
r the powder particles. However, Lc incremental is only a function of
the cube root of the bridge volume.
Theoretical studies suggested that W0 is a parameter that should In essence, these plots indicate how to fabricate a 3D object
be experimentally determined [28]. As an estimation, experimental with minimum amount of the products of solvent-powder inter-
and validated simulation-based investigations indicated that the action in the interparticle necks, which in turn lead to negligible
minimal liquid content can be in the range of 3  104 to 2.4  102 change in the chemical composition of sintered parts. For
[6,29]. example, the products of solvent-powder interaction can only
The liquid content in free space Wf, that is, the amount of occupy 1.67 vol % in as-printed 3D objects made of loose random
available pore space within a wet granulate which is filled with packed powder bed (i.e. r ¼ 0.59). It should be pointed that the
added liquid, is related to the liquid content by Eq. (5): bridge volume (Eq. (8)) is calculated in the absence of liquid
evaporation and with the assumption that all the liquid content
W transfers/accumulates into the bridge. From a practical standpoint
Wf ¼ (5)
ð1  rÞ to further reduce the bridge per particle volume, excess amount of
a solvent, either inside the interparticle bridge or far from it on the
The definition of Wf is equivalent to a parameter well known as
surface of particles, could be evaporated after liquid bridges form
the saturation level(SL) in inkjet-based 3D printing approach which
in each layer of powder during 3D printing build process. Such
is the ratio of liquid volume to the total free space of powder bed
evaporation can be achieved by using an external heat source such
[23]. Accordingly, Eq. (5) can be rewrite as:
as an infrared heater to scan each layer of powder before solvent
" 1=3 # deposition on a layer.
3r rm W0
Wf ¼ 1 þ ðr  rm Þ (6) To put these calculations in perspective, the conceptual illus-
ð1  rÞ r ð1  rÞ
tration of the overall procedure for capillary-mediated binderless
The bridge volume, V, for mono-dispersed spherical particles 3D printing is depicted in Fig. 3. Prior to start with the printing
can be calculated by Ref. [30]: process, a suitable solvent must be selected in light of chemical
composition of a powder feedstock in a manner that a single or
V ¼ 2pR2 H sin2 b (7) multiple solid product can be formed on the superficial layer of
powder particles when the solvent-powder interactions proceed
Where b is the bridge angle (Fig. A.1, Appendix A) which can vary (e.g. chemical or electrochemical reactions). The printing process
from very small value to 90 . Substituting H from Eq. (2) into Eq. (7) starts with selective deposition of the solvent in the form of
and rearranging yields droplets of a few tens of micrometers size through a print head onto
a stationary layer of powder within the powder bed (Fig. 3a). The
2pR3 W sin2 b kinetic energy of the droplets assists their rapid spreading over the
V¼ (8) particles surface to form networks of liquid bridges connecting
3r
adjacent particles in contact as time proceeds in the order of
A dimensionless quantity of the bridge per particle volume, V*, microsecond until the energy has been consumed [33]. Upon
is expressed as: maintaining the wet layer, single or multiple compounds which
differ from the powder and the solvent but originate from their
W sin2 b interactions trigger to form in the liquid bridges so that solid
V* ¼ (9)
2r interparticle necks can be created (Fig. 3b). These compounds are
also likely to form superficially in the adhering liquid layers far
In view of the hysteretic phenomenon, the critical separation at
from the liquid bridges that can transfer to the evolving bridges. In
which the liquid bridge ruptures can be estimated by Lc z V1/3
view of the hysteretic nature of capillary bridging assisted with
[30,31]. Combining Eqs. (8) and (2), Lc can be written as:
evolutionary progress of the compounds being formed in the
 1=3 interparticle necks, the next layer of powder can be spread on the
2pR2 sin2 b
Lc ¼ H (10) preceding layer without being displaced (Fig. 3c). After depositing
H2 the solvent into the new layer, liquid bridges form between parti-
Since 2pR2 >> H2, one readily observes that the critical sepa- cles in both interlayer and intra-layer (Fig. 3d). These steps of sol-
ration is remarkably larger than the thickness of liquid layer on vent deposition and powder spreading are repeated until the entire
particle surfaces. 3D object has built. Then, the whole powder bed can be dried to
Fig. 2 shows the plot of the liquid content in free space, syn- fully evolve interdigitate networks of solid interparticle necks in
onymous with the SL, required for the formation of liquid bridges as the as-printed object (Fig. 3e). Finally, the as-printed object can be
a function of particle packing fraction (i.e. Eq. (6)). The corre- removed from the surrounding loose powder within the powder
sponding V* against the packing density is also plotted in Fig. 2. It bed for sintering.
298 M. Salehi et al. / Acta Materialia 165 (2019) 294e306

