Calphad 66 (2019) 101621

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Calphad
journal homepage: www.elsevier.com/locate/calphad

Thermodynamic assessment and experimental investigation of the systems T

Al–Fe–Mn and Al–Fe–Mn–Ni
Alexander Walnsch, Mario J. Kriegel∗, Olga Fabrichnaya, Andreas Leineweber
TU Bergakademie Freiberg, Institute of Materials Science, Gustav-Zeuner Str. 5, 09599, Freiberg, Germany

ABSTRACT

The ternary Al–Fe–Mn and the quaternary Al–Fe–Mn–Ni systems were re-assessed/assessed with special emphasis on compositions relevant for Fe-based shape
memory alloys (SMAs), to further improve materials properties and to reliably predict phase transformation in these systems. The thermodynamic assessment was
based on literature data, as well as experimental investigations regarding the phase equilibria formed between the phases A1, A2, B2 and β-Mn. Key isothermal
sections were studied at 725 and 1000 °C in the Al–Fe–Mn system and at 1000 and 1175 °C in the Al–Fe–Mn–Ni system, respectively. For the quaternary Al–Fe–Mn–Ni
system, additional diffusion-couple experiments were conducted to investigate target regions of the phase diagram. Calculations based on the present description are
in excellent agreement with the data available in literature and the experimental investigations of the present work for both, the Al–Fe–Mn and the Al–Fe–Mn–Ni
systems.

1. Introduction based SMAs [10–15].

Iron-based shape memory alloys (SMAs) have attracted the atten-
tion of many research groups in recent years [1–9] due to promising
advantages compared to conventional NiTi-based alloys in several ap-
plication fields like damping in constructions for the civil infrastructure
and actuation for aerospace applications. The main advantages are low
material costs and easy manufacturing due to the good cold workability
and the possibility of applying steel based processing procedures.
Moreover, iron-based SMAs provide the pseudoelastic effect over a wide
temperature range due to the low slope of the Clausius-Clapeyron
equation, which describes the temperature dependence of the pseu-
doelastic stress [3]. Due to the importance of these materials systems, a
thermodynamic description of the Al–Fe–Mn–Ni system was developed
with special emphasis on the target composition 43.5Fe-34Mn-15Al-
7.5Ni (at.%) to explore new compositional regions relevant for Fe-based
SMAs and to adjust necessary heat-treatment procedures. The phases
relevant for SMAs are the parent high-temperature A2 (bcc), the or-
dered B2 (CsCl) precipitates, the A1 (fcc, also martensite) phase and at
low temperatures the β-Mn phase.
Even though, the present thermodynamic assessment aims at the
development of iron-based SMAs, the quaternary Al–Fe–Mn–Ni data-
base can further contribute to the understanding of high-strength
multiphase spinodal alloys for aerospace applications. This is accom-
plished, since the phases involved in these alloys were the same as for
the SMAs and the chemical composition of these alloys, 35Mn-30Fe-
20Ni-15Al (at.%), were located close to the target composition of Fe-
Experimental investigations by means of EDS and EPMA analyses of
several heat-treated and quenched samples, as well as diffusion couples
were conducted. For the ternary Al–Fe–Mn system, special focus was set
to the refinement of the experimental data near the tie-triangle A1 +
A2 + β-Mn in the compositional region from 6 to 21 at.% Al and 29 to
61 at.% Mn. In the quaternary Al–Fe–Mn–Ni system, extensive experi-
mental investigations, by means of heat-treated and subsequently
quenched alloys as well as diffusion couples, involving the phase
equilibria between the solution phases A1, A2 and B2, were executed to
provide a profound basis for the thermodynamic optimization.
2. Experimental procedure
Eight ternary and six quaternary alloys were prepared by arc
melting of high purity metal mixtures (Al: 99.9995%, Fe: 99.99%, Mn:
99.95%, Ni: 99.995%). These alloys will be denoted in the following by
the nominal chemical compositions as pAl-oFe-nMn-mNi with p, o, n
and m indicating the Al, Fe, Mn and Ni contents in at.%, respectively.
The pure metal mixtures were melted by conventional arc melting
(Edmund Buehler GmbH, Germany) on a water-cooled copper mold. In
order to achieve sufficient homogeneity, the samples were turned over
and re-melted at least three times. Prior to the heat-treatment process,
the samples were sealed in fused silica ampoules under controlled Ar
pressures between 200 and 300 mbar, depending on the subsequent
heat-treatment temperature. The investigated alloys, together with the
applied heat-treatment temperature are summarized in Tables 2–4.

