Additive Manufacturing 30 (2019) 100787

Contents lists available at ScienceDirect

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

Full Length Article

Production of net-shape Mn-Al permanent magnets by electron beam T

melting
⁎
I.A. Radulova, , V.V. Popov Jr.b, A. Koptyugc, F. Maccaria, A. Kovalevskyb, S. Esselb,
J. Gassmannd, K.P. Skokova, M. Bambergere
a
Technische Universit at Darmstadt, Alarich-Weiss-Str. 16, 64287, Darmstadt, Germany
b
Israel Institute of Metals, Technion R&D Foundation, Technion City, 3200003, Haifa, Israel
c
Sports Tech Research Centre, Mid Sweden University, Akademigatan 1, SE-831 25, Ostersund, Sweden
d
Fraunhofer Research Institution for Materials Recycling and Resource Strategies IWKS, Rodenbacher Chaussee 4, 63457 Hanau, Germany
e
Department of Materials Science and Engineering, Technion Israel Institute of Technology, Technion City, Haifa, 3200003, Israel

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

Keywords: The main goal of this work is the adoption of additive manufacturing for the production of inexpensive rare-
Additive manufacturing earth free MnAl-based permanent magnets. The use of more advanced binder-free additive manufacturing
Printed magnets technique such as Electron Beam Melting (EBM) allows obtaining fully-dense magnetic materials with advanced
Electron beam melting topology and complex shapes. We focus on the feasibility of controlling the phase formation in additively
Mn-Al alloys
manufactured Mn-Al alloys by employing post-manufacturing heat treatment. The as-manufactured EBM sam-
Permanent magnets
ples contain 8% of the desired ferromagnetic τ-MnAl phase. After the optimized annealing treatment, the content
of the τ-phase was increased to 90%. This sample has a coercivity value of 0.15 T, which is also the maximum
achieved in conventionally produced binary MnAl magnets. Moreover, the EBM samples are fully dense and have
the same density as the samples produced by conventional melting density.

1. Introduction temperature range from 400 to 700°C. Such treatment provides a

Complex alloy development and processing procedures of magnetic
materials are essential for improving the efficiency and performance of
devices in electric power generation, conditioning, transportation, and
other sectors of economy dependent on electric power. At present, the
permanent magnets (PM) market is dominated by two material classes:
rare-earth magnets (mostly Nd-Fe-B) and hard ferrites. The former
being of high cost and high performance, whereas the latter being of
low cost and low performance [1–6] Therefore, the development of a
new low-cost material with magnetic properties in-between ferrites and
Nd-Fe-B magnets is of a great scientific and technological interest. In
this context, the Mn-Al alloys containing τ-phase (L10 structure) have
the potential to fill this gap as they exhibit a significant magnetocrys-
talline anisotropy constant K1 of 1.5 MJ/m3 and, in the case of ideal
texture, an upper limit of maximum energy product is 95.5 kJ/m3.
However, the τ-phase in this system is metastable; thus, processing
requires different additional steps in order to avoid the formation of
equilibrium non- ferromagnetic phases [7]. For example, as proposed in
[8], in order to obtain the ε-phase, the heat treatment of the material at
1100°C is followed by quenching and short isothermal annealing in the
transformation of the ε-phase into the τ-phase. The drawback of this
route is the possibility of further decomposition of the desired τ-Mn-Al
phase into γ2 and β phases during longer annealing. Most of the alter-
native techniques for the production of Mn-Al permanent magnets re-
ported in the literature are based upon rapid solidification and me-
chanical alloying [9–11]. All these processes are time- and energy
consuming, and great efforts are directed to finding a more efficient
synthesis route for production of rare-earth free permanent magnets.
New options for the processing of functional materials in complex
three-dimensional shapes are arising with the progress in various ad-
ditive manufacturing (AM) techniques. These methods initially
emerged as a prototyping technique in polymers, but were further de-
veloped to include metal and alloys.
One of the main obstacles in successful additive manufacturing of
hard magnetic materials is the engineering of a desired microstructure
in fully dense printed blocks or complex geometries, and this problem
has not yet been solved. In fact, the functional magnetic properties of
permanent magnets (both Br and Hc) are extrinsic in nature and com-
pletely determined by the microstructure developed during the magnet
processing. Thus, the developing the additive manufacturing technique,

⁎
Corresponding author.
E-mail address: radulov@fm.tu-darmstadt.de (I.A. Radulov).