Fig. 2. The liquid content in free space (Wf) together with the corresponding bridge per particle volume (V*) as a function of particle packing fraction. Relative density of the dense
random packing structure (i.e. 0.63) and the minimal liquid content of 3  104 are assumed as rm and W0, respectively, and 45 is assumed as the bridge angle in Eq. (9).

Fig. 3. Principle of capillary-mediated binderless 3D printing, a) a formulated solvent is selectively deposited into the powder bed, b) capillary bridges among adjacent particles
form once the particles are wet, in turn, the products of solvent-powder interactions form an evolving interparticle neck, c) the next layer of powder is spread, and the solvent is
selectively dispensed, d) capillary bridges between particles form within the new layer as well as the previous layer which will evolve into interparticle necks in both inter- and
intra-layers, and e) fully developed solid interparticle necks in each inter-and intra-layers of powder bed after complete drying of the whole powder bed form an as-printed object
which is ready for sintering.

3.2. Capillary-mediated binderless 3D printing of pure Mg powder
3.2.1. SEM and TEM studies
Fig. 4a shows macrograph of some as-printed pure Mg parts
fabricated via capillary-mediated binderless 3D printing, exhibiting
the capability of introduced approach to fabricate scalable parts.
Interdigitate networks of interparticle necks in the as-printed
condition connecting adjacent particles in contact to form a 3D
object is illustrated in Fig. 4b. Fig. 4c displays representative
interparticle bridges for the as-printed condition of samples fabri-
cated with SL of 80% wherein the center particle is connected to at
least six particles. The mean coordination number of particles in the
networks should be greater than 5.6 in view of the packing density
of powder used in this study [34]. Fig. 4d shows the micrograph of
fabricated parts with SL 80% in the as-sintered condition that in-
dicates all compounds formed in the as-printed condition was
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
Fig. 4. Capillary-mediated binderless 3D printed pure Mg parts, a) macrograph of parts made of pure Mg using SL of 80% in the as-printed condition, b) a representative SEM
micrograph of the interdigitate networks between particles in the as-printed condition for fabricated parts with SL of 80%, c) interparticle necks formed among particles in the as-
printed condition at higher magnification for fabricated parts with SL of 80%, and d) micrograph of fabricated parts with SL 80% after sintering in the as-sintered condition.
decomposed during the sintering process, and sinter necks be-
tween particles created after sintering.
Figs. 5 and 6 display cross-sectional TEM and SEM micrographs
of a pendular bridge formed by solvent-powder interactions for
printed sample with SL 80% in the as-printed condition. Table 1
summarizes the results of EDS analysis carried out on selected re-
gions on Fig. 6aec. The TEM micrograph of associated interparticle
neck region with corresponding elemental mapping analysis are
also illustrated in Fig. 7. In view of Figs. 5a and Fig. 6def, the
pendular bridge can be divided into three major regions, namely, (i)
region 1: the surface film far from the interparticle neck region
covering particle I; (ii) region 2: the interparticle neck region in
between the particle I and particle II; and (iii) region 3: the surface
film far from the interparticle neck region covering particle II. The
region 1 consists of surface film having up to 300 nm thickness that
convers the Mg particle I. Fig. 6d indicates the presence of a phase
with plate-like morphology along with two other phases (phases in
light gray and dark gray), which are also distinguishable in TEM
micrographs of this region (Figs. 5b and 6a). In view of EDS results
(Table 1, spectra 3e5) and in accordance with literature [35], the
phase with plate-like morphology could be Mg(OH)2 and the film
with less than 20 nm thickness covering the particle I could be
MgO. EDS results (Table 1, spectra 6 and 7) imply that the third
phase comprising majority of the region 1 could be MgH2. It should
be noted that formations of these three phases are plausible as a
result of the interaction between the solvent and Mg powder, ac-
cording to thermodynamic calculations [36]. The region 2 has a
porous structure that can be seen in Fig. 5d and e. Taking Fig. 5def,
Fig. 7, and EDS results (Table 1, spectra 12e16) into accounts, the
porous structure is made of a magnesium carbonate phase that
connected to MgO film on the surface of particle I and II, binding the
two particles. In the region 3, the plate-like morphology which is
indicative of Mg(OH)2 phase was not observed (Figs. 5c and 6c). EDS
results (Table 1, spectra 8e11) imply that the particle II could be
covered by a film composed of MgO and MgH2 with thickness
ranging from 20 nm to 80 nm.
299
3.2.2. Vibrational spectroscopy
The FTIR spectra of the samples printed with two different SLs of
80% and 120% in the as-printed condition are shown in Fig. 8a. MgH2
reveals two broad MgeH bands in FTIR spectrum. One is centered at
560 cm1 and the other is a flattop band in the range of
1000e1300 cm1 [37,38], both of which were observed in Fig. 8a. The
FTIR band at 855 cm1 was attributed to the out-of-plane bending
mode of CO23 unit of nesquehonite (MgCO3.3H2O), and the bands at
1405 and 1515 wavenumbers to its antisymmetric stretching mode
vibrations [39e41]. The 1650 cm1 band ascribes to the OeH
bending mode of structural H2O of nesquehonite which could be in
the range 1640e1691 cm1 [40,42]. The bands that can be seen
outside the fingerprint region in the wavenumbers between 1950
and 2550 cm1 are attributed to the asymmetric OCO stretching
mode and the second overtone of the symmetric OCO stretching
mode [43]. In addition, several low intensity bands in the range of
620 cm1 to 790 cm1, which were more visible in the spectrum of SL
120% sample, can be ascribed to nesquehonite [44]. MgO exhibits a
band at 434 cm1 which is related to the MgeO stretching vibration
[45e47]. Mg(OH)2 displays its characteristic band at 3698 cm1 [48].
The Raman spectra of the SL 80% and SL 120% in the as-printed
condition are shown in Fig. 8b. MgH2 can exhibit several bands in
Raman spectrum: the 120 cm1 and 953 cm1 bands are sharp
while the other bands centered around 268, 365, 555 and
1281 cm1 are broad [49]. The bands at lower frequency (below
300 cm1) are dominated by Mg atoms while the higher frequency
ones (above 450 cm1) are governed by H atoms [49e51]. The
positions and relative intensities of these bands perfectly matched
with the Raman spectra of the SL 80% and SL 120% samples (Fig. 8b).
The strongest nesquehonite Raman shift due to the CO2 3 sym-
metric stretching mode appears around 1098 cm1 [39,42] that
overlapped with the bands of MgH2. Furthermore, MgO has a broad
Raman shift centered at 618 cm1 [52,53]. This MgO band presents
as a shoulder in the Raman spectra of both SLs; however, it is more
discriminable in the SL 120% spectrum. The band at Raman shift of
3650 cm1 is assigned to Mg(OH)2 [54,55].
300 M. Salehi et al. / Acta Materialia 165 (2019) 294e306

Fig. 5. Cross-sectional TEM and SEM micrographs of a pendular bridge between pure Mg particles in as-printed parts using the SL 80%; a) The overall TEM representation of the
pendular bridge; b, c, e, and f) TEM micrographs of the selected regions at higher magnifications; and d) SEM micrograph of the interparticle neck.