∗
Corresponding author.
E-mail address: mario.kriegel@iww.tu-freiberg.de (M.J. Kriegel).

https://doi.org/10.1016/j.calphad.2019.04.006
Received 15 February 2019; Received in revised form 1 April 2019; Accepted 14 April 2019
Available online 19 June 2019
0364-5916/ © 2019 Elsevier Ltd. All rights reserved.
A. Walnsch, et al. Calphad 66 (2019) 101621

The diffusion couples were plated using the Spark Plasma Sintering literature focusing different regions of the phase diagram [38–41]. The
unit HDP 25 (FCT Systeme GmbH, Germany). To achieve a sufficient thermodynamic description of Lindahl and Selleby [39] reproduces the
connection of the end-members, the samples were polished before solubility ranges of the phases without considering the ternary inter-
plating (up to 1 μm diamond suspension). Afterwards, the polished metallic phases. The descriptions of Zhou et al. [40] and Zheng et al.
samples were bonded for 120 s at 1000 °C under a pressure of 5000 Pa [41] include the modelling of ternary intermetallic phases, using new
with a heating rate of 300 K·min−1 and subsequently cooled with a experimental findings of Balanetskyy et al. [19]. In the assessment of
cooling rate of 100 K·min−1. Zhou et al. [40] the ternary phases were modeled as stoichiometric
The chemical composition of each phase and the overall composi- compounds and the binary intermetallic phases were modeled as line
tion of the alloys were determined using electron-probe microanalysis compounds to reproduce their ternary extensions. In the most recent
with wavelength-dispersive X-ray spectroscopy (EPMA/WDS). The assessment of Zheng et al. [41] the homogeneity ranges of the binary, as
chemical compositions of the individual phases were measured locally, well as the ternary intermetallic phases were modeled in consistency
whereas the overall chemical compositions were obtained from aver- with the experimental data of Balanetskyy et al. [19]. However, the
aged EPMA line scans over 1 mm with a step size of 1 μm. The mea- recent binary Al–Fe assessment, where the description of the inter-
surements were performed using a JEOL JXA-8900 RL microprobe at metallic phases is based on heat capacity measurements, was not used
20 kV accelerating voltage. as a subsystem for their databases.
The spatial distribution of the individual phases was obtained from Moreover, in all descriptions, inconsistencies regarding the solubi-
micrographs of a scanning electron microscope (SEM). These micro- lity ranges of the phases (A1, A2, B2 and β-Mn), which are important
graphs were taken using backscattered electrons (BSE) as well as sec- for the application on Fe-based SMAs, were found. Since the ternary
ondary electrons (SE) with a JEOL JSM-7800 F. In order to correlate the intermetallic phases affect the homogeneity range of the B2 phase, the
SEM contrasts with the local chemical compositions measured by thermodynamic descriptions of Lindahl and Selleby [39] was excluded.
EPMA, energy-dispersive X-ray spectroscopy (EDS) point measurements In the thermodynamic description of Zhou et al. [40] the A1 phase
were performed on the respective grains using an EDAX EDS system. In seems to be too stable at temperatures above 1100 °C. Therefore, dis-
order to relate information about the crystallography of the different crepancies arise between the calculations and the experimental tie-line
phases to the local chemical compositions, electron backscatter dif- data. Moreover, at 1200 °C, the β-Mn phase was found to be stable in
fraction (EBSD) was performed with an EDAX EBSD system equipped the Al-rich portion of the phase diagram. The assessment of Zheng et al.
with a Hikari camera. Moreover, to directly correlate the observed [41] could not be used as a subsystem for the present work, since the
microstructure with the chemical compositions, the chemical compo- phase equilibria between A1, A2 and β-Mn at temperatures above