https://doi.org/10.1016/j.addma.2019.100787
Received 14 February 2019; Received in revised form 31 May 2019; Accepted 6 July 2019
Available online 06 September 2019
2214-8604/ © 2019 Elsevier B.V. All rights reserved.
I.A. Radulov, et al.
which potentially offers an effective way for fabricating full-dense high-
energy permanent magnets is a challenging task. On the other hand,
freedom of shapes achievable with the AM methods could still be
combined with certain post-processing resulting in industrially attrac-
tive technological process. The same time the drive to increasing sus-
tainability of the manufacturing and decreasing dependence on certain
critical materials like RE metals are strong motivators towards devel-
oping new materials and technologies promising viable alternatives to
conventional processing techniques used for production of high-energy
permanent magnets.
At present, AM in metallic materials is successfully applied in dif-
ferent technological areas including automotive and aerospace [12], as
well as in biomedicine for implant and special medical tool manu-
facturing [13,14] Though AM of magnetic materials is in its infancy of
development, it offers new possibilities for the production of parts with
complex geometries and net-shape structures from known and new
materials for bonded and fully dense magnets [15]. Some initial reports
are available for the use of AM for polymer-bonded magnets through
different techniques, mainly focused at Nd-Fe-B compounds [15–18].
First attempts were conducted using Selective Laser Melting (SLM) to
produce an isotropic fully dense Nd-Fe-B magnet [17,19] and the use as
a fast solidification technique for microstructural design [18]. However,
the control of grain size, microstructure and oxidation is challenging for
achieving desired magnetic properties by using SLM. Others yet un-
addressed challenges are full densification and texture in a 3D printed
polycrystalline magnet.
Electron Beam Melting (EBM) is another powder bed additive
manufacturing (PB-AM) method, which along with the laser-based PB-
AM is quite rapidly developing and finding multiple applications in
different areas of technology. EBM has certain specific features that
should be very relevant in context of magnetic materials manu-
facturing. First, manufacturing is carried out in high vacuum (10−5 bar
or better) and high temperatures [20,21], which are desirable for
processing highly oxidizing materials and for obtaining fully dense
magnets. Extremely fast and highly localized melting-cooling achieved
by the beam-based AM methods like EBM are also beneficial for pre-
serving metastable phases in the manufactured components, as it was
shown by the manufacturing of bulk metallic glass [21]. However, no
attempts to manufacture magnetic materials by EBM were reported in
the literature to date.
In principle, an advanced binder-free AM technique such as EBM
allows obtaining full-dense Mn-Al alloys, but this process inevitably
leads to melting of the powder and the appearance of a new micro-
structure, which is likely to be unfavorable for a high coercivity of the
resulting material if not controlled properly.
In this work, we aimed to adapt the EBM technique to produce fully
dense rare-earth-free Mn-Al permanent magnets. We focused on con-
trolling the de- sired micro-structure responsible for high coercivity (i)
during the EBM processing and (ii) by means of post-manufacturing
heat treatment.
2. Materials and methods
Mn53Al47 ingot was prepared by induction melting of 99.99% pure
Mn and Al under protective argon atmosphere. To compensate the
evaporation during the melting process the initial Mn content was in-
creased by 3 wt.%. The molten Mn-Al binary alloy was directly quen-
ched by casting it into a rectangular copper mold. The as-cast bulk alloy
ingot (5 kg) was prepared for ball milling by crashing it into 2–5 mm
chips. The milling was performed in a planetary ball mill (Pulverisette
6, Fritsch) at a rotation speed of 250 rpm with a powder to balls mass
ratio of 1:10. The as-milled binary powder was sieved and the powder
fraction with particle size below 100 μm was used for the EBM ex-
periments (see Fig. 1).
Poor powder bed properties due to non-spherical and not optimized
powder was an additional challenge. This powder was very far from
2
Additive Manufacturing 30 (2019) 100787
Fig. 1. The Mn-Al ball-milled powder used in experiment (SEM).
machine manufacturer requirements both in powder particle size dis-
tribution and its flow ability.
Particle shapes of the used powders were quite irregular, and sig-
nificant amount of the grains with sizes below 10 μm was present. Such
powders have generally tighter packaging (and thus- higher apparent
densities), and strongly reduced flow ability. Our setup with vertical
powder feeding [22,23] allows working with such powders, though
with the layers thicker than 75-100 μm. Consecutive adjustments are
needed to the preheating, sintering and melting parameters, accom-
modating for relatively thick layers of the powder, and larger than usual
volume of molten metal as compared to the volume of powder de-
posited.
There are no commercial gas atomized Mn-Al powders available up
to date. The ball-milling for Mn-Al magnet manufacturing is also a
beneficial method, as it provides necessary microstructure refinement
and defects propagation. Our previous experiences with material de-
velopment indicate that despite the suggestion that powder is com-
pletely remelted in EBM process, initial microstructure of the material
in the powder does matter. Hence, ball-milling was chosen as a valid
powder preparation method.
The additive manufacturing was carried out in an adjusted for the
research applications Arcam EBM A2 machine (Arcam EBM, Sweden).
The EBM system was modified for the development of new materials,
and optimized for the experiments with small powder batches up to
500 ml (see [12,17] for details). Present design of the powder delivery
system in this modified setup allows using powders with rather wide
particle size distribution and relatively poor flowability, which is not
common for the commercial production-oriented Arcam machines (see
Fig. 2). This setup uses round start plates of 82 mm in diameter (see
Fig. 2c) and powder container with vertical powder delivery “riding” on
the rake system leveling the powder layer (see Fig. 2a).
Essential requirement of the EBM process is the need of preheating
step prior to the powder melting. We have found that for Mn-Al alloys,
the adequate temperature of the platform is about 830°C. Preheating
stage of the process is needed for semi-sintering of the powder and
avoiding forming a “cloud” in the chamber due to the intense charging
(effect known with EBM users as “smoke”). It has a potential of da-
maging the machine, and when this occurs, the process must be
aborted. Thus, powder layers should be semi-sintered by softer beam