3.2.3. Chemical composition analysis 3.3. Capillary-mediated binderless 3D printing of magnesium-zinc-

Chemical analysis results of the pure Mg parts printed using two
different SLs in both the as-printed and as-sintered conditions
along with the results of as-received pure Mg powder are sum-
marized in Table 2. The results demonstrated a slight increase in the
overall chemical composition of the as-printed condition than that
of the as-received powder in terms of C, O, and H elements, espe-
cially for the SL 80%. As can be seen in Table 2, the chemical
composition of the SL 80% in the as-sintered condition returned to
the composition of as-received powder. Likewise, after sintering of
the SL 120% samples, C and H contents reached the same levels as in
the as-received powder, and only the level of O marginally
increased than that of the as-received powder.
3.2.4. Thermal analysis
TGA and DTA results of printed samples using two different SLs
of 80% and 120% are shown in Fig. 9. Thermal decomposition began
around 50  C and continued progressively to 270  C that followed
by another decomposition in the range of 350  Ce400  C. The total
mass loss for the SL 80% and SL 120% between 50  C and 442  C
were found to be 0.39% and 0.74%, respectively. In the DTA pattern,
endothermic peaks were clearly observed around 70  C and 380  C
for both the SL 80% and SL 120%. Another obvious endotherm in
DTA patterns of the SL 120% was at 115  C.
zirconium powder
Fig. 10a shows a SEM micrograph of Mg-5.9Zn-0.13Zr alloy in the
as-printed condition wherein the funicular interparticle bridges
formed the interdigitate networks between particles in accordance
with the introduced concept of capillary-mediated binderless 3D
printing. Results of chemical analysis are summarized in Table 3.
The chemical composition of starting powder in the as-received
condition was slightly changed in the as-printed condition in
terms of O, H and C elements. After sintering the as-printed sam-
ples, not only the primary chemical composition of the as-received
powder was regained, the oxygen content in the as-sintered con-
dition also reduced. The optical micrograph of sintered sample at
577  C for 100 h is illustrated in Fig. 10b, and curves showing its
mechanical response under compression and tension are shown in
Fig. 10c and d. The mechanical properties of samples sintered at
577  C for two different holding periods of 40 h and 100 h, along
with the properties of polycaprolactone and various bone types are
tabulated in Table 4. In comparison, while the associated tensile
strength of the sintered sample is lower than the bone types, the
elastic modulus of the both sintered samples could fall in the ranges
of bone (~3e30 GPA) and the compressive mechanical properties
exceed the bone types. As can be seen, the obtained mechanical
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306 301

Fig. 6. TEM and SEM micrographs taken from the FIB milled SL 80% specimen in the as-printed condition, a-c) TEM images of the selected regions (numbers on each image
correspond to EDS locations, for which chemical composition is given in Table 1), e) SEM image of the pendular bridge, and d & f) SEM images of the selected regions at higher
magnifications.

Table 1
Chemical composition of various locations on TEM micrographs in Fig. 6aec.

Spectrum label 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

O (at. %) 2.70 3.21 48.20 44.18 41.96 17.63 13.59 10.24 26.77 36.30 27.93 45.9 41.31 44.02 47.25 39.47
Mg (at. %) 97.30 96.79 51.80 55.82 58.04 82.37 86.41 89.76 73.23 63.70 72.07 54.1 42.17 46.26 40.89 60.53
C (at. %) 0 0 0 0 0 0 0 0 0 0 0 0 16.52 9.72 11.66 0