sitions of the diffusion couples along the diffusion path was measured 1000 °C, essential for Fe-based SMAs, are not in agreement with existing
by EDS. literature data.
In the present assessment, the recent thermodynamic description of
3. Phase equilibria in the Al–Fe–Mn system the Al–Fe system of Zienert and Fabrichnaya [16] was used as a binary
subsystem. This thermodynamic description (i) reproduces the A2/B2
3.1. Literature review ordering and the A2 + B2 two-phase field below the critical point and
(ii) includes an improved modelling of the intermetallic phases based
The crystallographic data of the solid phases in the Al–Fe–Mn on experimentally studied heat capacities. The thermodynamic assess-
system are given in Table 1. The phase diagrams calculated from pre- ment of the ternary Al–Fe–Mn system was based on constitutional data
viously developed thermodynamic descriptions of the binary sub-sys- experimentally studied by Balanetskyy et al. [19], Umino et al. [34],
tems Al–Fe [16], Fe–Mn [17] and Mn–Al [18] are illustrated in Fig. 1. Liu et al. [27], Sato et al. [33] and Priputen et al. [31]. Balanetskyy
The ternary Al–Fe–Mn system was investigated experimentally et al. [19] have investigated the Al-rich corner of the phase diagram in a
thoroughly over the last decades, providing a good understanding of the wide temperature range from 650 to 1070 °C showing the solubility
phase relations across the complete compositional range [19,21–37]. ranges of the majority of the intermetallic compounds of both, the
Additionally, several thermodynamic descriptions are available in Al–Fe and the Al–Mn, binary systems. The Al–Fe-based intermetallic
compounds, Al5Fe2 and Al2Fe were found to dissolve up to 10 at.% of
Table 1 Mn, while Al13Fe4 is stable up to Mn contents of 15 at.%. A remarkable
Stable solid phases in the Al–Fe–Mn system. The references for the different solubility for iron was found for the Al8Mn5 phase, which is able to
phases can be found in Refs. [19,20]. dissolve up to 30 at.% of Fe at elevated temperatures of approx.
1000 °C. This high solubility of Al8Mn5 was confirmed by Priputen et al.
Phase Prototype Pearson symbol Space group
[31] where the Al-rich portion of the phase diagram at 1000 °C was
Al12Mn Al12W cI26 Im3̄ investigated. Besides the solubility of the binary intermetallic phases,
Al13Fe4 mC102 C2/m Balanetskyy et al. [19] also discovered three stable ternary phases
Al2Fe Al2Fe aP18 P1̄ forming below 1070 °C. The ternary φ phase is formed below 1022 °C
Al4Mn μ-Al4Mn hP563 P63 /mmc
and has a small solubility range between 74 and 77 at.% Al, 2 and 11 at.
Al5Fe2 oC24 Cmcm
Al8Fe5 Cu5Zn8 cI52 I4̄ 3m % Fe and 15 and 21 at.% Mn as a function of temperature. The dec-
Al6Mn CrB oC8 Cmcm agonal D3 phase forms below 1026 °C at an almost constant composi-
Al8Mn5 R-Al8Cr5 hR26 R3̄ m tion of Al74Fe11Mn15 and exhibits the same crystal structure as the
A2 W cI2 Im3̄ m corresponding D3 phase in the Al–Cr–Fe system [30]. The third stable
B2 CsCl cP2 Pm3̄ m ternary phase discovered by Balanetskyy et al. [19] is the hexagonal κ
α-Mn α-Mn cI58 I4̄ 3m
phase which is stable at around 80 at.% of Al while exhibiting a limited
β-Mn β-Mn cP20 P4132
A1 Cu cF4
solubility of Fe and Mn and is found to be isostructural to the κ phase of
Fm3̄ m
ε Mg hP2 P63 /mmc the Al–Mn–Ni system.
HT-Al11Mn4 Al3Mn oP156 Pnma Comprehensive experimental investigations of the Fe–Mn side of the
LT-Al11Mn4 Al11Mn4 aP30 P1̄ phase diagram were performed by Umino et al. [34], Liu et al. [27] and
R-Al4Mn NbSe2 hP6 P63 /m Sato et al. [33]. While the work of Sato et al. [33] is mainly focused on
φ hP28 P63 /mmc
the Fe-rich portion of the phase diagram and the determination of the
κ κ-Al14,4Cr3,4Ni1,1 hP227 P63 /m
D3 decagonal crystal structure phase equilibria between the A1 and A2 phase in a temperature range
between 800 and 1100 °C, the other works cover the whole Fe–Mn-rich