during separate preheating step. Additional heating steps may also be
needed within each layer processing to upkeep the desired process
temperature of the build. Accordingly, the development of the process
settings for the powders in new material is starting with powder char-
acterization and involves adjustments for:
(i) initial preheating, (ii) melting, and (iii) additional heating stages.
I.A. Radulov, et al.
Fig. 2. a - The modified Arcam EBM system: (1) heat shields, (2) powder hopper, (3) rake, (4) start platform; b EBM process in modified A2 machine as seen through
inspection window; c - start platform (3) with the manufactured cubic specimens (1) surrounded by the sintered powder (2).
Table 1
Processing parameters used by the EBM of Mn-Al.
Layer thickness 100 μm
Line offset 100 μm
Maximum beam current (EB) 30 mA
Average chamber temperature 830 °C
Further development of the manufacturing process and its transfer from
research to industrial environment commonly involves thorough opti-
mization. Fig. 2b shows the glow of the powder and metal components
as it is seen through the inspection window of the ARCAM machine
during the preheating stage of process. Fig. 2c shows support plate risen
over the working table with a few layers completed and loose powder
removed. The larger rectangular ‘cake’ of the semi-sintered powder (2)
encrusts eight solid samples (1), with clearly visible upper surfaces of
the last molten layer and start platform (3). The proper preheat stage
adjustment should provide powder that is just enough semi-sintered to
avoid ‘smoke’ events, but can be broken so the powder in an industrial
process can be reused. The main goal of the present work was to assess
through the series of experiments a possibility of EBM- manufacturing
of the non rare-earth-based materials for permanent magnets. Thus, no
advanced parameter optimization for more stable process and for
complex structures such as lattices and supports were performed. In our
experiments, the layer thickness was chosen to be 100 μm, a compro-
mise between faster sample manufacturing and deeper layer re-melting.
Though it may be not optimal, parameters were adjusted (as given in
Table 1) for it to produce test samples with adequate quality. As a re-
sult, series of 10 × 10 x 10 mm3 Mn-Al samples were produced. The as-
printed material was carefully removed from the support plate for
further characterization and investigation of the phase formation in
Mn-Al in as-printed state and in the samples subjected to three different
heat treatment.
The choice of sample dimensions is governed by the protocol used
for the material development at Mid Sweden University. Initial tests are
performed on the identical in size prismatic samples with the base
10 x 10 mm. Sample height is chosen between 5 and 30 mm depending
on the availability of the precursor powder. Initially, all samples are
manufactured using the same process parameters, exactly the strategy
used in present research. After initial process yields solid samples, all
samples are manufactured with varying parameters for the process
optimization. However, the full process parameter optimization was
beyond the scope of present study.
Based on the literature data [24], two different approaches can be
applied in order to produce the ferromagnetic τ-phase in Mn-Al as-
manufactured samples. The first approach is a direct low temperatures
annealing, and the second one is a two-step annealing with first step at
higher temperatures (1100°C), in order to transform the entire sample
to ε-phase, followed by second low temperature annealing to transform
ε-phase into τ-phase, as described in the following paragraph.
3
Additive Manufacturing 30 (2019) 100787
The manufactured bulk samples were sliced into 1-mm-thick plates.
The plates were separated into four sets, sealed in quartz tubes under
protective argon atmosphere, and annealed under different conditions.
The annealing of all samples was performed in a pre-heated furnace.
After annealing, the quartz tubes were quenched into cold water in
order to ensure fast cooling rates. The as-printed material further in the
text named as samples of series A was used as a reference. Samples
treated in different ways, as described below, are referred to as series B,
C and D. Samples of series B were annealed at temperatures between
450 and 550°C for a period of 30–120 min to induce the ε→τ phase
transformation. Samples of series C were homogenized for 60 h at
temperature of 1100°C and quenched in the water. Samples of series D
were first homogenized at 1100°C and then annealed at temperatures
between 450°C and 550°C for a period of 30–120 min (see Table 3).
The crystallographic structure of all samples was characterized by
X-ray powder diffraction. The measurement was carried out on a
StoeStadi P powder diffractometer with Mo Kα1 radiation, in trans-
mission geometry, in the 2θ range between 5 and 50°. Phase matching
and unit cell refinements were done using FullProf/WinPLOTR. The
phase purity and the elemental composition were evaluated using a
Scanning Electron Microscopy (SEM) with energy dispersive X-ray
spectroscopy (VEGA 3 system by Tescan). SEM images in the back-
scattered contrast were obtained using polished samples without
etching. The magnetic domain structure was studied by magneto-op-
tical Kerr effect (MOKE) microscopy (Zeiss Axio Imager.D2m – evico
magnetics). To analyze the transformation of magnetic domain struc-
ture during magnetization/demagnetization of the sample, a Halbach
cylinder made of Nd-Fe-B magnet was used. The applied magnetic field
was of 1.3 T. The image contrast was enhanced by subtracting the non-
magnetic background image from the collected average image using
KerrLab software. The magnetic properties were measured at room
temperature under external magnetic fields up to 2 T using a PPMS
(Quantum Design PPMS-14). The measurements were performed before
and after annealing samples; to minimize the demagnetization due to
the shape anisotropy, 1 × 1x5 mm3 needle-shaped samples were cut
from the initial bulk by a wire saw.
3. Results and discussion
Typical as-printed Mn-Al cubic sample is shown on Fig. 3a. The
surface of the sample is rough and contains parts with reduced density.
Such undesirable effects are commonly caused by not optimized pre-
heating and melting parameters not matching certain powder proper-
ties (flowability, wettability etc.). Among other critical factors, one can
also mention a significant difference in the evaporation efficiency of the
alloying elements from the melt pool, which is significantly overheated
above the melting point [25,26]. The typical sample cross-section
image is shown in Fig. 3b. Here, most of the sample contains dense bulk
material, as also shown by the fractured surface (Fig. 3c) with typical
intergranular fracture characteristics; however, some areas are
I.A. Radulov, et al. Additive Manufacturing 30 (2019) 100787