properties of sintered sample are remarkably greater than poly-
caprolactone which is commonly used as a biodegradable polymer
for bone tissue engineering.
4. Discussion
4.1. Capillary-mediated binderless 3D printing of Mg powder: A
compositionally zero-sum process
Conserving oxygen content throughout the course of any AM
process for Mg based materials is a crucial factor in obtaining
successful parts. Oxidation of Mg causes several difficulties in AM
due to the enormous difference in the melting temperature of Mg
and MgO. Presence of oxygen as an impurity in a fabricated Mg part
could deteriorate its properties. Despite high affinity of Mg to ox-
ygen, oxidation prevention is always advantageous because
reducing MgO to Mg is much more challenging. In view of the
chemical analysis results (Table 2), preserving the oxygen content
in low level and minimal changing in the overall chemical
composition of the as-printed parts compared to the as-received
powder demonstrate the promise of the solvent and built cycle
used.
Vibrational spectroscopy (Fig. 8) confirms the presence of four
phases, namely, magnesium hydride (MgH2), nesquehonite
(MgCO3$3H2O), magnesia (MgO), and magnesium hydroxide
Mg(OH)2. Taking SEM and TEM studies for the region 1 together
with the FTIR and Raman spectroscopy into accounts, the particle I
is covered by a mixed film composed of MgH2 and a bi-layer of
MgO/Mg(OH)2. In SEM micrographs (Fig. 4b and c), MgH2 is
distinguishable as discrete micron/submicron sized particles
attached to the surface of some Mg powder, forming the bumpy
topography on outermost layer of particles as observed in the FIB
milled SEM and TEM micrographs for the region 1. In view of SEM
and TEM studies for the region 2 together with the vibrational
spectroscopy results, the particle II is covered by a bi-layer film
composed of MgO and MgH2. The presence of brucite on the surface
of particle I (the region 1) and its absence on the surface of particles
II (the region 3) indicate that the ionic species forming on the
surface of particles far from the bridge zone can transport to the
liquid bridges during the filling process. In accordance with the
introduced concept of capillary-mediated binderless 3D printing,
when the solvent is deposited, liquid bridges form instantly fol-
lowed by a slower filling process in which liquid transports from
the liquid layer on the surface of particles into the bridges. Mean-
while, the interactions between the solvent and the MgO film
surrounding the outermost surface of Mg particles trigger. Partial
dissolution of the MgO film in the solvent leads to release of Mg2þ
ions upon the exposure of solvent to the particles. When the liquid
(i.e. solution) becomes supersaturated, the precipitation of
Mg(OH)2 takes place on the surface of MgO film (Eq. (11)). Both
MgO and Mg(OH)2 are soluble in the solvent but the lower solu-
bility of Mg(OH)2 enables its precipitation at the expense of thin-
ning the MgO film. This causes a bi-layer film to form that gives
some corrosion protection [56].
Assisted by solvent evaporation during the printing process, the
solvent layer rupture occurs when the solvent drains into the
302 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
Fig. 7. TEM micrograph with corresponding elemental analysis maps of C, Mg, and O
elements, taken from the FIB milled SL 80% specimen in the as-printed condition.
bridges. This may leave discrete microdroplets on the surface of
particles. These local spots provide a susceptible location for
breakdown of the bi-layer film of MgO/Mg(OH)2 given that the
open circuit potential may exceed the breakdown potential
required. Accordingly, it provides sites for hydrogen reduction [57].
Further breakdown of the bi-layer film can be promoted by
hydrogen embrittlement [57]. The occurrence of film breakdown
also exposes an active oxide-free layer from Mg metal particles to
the solvent, resulting in the release of a local flux of Mg2þ ions into
the microdroplets. According to Perrault [58], three possible
cathodic reactions for corrosion of Mg are: (i) formation of MgH2,
(ii) generation of hydrogen, and (iii) co-existence of the MgH2 for-
mation and hydrogen generation. MgH2 can form in the whole pH
range during the corrosion of Mg either via the chemical reaction