2
A. Walnsch, et al.
Fig. 1. Calculated phase diagrams of the binary sub-systems: (a) Al–Fe system [16], (b) Fe–Mn system [17], (c) Mn–Al system [18]. The dashed lines mark the
second-order transition between the phases A2 and B2.
side up to Al contents of 40 at.%, including phase equilibria between
A1, A2, B2 and β-Mn. Umino et al. [34], as well as Liu et al. [27],
performed experimental investigations by means of EPMA analyses of
heat-treated samples and diffusion couples together with thermal ana-
lysis methods like DSC and DTA. Especially the DSC measurements
focusing on the A2/B2 transition of Umino et al. [34] were of high
importance for the present assessment, since phase transformations
involving these phases need to be described highly accurately for the
application on iron-based SMAs.
3.2. Experimental investigations
Due to the importance of the phase equilibria between the A1, A2,
B2 and β-Mn phases relevant for Fe-based SMAs and the inconsistencies
within the literature data, additional samples were prepared, heat-
treated, quenched and subsequently studied by complementary
methods to refine the thermodynamic database in SMA-target compo-
sitional regions. Five samples with the nominal chemical compositions
6Al-33Fe-61Mn, 12Al-38Fe-50Mn, 14Al-48Fe-38Mn, 16Al-38Fe-46Mn
and 21Al-38Fe-41Mn were heat treated at 1000 °C for 72 h and three
samples with the nominal chemical composition of 14Al-45Fe-41Mn,
15Al-48Fe-37Mn and 17Al-54Fe-29Mn were heat treated at 725 °C for
504 h and subsequently quenched in ice water. Exemplary the SEM/BSE
micrographs of 17Al-54Fe-29Mn, 14Al-48Fe-38Mn, 16Al-38Fe-46Mn
and 21Al-38Fe-41Mn were illustrated in Fig. 2, the microstructures of
the samples 6Al-33Fe-61Mn and 12Al-38Fe-50Mn were similar to 16Al-
38Fe-46Mn and, therefore, not shown in Fig. 2. All the samples, except
14Al-45Fe-41Mn and 15Al-48Fe-37Mn, which were found to be located
inside the β-Mn single-phase region, exhibit two-phase microstructures
of the above-mentioned phases. The difference in the contrasts in the
grains of the same phase originates from different orientations of the
sub-grains, as well as from twinning in the A1 phase. The chemical
compositions of these phases and the measured overall chemical com-
position of the samples are summarized in Table 2.
4. Phase equilibria in the Al–Fe–Mn–Ni system
4.1. Literature review
For a better understanding of the phase equilibria in the quaternary
Al–Fe–Mn–Ni system, the isothermal sections at 1000 °C of the four
ternary sub-systems Al–Fe–Mn, Al–Fe–Ni [42], Al–Mn–Ni [43] and
Fe–Mn–Ni [44] are illustrated in Fig. 3. It should be noted that the
parameters of the ternary Al–Fe–Ni system were slightly adjusted, since
the binary Al–Fe sub-system was changed to the description of Zienert
3
Calphad 66 (2019) 101621
and Fabrichnaya [16].
In the quaternary Al–Fe–Mn–Ni system only a small amount of ex-
perimental constitutional investigations are available in literature.
The majority of these works were dealing with microstructural in-
vestigations of as-cast alloys and the phase transformations taking place
upon cooling, without the aid of thermal analysis methods like DTA or
DSC [11–14,45–48]. Consequently, transformation temperatures were
not determined yet. Moreover, the works of He and Zhou [49] and
Kaputkina et al. [50] investigated small parts of the quaternary system
with several heat-treated and quenched samples. He and Zhou [49]
focused mainly on the determination of the martensitic transformation
temperature in the alloy 19Al-5Fe-16Mn-60Ni by means of DSC mea-
surements. Besides that, the alloy 19Al-5Fe-16Mn-60Ni was heat
treated at 1100 °C revealing an A1 + B2 two-phase microstructure. In
the investigations of Kaputkina et al. [50] several phase equilibria be-
tween the A1 and A2 phases were determined in the Fe-rich portion of
the phase diagram. Unfortunately, the chemical composition of the
phases were presented incompletely in their work and, therefore, these
data were not considered the thermodynamic assessment performed in
the present work.
4.2. Experimental investigations
To develop a reliable thermodynamic database for Fe-based SMAs,
key investigations considering the relevant phases (A1, A2, B2) were
carried out by means of equilibration heat treatments, as well as dif-
fusion-couple experiments. Since for the application of iron-based SMAs
the phase transformations taking place at elevated temperatures be-
tween 1000 and 1200 °C are of high importance for the adjustment of
heat-treatment procedures, the annealing of the samples was carried
out at 1000 and 1175 °C. The samples 15Al-43.5Fe-34Mn-7.5Ni and
13.5Al-65Fe-14Mn-7.5Ni were heat treated at 1000 °C for 72 h showing
an A1 + A2 two-phase microstructure, as illustrated exemplary for the
sample 15Al-43.5Fe-34Mn-7.5Ni in the SEM/BSE image in Fig. 4. The
difference in the contrast of the same phases for sample 15Al-43.5Fe-
34Mn-7.5Ni originates from different orientations of the sub-grains, as
well as from twinning in the A1 phase. Moreover the samples 12Al-
61Fe-19Mn-8Ni, 15Al-36Fe-18Mn-31Ni and 14Al-14Fe-20Mn-52Ni
were heat treated at 1175 °C for 24 h revealing two-phase micro-
structures, as exemplary illustrated for the sample 15Al-36Fe-18Mn-
31Ni in Fig. 4. For the sample 12Al-61Fe-19Mn-8Ni the phases, which
were in equilibrium at 1175 °C, were determined as A1 and A2, while
for the samples 15Al-36Fe-18Mn-31Ni and 14Al-14Fe-20Mn-52Ni A1
and B2 were found to be in equilibrium. The illustrated microstructure
of the sample 15Al-36Fe-18Mn-31Ni show different contrasts in the
A. Walnsch, et al. Calphad 66 (2019) 101621