Fig. 3. a - Mn-Al cubic samples produced by EBM, b - inhomogeneity regions inside the as-printed Mn-Al sample, c - crystallinity in the as-printed Mn-Al bulk sample,
d - SEM image of the as-printed Mn-Al bulk sample. The arrow indicates the needle-shaped exclusions of pure aluminum caused by segregation.

inhomogeneous (lack of fusion and so-called balling defects). Such

defects are common in samples produced without optimization of
preheating and melting processes. The present study aimed to assess the
feasibility of EBM-manufacturing and functional magnetic properties of
Mn-Al magnets, thus for further investigation of structural and mag-
netic properties full-dense part of Mn-Al samples were used. The SEM
and EDX analysis shows that the chemical composition of the as-man-
ufactured bulk samples remain the same as of the starting powder -
Mn53Al47. EDX analysis has shown that tiny needle-shaped exclusions of
pure aluminum (see Fig. 3d). Additional experiments reveal possible
reason for the formation of such inclusions: it can be due to the over-
heating of the samples during EBM process. Thus, for further optimi-
zation of the process, it may be necessary to adjust the average working
temperature at which the processed parts are kept. The inner parts of
the as-printed samples contain a mixture of different phases; therefore,
an additional heat treatment is required in order to transform the Mn-Al
alloy to bulk samples with dominating L10 phase.
The as-manufactured samples from series A were used as a re-
ference. From the magnetization curves presented in Fig. 4, it is clear Fig. 4. Magnetic properties of the samples from series A (as printed); series B
that as-manufactured samples (Sample A, solid black line) already show (annealed for 30 min at 500°C); series C (annealed for 60 h at 1100°C); and
ferromagnetic behavior and coercivity of about 0.1 T. This is a clear series D (annealed for 60 h at 1100°C and for 30 min at 500°C). The inset shows
indication that a certain amount of the metastable ferromagnetic τ- the properties of initial and annealed powder.
phase can be obtained through direct EBM manufacturing (similar ef-
fect - the metastable state formation during the EBM processing of bulk Table 2
metallic glasses was reported earlier by Koptyug et al. [21]). The figures of merit of the Mn-Al as-printed and annealed samples.
The obtained coercivity and magnetization of 10 A m2/kg for the as- Sample Br (T) Hcj (T) Hbc (T) BHmax (kJ/m3)
manufactured samples (Sample A at Fig. 4) are rather low as compared
to what can be achieved with other fabrication techniques (for example, A 0.02 0.1 0.015 0.05
B 0.04 0.11 0.030 0.25
coercivity and magnetization of 0.4 T and 75 A m2/kg, respectively, as
C 0.12 0.08 0.050 1.20
reported in [27]). The figures of merit for all Mn-Al samples are sum- D 0.18 0.06 0.050 1.85
marized in Table 2.
The XRD pattern of the as-printed Sample A is shown in Fig. 5
(bottom line). The observed diffraction maxima point to the coexistence Based on the XRD data the theoretical bulk density was calculated to
of three different phases: stable γ2-phase, high temperature ε-phase and be 5.2 g/cm3, while the geometrical sample density was found to be
desired metastable ferromagnetic τ-phase. The quantitative results of 5.1 g/cm3.
the Rietveld refinement are presented in Table 3. Therefore, it can be stated the samples produced by EBM process are

4
I.A. Radulov, et al. Additive Manufacturing 30 (2019) 100787

Table 3 fully dense.

XRD Results for Mn-Al as-printed and annealed samples. Fig. 6a presents the typical SEM image of the sample from series A.
Sample phase fraction (wt. %) The microstructure consists of the matrix γ2-phase with inclusions of ε-
phase and τ-phase. The phases were identified based on the back-
Name Annealing ε γ2 τ scattered contrast (which gives information about different composi-
tions) and the EDS analysis (quantitative chemical composition) of each
A as printed 20 ± 2 72 ± 3 8 ± 4
B 30 min @ 500 °C N.D. 77 ± 3 23 ± 2 phase.
C 60 h @ 1100 °C 43 ± 8 7± 3 50 ± 5 Kerr microscopy image of Sample A is shown in Fig. 7a. The po-
D 60 h @ 1100 °C N.D. 10 ± 1 90 ± 2 larized light microscopy allows to distinguish the ε-phase (with its
30 min @ 500 °C homogeneous internal microstructure) and the τ-phase, where twinning
structure is well pronounced due to its high magneto-optical Kerr
N.D. - not detected.
contrast. Obviously, the phase content and microstructure of the as-
manufactured samples (series A) are not optimal and need to be further
enhanced by annealing.
The samples from series B were subject to annealing for 30 min at
temperatures between 450°C and 600°C with temperature steps of 25°C.
Due to the transformation of the high temperature antiferromagnetic ε-
phase to metastable ferromagnetic τ-phase after short heat treatment at
500°C the magnetization of the sample B is increased (see Fig. 4, red
dotted line). The optimal temperature leading to the highest magneti-
zation and coercivity was found to be 500°C. Additional annealing at
500°C with varying the dwelling time between 10 and 180 min were
carried out for optimization of magnetic properties, but we found that
an optimal annealing time is 30 min. The optimal magnetic properties
of series B samples were MS = 20 Am2/kg and HC = 0.1 T corre-
spondingly.
The samples from series B were subject to annealing for 30 min at
temperatures between 450°C and 600°C with temperature steps of 25°C.
Due to the transformation of the high temperature antiferromagnetic ε-
phase to metastable ferromagnetic τ -phase after short heat treatment at
500°C the magnetization of the sample B is increased (see Fig. 4, red
Fig. 5. XRD patterns of the samples from series A, B, C and D (as described in dotted line). The optimal temperature leading to the highest magneti-
Table 3). zation and coercivity was found to be 500°C. Additional annealing at
500°C with varying the dwelling time between 10 and 180 min were
carried out for optimization of magnetic properties, but we found that
an optimal annealing time is 30 min. The optimal magnetic properties

Fig. 6. SEM images using the backscattered contrast of the sample from a) series A (ε, γ2 and τ-phase), b) series B (γ2 and τ-phase), c) series C (ε and τ-phase) and d)
series D (mostly τ-phase).