(Eq. (12)) or electrochemical reactions (Eqs. (13)e(15)) [59]. In view
of the chemical analysis results and formation reactions of MgH2,
required Mg for the formation of magnesium hydride is mostly
supplied by the exposure of metallic layer beneath either the bi-
layer or MgO films to the solvent. As can be seen in Fig. A.2
(Appendix A) the breakdown of surface film on the particle I took
place in close proximity of the intersection between grain bound-
aries and the surface of particle that can provide the required Mg
with more ease through grain boundary diffusion.
Mg2þ (aq) þ 2OH (aq) 4 Mg(OH)2(s) (11)
Mg þ 2H (aq) 4 MgH2 (12)
Mg2þ þ 2Hþ þ 4e 4 MgH2 (13)
Mg(OH)2 þ 2Hþ þ 4e 4 MgH2 þ 2OH (14)
Mg þ 2Hþ þ 2e 4 MgH2 (15)
Confirmed by vibrational spectroscopy, SEM and TEM studies
demonstrate that the interparticle neck area (the region 2) with
highly porous structures is composed of MgCO3$3H2O which
nucleated and grew on the MgO film presented on the surface of Mg
particles, binding the particles I and II by forming the solid inter-
particle neck. According to the introduced concept of capillary-
mediated binderless 3D printing, contacts of the solvent with the
particles in the bridge areas commence with solvent deposition and
end by complete drying of printed parts during the 1-h holding
step. Formation of MgCO3.3H2O proceeds through dissolution-
precipitation from the MgO film as well as the ionic species
transported from the surface of particles to the bridge. As can be
seen in Fig. 5def, Figs. 6b, and Fig. 7, MgCO3.3H2O grew on the MgO
film both vertically and laterally. The lateral growth of the pre-
cipitates on each particle and their coalescence cause a solid
interparticle neck to form between the particles. The vertical
growth of the precipitates results in covering the MgO film that
suppresses the interaction of solvent with powder by blocking the
cathodic and/or anodic sites and lowering the conductivity of the
solvent within the bridge [56]. Thus, the formation of MgCO3.3H2O
can insulate the MgO film and underneath Mg metal particle
against the solvent. According to the thermodynamic calculations
[36], this hydrated magnesium carbonate is thermodynamically
stable in contact with the solvent which means that MgCO3.3H2O
no longer reacts with the solvent upon its formation. In other
words, nesquehonite can preserve the solvent within its porous
structure without undermining the formed solid interparticle
necks so that the excess solvent pocketed in the bridge area could
be evaporated during the 1-h holding step. Comparison made be-
tween the carbon contents of the SL 80% and SL 120% in the as-
printed condition (Table 2) shows almost the same amount of
carbon. This demonstrates that the nesquehonite phase could
effectively preserve the excess solvent in its highly porous struc-
tures. The presence of nano-sized nodules on the inner surface of
nesquehonite velum (Fig. 5d), and the Mg content along the nes-
quehonite septum (Table 2, spectra 13e15) indicate that the ionic
species existing in the solvent trapped in the nesquehonite velums
can be deposited as MgH2 while the excess solvent is being evap-
orated. In view of the minimum liquid content required for for-
mation of liquid bridges and the corresponding bridge per particle
volume as discussed in section 3.1, having nesquehonite with a
highly porous structure and such an insulating and stability enables
to further minimize the bridge per particle volume as well as the
solvent-powder interactions, resulting in the minimal change in
the overall chemical composition of as-printed parts (Table 2).
All products of the solvent-powder interactions can be ther-
mally decomposed into their primary constituents without leaving
any residue behind during sintering of as-printed parts. Thermal
decomposition of nesquehonite consists of a three-step dehydra-
tion reaction and a single step decarbonation of anhydrous mag-
nesium carbonate, according to the following steps. In particular,
the three-step dehydration reaction occurs in the range
55  Ce109  C, 109  Ce160  C, and 160  Ce270  C, respectively, and
the loss of CO2 takes place between 300 and 442  C [42].
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306 303