Fig. 2. SEM/BSE micrographs of the cross-sectional polished 17Al-54Fe-29Mn alloy annealed at 725 °C for 504 h and subsequently quenched in ice water, as well as
the alloys 14Al-48Fe-38Mn, 16Al-38Fe-46Mn and 21Al-38Fe-41Mn annealed at 1000 °C for 72 h and subsequently quenched in ice water. The labels indicate the
present phases (Table 1). The differences in the contrasts in the grains of the same phase originate from different orientations of the sub-grains, as well as from
twinning in the A1 phase.

individual phases, caused by residual stresses, as well as slight topo-
graphy, due to the polishing procedure. The overall chemical compo-
sition of the alloys together with the chemical composition (EPMA) of
the individual phases in the microstructures is summarized in Table 3.
To cover larger compositional regions of the phase diagram, three
diffusion-couple experiments D1-D3 were carried out at 1000 °C for
168 h (D1, D2) and at 1175 °C for 72 h (D3). The employed end-member
alloys, the heat treatment conditions and the main outcome of the
microstructure analyses are summarized in Table 4.
Diffusion couple D1 was assembled from the alloys 20Al-70Fe-10Mn
and 5Al-50Fe-10Mn-35Ni. The microstructure near the bonding plane is
illustrated in the SEM/BSE image in Fig. 5 (a), together with an overlay
of the local chemical composition (EDS) of the single-phase regions
along the selected part of the diffusion couple. After the heat treatment
a broad diffusion zone has formed in the sample D1 with wide single-
phase regions (A2 for the ternary side and A1 for the quaternary side).
Near the bonding plane, on the former ternary side, a sharp change in
the slope of the chemical composition was determined, most likely
being the consequence of the second-order phase transition to the or-
dered B2 phase taking part at the heat treatment temperature. This
view is supported by the occurrence of the same transition at the same
temperature at a similar composition in the Al–Fe–Ni system [42]. After