5
I.A. Radulov, et al.
Fig. 7. Kerr-microscopy images of samples A–D confirm the results about the τ -phase formation obtained by XRD and listed in Table 3.
of series B samples were MS = 20 A m2/kg and HC = 0.1 T corre-
spondingly.
The XRD pattern of sample B and the phase fractions obtained by
Rietveld refinement (see Table 3) show that the high temperature ε-
phase vanishes. At the same time, an insignificant increase in the phase
fraction of the stable γ2-phase is observed. This can be attributed mostly
to the ε→τ phase transformation together with a negligible decom-
position of the ferromagnetic phase into the thermodynamic stable γ2-
phase, as reported earlier [7,9]. The increase of the magnetization can
be also partially assigned to the removal of stresses and defects (caused
by EBM process) from the lattice, which leads to a recovery of mag-
netization, as pointed out by Bittner et al. [24].
The typical SEM image of the sample from series B is shown in
Fig. 6b. It is noticeable that the low temperature annealing does not
change the amount of matrix phase and the inclusions; however, the
Kerr microscopy image Fig. 7b illustrates that all inclusions in the
sample B have a twinning structure, that confirm the completeness of
the ε→τ phase transformation. The magnetization value of 20 Am2/kg
is still low and indicates that the stable γ2-phase preventing the for-
mation of the desired τ-phase and the high temperature annealing is
still present. The samples from series C were prepared from as manu-
factured ones using high temperature annealing (60 h at 1100°C), while
the samples from series D were prepared using additional low tem-
perature annealing of the series C samples (30 min at 500°C). The
magnetization of the samples C and D measured in magnetic field
μ0H = 2 T is increased up to 50 Am2/kg and up to 100 Am2/kg, re-
spectively. The high magnetization of the D sample indicates that it
mainly contains ferromagnetic τ-phase [28]. In addition, the inset
graph in Fig. 4 shows the magnetization curve of the powder used for
EBM processing in two conditions, starting powder and annealed
powder in the optimized condition- the same used for samples D. The
starting powder is nonmagnetic, as can be seen from the linear behavior
and low magnetization value, and has ferromagnetic behavior after
annealing with magnetization of 66 Am2/kg, which is lower than the
EBM sample annealed in the same condition.
The XRD patterns of series C and D samples show that after high
6
Additive Manufacturing 30 (2019) 100787
temperature annealing the amount of the ε-phase is increased (sample
C), while the γ2-phase is decreasing, compared to the as-printed state
(see Fig. 5). Consequently, after two step annealing (sample D), the
fraction of τ-phase reached 90% (see also Table 3). Despite the increase
in the magnetization, the heat treatment of the EBM-manufactured Mn-
Al samples does not affect the coercivity and all the samples from series
A, B, C and D have nearly the same HC of approximately 0.1 T, which
also holds true for the annealed powder (in- set graph in Fig. 4). It is
known that the coercivity mechanism in the Mn-Al alloy is inherently
linked to the presence of microstructure features (defects) such as anti-
phase boundaries and twinning planes [28,29]; however, the liaison
between nucleation, propagation and pinning-depinning of a domain
walls at these defects is still poorly understood. In the ref [29], the
author’s demonstrated that magnetic domain walls nucleate readily at
anti-phase boundaries and are strongly pinned by them, due to anti-
ferromagnetic coupling. Likewise, twin boundaries reduce the external
field required to nucleate domain walls and provide strong pinning
potentials, with the pinning strength dependent on the twinning angle.
The simulations ref [29] confirm experimental observations that sam-
ples with many twins have a much lower coercivity than those with
anti-phase boundaries.
As it was shown recently by D. Palanisamy et al. [30], only one type
of defects is forming in Mn-Al alloys during the transformation of high
temperature ε-phase to metastable L10 τ -phase, namely the twinning
boundaries. Moreover, the formation of such kind of defects is always
accompanied by the compositional gradients of Mn and Al across the
twin boundaries of 10–25 nm width, and this length scale is comparable
to the width of domain walls. An enrichment of about 8 at.% of Mn
along the twin boundary coexists with a confined depletion outside the
twin boundary [30]. Such significant variation in concentration leads to
a serious change in magnetic properties across the twin boundary,
making the twins a good pinning center hindering propagation of do-
main wall and impeding demagnetization processes in the field range
up to 0.15 T [31–33].
Fig. 8 presents the microscopic Kerr images of series D sample ob-
tained in magnetic fields of 1.3 T. The direction of the field is shown by
I.A. Radulov, et al.
white arrows. In Fig. 8 two randomly selected grains are indicated as
grain 1 and 2. Before observation of domain structure transformation in