Fig. 8. Vibrational spectroscopy of pure Mg samples printed by SL 80% and 120% in the as-printed condition, a) ATR-FTIR spectra and b) Raman spectra.

Table 2 MgCO3.H2O / MgCO3 þ H2O [ (18)

Elemental analysis of pure Mg alloy in different conditions.

Specimen condition Oxygen (wt.%) Hydrogen (wt.%) Carbon (wt.%) MgCO3 / MgO þ CO2 [ (19)
As-received powder 0.010 0.086 ± 0.006 0.031 ± 0.002
As-printed- SL 80% 0.055 ± 0.005 0.183 ± 0.009 0.089 ± 0.003
The dehydrogenation of magnesium hydride and dihydrox-
As-sintered- SL 80% 0.013 ± 0.001 0.024 ± 0.002 0.020 ± 0.002 ylation of brucite are shown as follows [49,60]:
As-printed - SL 120% 0.325 ± 0.021 0.290 ± 0.035 0.097 ± 0.005
As-sintered- SL 120% 0.017 ± 0.001 0.029 ± 0.004 0.020 ± 0.001 Mg(OH)2 / MgO þ H2O [ (20)

MgH2 / Mg þ H2 [ (21)
MgCO3.3H2O / MgCO3.2H2O þ H2O [ (16)
The decomposition of brucite and magnesium hydride occur in
MgCO3.2H2O / MgCO3. H2O þ H2O [ (17) the range of 263  Ce459  C and 330  Ce404  C, respectively
304 M. Salehi et al. / Acta Materialia 165 (2019) 294e306

Fig. 9. TGA and DTA curves of as-printed pure Mg samples using, a) SL of 80% and b) SL of 120%.

Fig. 10. Capillary-mediated binderless 3D printed magnesium-zinc-zirconium alloy, a) SEM micrograph of the interdigitate networks between particles in the as-printed condition,
b) optical micrograph of sintered samples at 577  C for 100 h, c) compressive and tensile stress-strain response of sintered sample at 577  C for 100 h.