Table 2
Chemical compositions (EPMA) of the Al–Fe–Mn samples heat treated at 725 °C for 504 h and 1000 °C for 72 h. The nominal alloy compositions were determined
from the initial mass ratio of the elements with the numbers indicating at.%.
Alloy Heat-treatment temperature [°C] Alloy composition [at.%] Phase Phase composition [at.%]

Al Fe Mn Al Fe Mn

14Al-45Fe-41Mn 725 14.0 45.4 40.6 β-Mn 14.0 45.4 40.6

15Al-48Fe-37Mn 725 14.8 48.4 36.6 β-Mn 14.8 48.4 36.6
17Al-54Fe-29Mn 725 16.9 53.8 29.2 A2 16.8 61.3 21.9
β-Mn 16.9 48.7 34.4
14Al-48Fe-38Mn 1000 13.9 48.4 37.7 A1 13.1 48.4 38.6
A2 15.6 48.9 35.6
16Al-38Fe-46Mn 1000 15.5 38.3 46.2 A1 13.4 42.5 44.1
β-Mn 15.9 37.4 46.7
21Al-38Fe-41Mn 1000 21.3 37.9 40.8 A2 21.4 39.6 39.0
β-Mn 21.3 35.0 43.7
12Al-38Fe-50Mn 1000 12.1 37.6 50.3 A1 11.2 40.7 48.2
β-Mn 12.8 35.7 51.5
6Al-33Fe-61Mn 1000 6.4 32.9 60.7 A1 6.4 40.8 52.8
β-Mn 6.5 31.3 62.2

4
A. Walnsch, et al.
Fig. 3. Calculated phase diagrams of the ternary sub-systems Al–Fe–Mn, Al–Fe–Ni (modified) [42], Al–Mn–Ni [43] and Fe–Mn–Ni [44] at 1000 °C. The dashed lines
mark the second-order transition between the phases A2 and B2.
traversing the single-phase B2 region, a two-phase region between A1
and B2 has formed, marked by the dashed region b. A more detailed
image of the microstructure of the two-phase region (A1 + B2) is il-
lustrated in Fig. 5 (b), showing a mixture of elongated B2 grains besides
coarse uniform A1 grains. EDS measurements across the different
phases along the two-phase microstructure showed, that the local
equilibria formed in the two-phase area are connected to a broad range
of tie-lines in the phase diagram.
Diffusion couple D2 was assembled from the alloys 45Al-25Fe-30Mn
and 5Al-50Fe-10Mn-35Ni. The overall microstructure of the sample D2
near the bonding plane, illustrated in Fig. 5 (c), together with an
overlay of the local chemical composition (EDS) of the single-phase
regions, nearly resembles the microstructure of D1. Since the ternary
alloy 45Al-25Fe-30Mn is in the field of single phase B2 at the heat-
treatment temperature of 1000 °C, a second-order phase transition was
not found in the sample D2. A two-phase area consisting of A1 and B2
has also formed in D2 and is indicated by the marked area d in Fig. 5
(c). The more detailed image of the two-phase area in sample D2 is
illustrated in Fig. 5 (d), showing a similar mixture of elongated B2
grains besides coarse uniform A1 grains as encountered in D1. EDS
measurements of this two-phase microstructure also showed, that the
local equilibria between the A1 and B2 phases at different points in the
5
Calphad 66 (2019) 101621
two-phase area are connected to a wide range of tie-lines.
The diffusion couple D3 consists of the quaternary alloy 12.5Al-
47Fe-32Mn-7.5Ni, which was plated to pure nickel. In the initial state,
at the heat treatment temperature of 1175 °C, the end-members of the
diffusion couple form a two-phase microstructure (A1 + A2) on the
quaternary side and a single-phase microstructure (A1) on the unary
side, respectively. The BSE/SEM image of the sample D3 after the dif-
fusion heat treatment, given in Fig. 5 (e), shows the microstructure near
the former bonding plane with an overlay of the EDS measurements
along the diffusion path of the single-phase A1 areas. After leaving the
two-phase microstructure (A1 + A2), the diffusion path extends across
a single-phase A1 region, leading to a two-phase area, marked by the
dotted lines and shown more in detail in Fig. 5 (f). Upon leaving the
marked two-phase area, the diffusion path continues in the single-phase
A1 region until reaching pure nickel. As illustrated in Fig. 5 (f), the
marked two-phase region in Fig. 5 (e) consists of the phases A1 and B2
in a range of local equilibria across the two-phase area, what results in
different tie-lines measured by EDS. This type of diffusion path, leading
from a single-phase region over a two-phase area back to the same
single-phase region, is described by Kondentsov et al. [51] as a region
of isolated precipitates.
Fig. 4. SEM/BSE micrographs of the cross-sectional
polished 15Al-43.5Fe-34Mn-7.5Ni alloy annealed at
1000 °C for 72 h and subsequently quenched in ice
water, as well as the alloy 15Al-36Fe-18Mn-31Ni
annealed at 1175 °C for 24 h and subsequently
quenched in ice water. The labels indicate the present
phases (Table 1). The differences in the contrasts of
the same phase for sample 15Al-43.5Fe-34Mn-7.5Ni
originate from different orientations of the sub-
grains, as well as from twinning in the A1 phase. For
the sample 15Al-36Fe-18Mn-31Ni the different con-
trast in each phase is connected to residual stresses
caused by the polishing procedure.
A. Walnsch, et al. Calphad 66 (2019) 101621