magnetic field, the sample was magnetized in magnetic field 2 T, the
direction of this field was the same as it is shown in Fig. 8a. One can see
that in Fig. 8a and Fig. 8b, there is no domain structure visible in both
grains 1 and 2.
When the magnetic field is rotated to 90 degrees, laminar domain
structure appears in grain 1 (Fig. 8c). When the direction of magnetic
field is changed by 135 degrees, laminar domain structure can be ob-
served in grain 2 (Fig. 8d), while grain 1 is fully demagnetized. The
domain patterns appearing during demagnetization are typical for the
hard magnetic materials with pinning mechanism of coercivity [34,35].
Indeed, for pinning controlled permanent magnets the coercivity of the
surface layer corresponds to the coercivity in the volume of the magnet,
and the results of observing the transformation of domain structure
allow us to make correct judgments about the mechanism of magneti-
zation reversal processes in the volume of the magnet. At the same time,
it is known that when the Mn-Al alloys are subjected to annealing, only
twin-like defects are presented in the ferromagnetic τ -phase, serving as
pinning centers and providing the coercivity only of 0.15 T. For ex-
ample, the same value of coercivity was reported in 3D-printed Mn-Al-
based composite materials, obtained using quasi-spherical gas atomized
ferromagnetic τ-MnAlC particles embedded in polyethylene matrix
[36]. For increasing coercivity even further, the anti-phase boundaries
should be developed in the sample, providing higher pining field and as
a result the higher coercivity. Commonly, this type of defects can be
engineered by ball milling or deformation/extrusion increasing the
coercivity values up to 0.4 T [27,29]. Unfortunately, in our printed Mn-
Al samples, such kind of treatment will drastically change the shape of
the samples; thus, the HC = 0.15 T is the maximum achievable one so
far.
4. Conclusions
One of the main obstacles in successful additive manufacturing of
hard magnetic materials is the engineering of a desired microstructure
in fully dense printed blocks or complex geometries, and this problem
has not yet been solved. In fact, the functional magnetic properties of
permanent magnets (both Br and HC) are extrinsic in nature and
7
Additive Manufacturing 30 (2019) 100787
Fig. 8. Kerr-microscopy images of sample D
demonstrate the magnetization-demagnetiza-
tion process in two randomly selected do-
mains, indicated with 1 and 2, in rotating
magnetic field of 1.3 T. The arrow in the upper
left corner indicates the field direction. Other
defects of the microstructure, like twin
boundaries (TWB), microtwins (μTW) and
grain boundaries (GB) are indicated as well.
completely determined by the microstructure developed during the
magnet processing. Thus, the developing the additive manufacturing
technique, which potentially offers an effective way for fabricating full-
dense high-energy permanent magnets is a challenging task. On the
other hand, freedom of shapes achievable with the AM methods could
still be combined with certain post-processing resulting in industrially
attractive technological process. The same time the drive to increasing
sustainability of the manufacturing and decreasing dependence on
certain critical materials like RE metals are strong motivators towards
developing new materials and technologies promising viable alter-
natives to conventional processing techniques used for production of
high-energy permanent magnets.
In this work, for the first time, the rare-earth-free Mn-Al permanent
mag- nets were additively manufactured by using Electron Beam
Melting technique. The modified Arcam EBM system and the specific
set of process parameters, including beam power, preheating settings,
layer thickness, hatching distance, made it possible to fabricate pre-
dominantly fully dense Mn-Al blocks.
Mn-Al samples were manufactured by EBM from the ball-milled
powder, not optimized for additive manufacturing. The as-printed
samples contain 8% of desired ferromagnetic τ-MnAl phase. This results
confirm, contrary to earlier reports, that not only conventional gas-
atomized powder could be used for beam-based AM. Moreover, the
phase formation in the printed samples can be improved further by
optimization of the EBM processing parameters.
However, the amount of τ -phase in the samples can increased also
by post processing, e.g. heat treatment allowed to obtain samples
congaing up to 90% τ-phase. Based on this, we report the first ever
MnAl magnets, manufactured by PB-AM, with coercivity of 0.15 T.
These results support the suggestion that manufacturing permanent
mag- nets in a single powder bed additive manufacturing process is
feasible, but so far, the two-stage process involving a post-treatment
(annealing of as-manufactured components) has higher potential for
manufacturing non-RE permanent magnets.
Future work on the optimization of the AM process parameters is in
progress for exploring the true potential of EBM manufacturing of
permanent magnets containing no critical materials.
I.A. Radulov, et al. Additive Manufacturing 30 (2019) 100787