Table 3 DTA pattern (Fig. 8), the endothermic peaks observed below 200  C
Elemental analysis of the Mg-5.9Zn-0.13Zr alloy in different conditions. are ascribed to the dehydration of nesquehonite. Another endotherm
Specimen condition Oxygen (wt.%) Hydrogen (wt.%) Carbon (wt.%) in DTA patterns of the SL 80% and SL 120% around 385  C can relate to
As-received powder 0.013 ± 0.001 0.071 ± 0.008 0.020 ± 0.001
the decomposition of brucite, anhydrous magnesium carbonate, and
As-printed 0.049 ± 0.002 0.304 ± 0.002 0.050 ± 0.002 magnesium hydride. In addition, the thermal analysis results exhibit
As-sintered 0.003 0.015 ± 0.001 0.020 ± 0.001 that the total mass loss in TGA curves for the SL 80% and SL 120% are
in accordance with the sum of H, C, and O elements obtained by the
chemical analysis (Table 2). Furthermore, the micrographs of SL 80%
[42,60,61]. The TGA results (Fig. 8) demonstrated that thermal samples before and after sintering (Fig. 4b and d) indicate that all
decomposition of nesquehonite begins around 50  C and continues superficially formed compounds in the printing process decomposed
progressively to 270  C that is followed by a liberation of CO2. In the during sintering step, and permanent necks formed among particles
 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
Table 4
Materials properties of the sintered Mg-Zn-Zr alloy and various bone types.
Material Ultimate compressive strength Compressive strain at maximum
(MPa) strength (%)
Sintered sample at 577  C for 179 ± 1.3 38.3 ± 4.1
40 h
Sintered sample at 577  C for 260.3 ± 6.4 41 ± 1.9
100 h
Polycaprolactone [71] 38.7 5.2
Tibia bone [72] 159 e 140
Femur bone [72] 167 e 121
Radius bone [72] 114 e 149
Humerus bone [72] 132 e 130
*Produced by selective laser sintering with nearly full density (>95%).
in the as-sintered condition. Given the aforementioned-formation
mechanisms of the products of solvent-powder interactions during
3D printing process, all the products can be totally decomposed into
their initial constituents in the starting Mg powder with no demand
for any debinding step in sintering profile, resulting in the initial
chemical composition of as-received powder remains intact in the
as-sintered condition (Table 2).
The promise of capillary mediated binderless 3D printing to
fabricate parts with zero contamination is further demonstrated by
developing a second Mg alloy made of magnesiumezincezirco-
nium powder. In a similar way to the pure Mg alloy, the interdigi-
tate networks between Mg-Zn-Zr particles stem from the
interactions between the solvent and powder, enabling 3D objects
to be fabricated in accordance with the concept of capillary-
mediated binderless 3D printing (Fig. 10a). Similarly, the chemical
composition was marginally changed in the as-printed condition,
and then the initial chemical composition was completely retrieved
by conducting sintering step (Table 3). As-printed parts can be
sintered to obtain various structures with a range of mechanical
and physical properties by adjusting sintering profiles. In view of
classification of Mg alloys as third generation biomaterials in terms
of clinical outcomes [62], mechanical characteristics of 3D printed
Mg alloys with an interconnected porous structure could be
tailored to match the properties of various bone types, offering
significantly greater properties compared to polycaprolactone
which is currently using as a biodegradable polymer for bone tissue
engineering (Table 4). Moreover, well established knowledge of
sintering realized in powder metallurgy process can be employed
to make properties of printed parts optimized in a manner that the
printed parts after sintering compete against traditionally fabri-
cated counterparts for structural applications. For example, using
tremendous flexibility of metal sintering, competitive properties in
binder jet 3D printed parts than those of casted or hot isostatic
pressed were accomplished after optimization of sintering condi-
tions for nickel-based alloy 625 [63e65].
4.2. Benefits of capillary-mediated binderless 3D printing
The notion of paradigm shift towards rapid, cost-effective, and
environmentally sustainable AM process at ambient temperature
based on capillary-mediated binderless 3D printing is clear. Mate-
rials deposition rate in inkjet-based 3D printing is up to 20-folds
faster than the other metal AM methods [23]. However, the need
for post-printing process including debinding step may compro-
mise the overall throughput of inkjet-based 3D printing. As there is
no result on binder jet 3D printing of Mg or Al based materials,
comparison could be made with literature on metal injection
molding of Mg that uses binder materials as binder jet 3D printing.
It has been reported that up to 20 h are required for debinding of
powder injection molded Mg parts in a combined solvent and
305
Ultimate tensile strength Elongation to Elastic modulus
(MPa) failure (%) (GPa)
e e 17.3 ± 0.1