Acknowledgments [18] D. Goll, D. Vogelgsang, U. Pflanz, D. Hohs, T. Grubesa, J. Schurr, T. Bernthaler,

D. Kolb, H. Riegel, G. Schneider, Refining the microstructure of Fe-Nd-B by selective
laser melting, Phys. Status Solidi (RRL) – Rapid Res. Lett. (2019) 1800536, https://
This work received funding from the EU Horizon 2020 NOVAMAG doi.org/10.1002/pssr.201800536 0 (0) URLhttps://onlinelibrary.wiley.com/doi/
project (NMBP 23-2015 research No 686056). The work of F. Maccari abs/10.1002/pssr. 201800536.
was supported by DFG-SPP1959 Fields Matter. [19] T. Kolb, F. Huber, B. Akbulut, C. Donocik, N. Urban, D. Maurer, J. Franke, Laser
beam melting of NdFeB for the production of rare-earth magnets, 2016 6th
International Electric Drives Production Conference (EDPC), IEEE, 2016, https://
References doi.org/10.1109/edpc.2016.7851311.
[20] V. Popov, A. Katz-Demyanetz, M. Bamberger, Heat transfer and phase formation
through EBM 3D-printing of Ti-6Al-4V cylindrical parts, Diffusion in Materials
[1] O. Gutfleisch, M.A. Willard, E. Brück, C.H. Chen, S.G. Sankar, J.P. Liu, Magnetic
DIMAT-2017, Vol. 383 of Defect and Diffusion Forum, Trans Tech Publications,
materials and devices for the 21st century: stronger, lighter, and more energy ef-
2018, pp. 190–195, https://doi.org/10.4028/www.scientific.net/DDF.383.190.
ficient, Adv Mater. 23 (7) (2010) 821–842, https://doi.org/10.1002/adma.
[21] A. Koptyug, L.-E. Räannar, M. Bäackström, R. Langlet, Bulk metallic glass manu-
201002180 https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.201002180.
facturing using electron beam melting, Proceedings from Additive Manufacturing;
[2] K.P. Skokov, O. Gutfleisch, Heavy rare earth free, free rare earth and rare earth free
3D Printing, Nottingham, UK, 2013 URL http://www.am-conference.com/index.
magnets - Vision and reality, Scr. Mater. 154 (2018) 289–294, https://doi.org/10.
php?main_page=document_product_info&products_id=288.
1016/j.scriptamat.2018.01.032 URL http://www.sciencedirect.com/science/
[22] A. Koptyug, L.-E. Räannar, C.A. Botero Vega, M. Bäackström, V. Popov, Blended
article/pii/S1359646218300599.
powders can be successfully used in electron beam melting yielding unique material
[3] M.D. Kuz’min, K.P. Skokov, H. Jian, I. Radulov, O. Gutfleisch, To- wards high-
compositions, EuroPM Proceedings (2018).
performance permanent magnets without rare earths, J. Phys. Condens. Matter 26
[23] A. Koptyug, M. Bäackström, C.A. Botero Vega, V. Popov, E. Chudinova, Developing
(6) (2014) 064205 URL http://stacks.iop.org/0953-8984/26/i=6/a=064205.
new materials for electron beam melting: experiences and challenges, THERMEC
[4] O. Gutfleisch, Controlling the properties of high energy density permanent mag-
2018, Vol. 941 of Materials Science Forum, Trans Tech Publications, 2019, pp.
netic materials by different processing routes, J. Phys. D Appl. Phys. 33 (17) (2000)
2190–2195, , https://doi.org/10.4028/www.scientific.net/MSF.941.2190.
R157 URL http://stacks.iop.org/0022-3727/33/i=17/a=201.
[24] F. Bittner, J. Freudenberger, L. Schultz, T.G. Woodcock, The impact of dislocations
[5] S. Hirosawa, M. Nishino, S. Miyashita, Perspectives for high-performance perma-
on coercivity in L10-MnAl, J. Alloys. Compd. 704 (2017) 528–536, https://doi.org/
nent magnets: applications, coercivity, and new materials, Adv. Nat. Sci. Nanosci.
10.1016/j.jallcom.2017.02.028 URL http://www.sciencedirect.com/science/
Nanotechnol. 8 (1) (2017) 013002 URL http://stacks.iop.org/2043-6262/8/i=1/
article/pii/ S0925838817304437.
a=013002.
[25] A. Koptyug, L.-E. Räannar, M. Bäackström, R. Surmenev, Additive manu- facturing
[6] J.M.D. Coey, Permanent magnets: plugging the gap, Scr. Mater. 67 (6) (2012)
in metal: technology advances generate new research challenges, Nanotechnology:
524–529, https://doi.org/10.1016/j.scriptamat.2012.04.036 viewpoint Set No. 51:
Development and Applications - XXI Century 4 (2016) 12–25 URL http://www.
Magnetic Materials for Energy. URL http://www.sciencedirect.com/science/
radiotec.ru/article/18802.
article/pii/S1359646212002990.
[26] A. Koptyug, L.-E. R¨annar, M. B¨ackstr¨om, New materials for additive manu-
[7] F. Bittner, L. Schultz, T.G. Woodcock, The role of the interface distribution in the
facturing in metal: Back to basics? Proceedings, Vol. 941, Trans Tech Publications
decomposition of metastable L10-Mn54Al46, J. Alloys Comp. 727 (2017) 1095–1099,
(2017) 2190–2195.
https://doi.org/10.1016/j.jallcom.2017.08.197 URL http://www.sciencedirect.
[27] H. Jian, K.P. Skokov, O. Gutfleisch, Microstructure and magnetic properties of
com/science/article/pii/S0925838817329262.
Mn–Al–C alloy powders prepared by ball milling, J. Alloys. Compd. 622 (2015)
[8] Y.J. Kim, J.H. Perepezko, The thermodynamics and competitive kinetics of me-
524–528, https://doi.org/10.1016/j.jallcom.2014.10.138 URL http://www.
tastable τ phase development in MnAl-base alloys, Mater. Sci. Eng.: A 163 (1)
sciencedirect.com/science/article/pii/S0925838814025675.
(1993) 127–134, https://doi.org/10.1016/0921-5093(93)90586-4 URL http://
[28] P.-Z. Si, H.-D. Qian, C.-J. Choi, J. Park, S. Han, H.-L. Ge, K. Shinde, In situ
www.sciencedirect.com/science/article/pii/0921509393905864.
Observation of Phase Transformation in MnAl(C) Magnetic Materials, Materials 10
[9] Z.W. Liu, C. Chen, Z.G. Zheng, B.H. Tan, R.V. Ramanujan, Phase transitions and
(9) (2017) 1016, https://doi.org/10.3390/ma10091016.
hard magnetic properties for rapidly solidified MnAl alloys doped with C, B, and
[29] S. Bance, F. Bittner, T.G. Woodcock, L. Schultz, T. Schrefl, Role of twin and anti-
rare earth elements, J. Mater. Sci. 47 (5) (2012) 2333–2338, https://doi.org/10.
phase defects in MnAl permanent magnets, Acta Mater. 131 (2017) 48–56, https://
1007/s10853-011-6049-8.
doi.org/10.1016/j.actamat.2017.04.004 URL http://www.sciencedirect.com/
[10] A.E. Berkowitz, J.D. Livingston, J.L. Walter, Properties of Mn-Al-C magnets pre-
science/article/pii/ S1359645417302872.
pared by spark erosion and other rapid solidification tech- niques, J. Appl. Phys. 55
[30] D. Palanisamy, D. Raabe, B. Gault, Elemental segregation to twin boundaries in a
(6) (1984) 2106–2108, https://doi.org/10.1063/1.333579.
MnAl ferromagnetic Heusler alloy, Scr. Mater. 155 (2018) 144–148, https://doi.
[11] R. Madugundo, O. Koylu-Alkan, G.C. Hadjipanayis, Bulk Mn-Al-C permanent
org/10.1016/j.scriptamat.2018.06.037 URL http://www.sciencedirect.com/
magnets prepared by various techniques, AIP Adv. 6 (5) (2016) 056009, , https://
science/article/pii/S1359646218304019.
doi.org/10.1063/1.4943242 URL https://doi.org/10.1063/1.4943242.
[31] T. Ohtani, N. Kato, S. Kojima, K. Kojima, Y. Sakamoto, I. Konno, M. Tsukahara,
[12] L.J. Kumar, C.G. Krishnadas Nair, Current Trends of Additive Manu- Facturing in
T. Kubo, Magnetic properties of Mn-Al-C permanent magnet alloys, IEEE Trans.
the Aerospace Industry, Springer, Singapore, Singapore, 2017, pp. 39–54, https://
Magn. 13 (5) (1977) 1328–1330, https://doi.org/10.1109/TMAG.1977.1059574.
doi.org/10.1007/978-981-10-0812-2_4 URL https://doi.org/. doi: 10.1007/978-
[32] P.C. Kuo, Y.D. Yao, J.H. Huang, S.C. Shen, J.H. Jou, Microstructural and magnetic
981-10-0812-2_4.
studies of Mn–Al thin films, J. Appl. Phys. 81 (8) (1997) 5621–5623, https://doi.
[13] V.V. Popov, G. Muller-Kamskii, A. Kovalevsky, G. Dzhenzhera, E. Strokin,
org/10.1063/1.364618.
A. Kolomiets, J. Ramon, Design and 3D-printing of titanium bone implants: brief
[33] Q. Zeng, I. Baker, J.B. Cui, Z.C. Yan, Structural and magnetic properties of nanos-
review of approach and clinical cases, Biomed. Eng. Lett. 8 (4) (2018) 337–344,
tructured Mn–Al–C magnetic materials, J. Magn. Magn. Mater. 308 (2) (2007)
https://doi.org/10.1007/s13534-018-0080-5.
214–226, https://doi.org/10.1016/j.jmmm.2006.05.032 URL http://www.
[14] V.V. Popov, G. Muller-Kamskii, A. Katz-Demyanetz, A. Kovalevsky, Usov,
sciencedirect.com/science/article/pii/ S0304885306008754.
D. Trofimcow, G. Dzhenzhera, A. Koptyug, Additive manufacturing to veterinary
[34] O. Gutfleisch, K.-H. Mu¨ller, K. Khlopkov, M. Wolf, A. Yan, R. Sch¨afer, T. Gemming,
practice: recovery of bony defects after the osteosarcoma resection in canines,
L. Schultz, Evolution of magnetic domain structures and coercivity in high-perfor-
Biomed. Eng. Lett. (2019), https://doi.org/10.1007/s13534-018-00092-7.
mance SmCo 2:17-type permanent magnets, Acta Mater. 54 (4) (2006) 997–1008,
[15] V. Popov, A. Koptyug, I. Radulov, F. Maccari, G. Muller, Prospects of additive
https://doi.org/10.1016/j.actamat.2005.10.026 URL http://www.sciencedirect.
manufacturing of rare-earth and non-rare-earth permanent mag- nets, Procedia
com/science/article/pii/ S1359645405006397.
Manuf. 21 (2018) 100–108, https://doi.org/10.1016/j.promfg.2018.02.199 15th
[35] H. Sepehri-Amin, J. Thielsch, J. Fischbacher, T. Ohkubo, T. Schrefl, O. Gutfleisch,
Global Conference on Sustainable Manufacturing. URL http://www.sciencedirect.
K. Hono, Correlation of microchemistry of cell boundary phase and interface
com/science/article/pii/ S2351978918302397.
structure to the coercivity of Sm(Co0.784Fe0.100Cu0.088Zr0.028)7.19 sintered magnets,
[16] J. Jaćimović, F. Binda, L.G. Herrmann, F. Greuter, J. Genta, M. Calvo, Tomse,
Acta Mater. 126 (2017) 1–10, https://doi.org/10.1016/j.actamat.2016.12.050 URL
R.A. Simon, Net shape 3D printed NdFeB permanent magnet, Adv. Eng. Mater. 19
http://www.sciencedirect.com/science/article/pii/ S1359645416309831.
(8) (2017) 1700098, https://doi.org/10.1002/adem.201700098 arXiv:https:
[36] E.M. Palmero, J. Rial, J. de Vicente, J. Camarero, B. Skärman, H. Vidarsson, P.-
//onlinelibrary.wiley.com/doi/pdf/10.1002/adem.201700098, URL https://
O. Larsson, A. Bollero, Development of permanent magnet MnAlC/polymer com-
onlinelibrary.wiley.com/doi/abs/10.1002/adem. 201700098.
posites and flexible filament for bonding and 3D-printing technologies, Sci.
[17] L. Li, B. Post, V. Kunc, A.M. Elliott, M.P. Paranthaman, Additive manufacturing of
Technol. Adv. Mater. 19 (1) (2018) 465–473, https://doi.org/10.1080/14686996.
near-net-shape bonded magnets: prospects and challenges, Scr. Mater. 135 (2017)
2018.1471321 pMID: 29887921..
100–104, https://doi.org/10.1016/j.scriptamat.2016.12.035 URL http://www.
sciencedirect.com/science/article/pii/ S1359646216306352.