70.9 ± 1 0.7 ± 0.1 21.5 ± 0.1
10.5 4.3 0.36
e 18.1
e 17.2
e 18.6
e 17.2
thermal debinding process [66e69]. Moreover, more reactive ele-
ments than Mg (e.g. calcium) are inevitably needed in starting
powder feedstock for powder injection molding of Mg so that the
molded Mg parts could be sintered since oxidation of Mg powder
may occur due to reactions of Mg powder with polymeric binder
materials as well as with by-products of debinding processes
[67,70]. This imposes restriction on the accessible choice of feed-
stock compositions. Regardless of reducing lead time by elimi-
nating the debinding step, using the binder-free 3D printing
method introduced here allows to further embrace the concept of
rapid prototyping inhered in AM techniques. Lower viscosity of a
solvent based ink compared to polymeric based binders enables a
print head to deposit the ink faster. Furthermore, the deposited ink
is able to rapidly penetrate through each layer of powder to create
intra- and inter-layer binding and therefore the build pace im-
proves. In the current work, the overall time to build a layer of Mg
powder with 100 mm thickness is only 12 s, and the final drying
period after the end of build cycle is 60 min which is conducted in
the 3D printer machine. Following the drying step, as-printed parts
can be immediately removed from the surrounding loose powder
within the powder bed. In the binder jet 3D printing, conversely,
the whole powder bed needs to be transferred in a curing oven and
heated to fully set the jetted polymer, only then as-printed parts
can be removed from the surrounding loose powder.
As-printed parts fabricated by the capillary-mediated binderless
3D printing approach can be sintered by using either the conven-
tional or microwave furnaces. In binder jet 3D printing, the pres-
ence of polymeric binder materials requires adjusted sintering
profile to facilitate pyrolysis and degassing of polymer binder
which is typically needed slow heating ramp rate. In addition, the
as-printed parts after debinding and before being sintered can
readily lose their structural integrity. These prevents binder jet
printed parts from sintering by microwave furnace during a single
step process. The flexibility in sintering could benefit the capillary-
mediated binderless 3D printing from environmental sustainability
and lead time, lending itself to an efficient and rapid AM technique
under ambient conditions while all microstructural trans-
formations occur during the following sintering step on the basis of
well-established knowledge of sintering in powder metallurgy.
The current work can be extended to a variety of materials,
especially the currently unprintable metals and ceramics via AM
techniques, by formulating suitable solvents. Furthermore, this
concept can be employed in other materials processing techniques
that involve use of ex-situ binder materials (e.g. metal injection
molding) to make them faster and more sustainable.
5. Conclusions
According to the described conceptual model, the hysteretic
nature of the capillary bridging provides a basis for ex-situ
306 M. Salehi et al. / Acta Materialia 165 (2019) 294e306
binderless 3D printing based on layer-by-layer assembly of powder
particles such that the capillary-mediated interactions of a solvent
and the powder particles autogenously derive solid interparticle
bridges among adjacent particles. The minimum content of a sol-
vent required for the formation of capillary bridges among powder
particles (i.e. Eq. (6)), along with the corresponding compositional
change as a result of the solvent-powder interactions in as-printed
objects (i.e. the bridge per particle volume as in Eq. (9)) is correlated
with the packing fraction of a given powder. Combining this con-
ceptual framework with chemistry adopted for Mg alloys, solid
interparticle bridges autogenously form in-situ among Mg particles
due to the interactions of selectively deposited liquid solvent with
the superficial oxide film of Mg powder during printing cycle,
enabling a 3D object of Mg alloys to form without sacrificing the
build speed. Engineered highly porous structures of the interpar-
ticle bridges composed of MgCO3.3H2O provide insulating and
stability characteristics that allow the solvent-powder interactions
to minimize. These bridges in the as-printed Mg object fully
decompose into their initial constituents in the starting Mg powder
over the course of sintering process in the absence of debinding
treatment, producing functional Mg parts with zero process con-
taminants. With no need for ex-situ binder and debinding treat-
ment, this rapid capillary-mediated binderless 3DP could be
extended to the other materials in order to provide an opportunity
for AM to simplify in line with conventional powder metallurgy
without compromising the benefits of AM.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.actamat.2018.11.061.
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