Table 3
Chemical compositions (EPMA) of the Al–Fe–Mn–Ni samples heat treated at 1000 °C for 72 h and 1175 °C for 24 h. The nominal alloy compositions were determined
from the initial mass ratio of the elements with the numbers indicating at.%.
Alloy Heat-treatment temperature [°C] Alloy composition [at.%] Phase Phase composition [at.%]

Al Fe Mn Ni Al Fe Mn Ni

15Al-43.5Fe-34Mn-7.5Ni 1000 13.8 46.4 32.4 7.4 A1 12.6 47.6 33.4 6.4
A2 19.2 41.6 27.9 11.3
13.5Al-65Fe-14Mn-7.5Ni 1000 13.3 65.3 13.9 7.5 A1 10.2 66.9 16.2 6.7
A2 13.9 65.0 13.5 7.6
12Al-61Fe-19Mn-8Ni 1175 11.8 61.0 18.8 8.4 A1 10.4 61.8 19.5 8.3
A2 13.3 60.1 18.2 8.4
15Al-36Fe-18Mn-31Ni 1175 14.6 35.7 18.3 31.4 A1 8.8 46.0 19.7 25.5
B2 22.5 21.6 16.4 39.5
14Al-14Fe-20Mn-52Ni 1175 14.2 14.2 20.1 51.5 A1 7.4 23.0 19.6 50.0
B2 17.6 9.8 20.3 52.3

Table 4
Chemical compositions (EDS) of the local equilibria in the diffusion couples heat treated at 1000 °C for 168 h and 1175 °C for 72 h. The nominal alloy compositions of
the end-members of the diffusion couples were determined from the initial mass ratio of the elements with the numbers indicating at.%.
Diffusion Couple: end-member alloys Heat-treatment Local Phase Phase composition [at.%]
temperature Equilibrium
[°C] Al Fe Mn Ni

D1: 20Al-70Fe-10Mn/5Al-50Fe-10Mn-35Ni 1000 A2/B2 20.5 64.8 7.7 7.0a

A1 11.5 61.7 9.6 17.2b

B2 32.0 26.8 7.2 34.0

A1 12.0 55.7 9.4 22.9b

B2 31.5 23.8 7.8 36.9

A1 11.8 52.1 9.2 26.9b

B2 30.8 21.8 8.3 39.1

D2: 45Al-25Fe-30Mn/5Al-50Fe-10Mn-35Ni 1000 A1 11.3 62.1 12.3 14.3b

B2 30.4 27.5 9.1 33.0

A1 10.0 61.4 11.6 17.0b

B2 30.5 22.4 9.6 37.5

A1 9.5 52.5 10.0 28.0b

B2 28.8 19.8 9.9 41.4

D3: 12.5Al-47Fe-32Mn-7.5Ni/Ni 1175 A1 11.5 48.1 32.9 7.5

A2 14.2 46.3 31.2 8.3

A1 9.8 36.9 17.7 35.6b

B2 23.3 15.7 16.5 44.5

A1 9.6 34.4 17.7 38.3b

B2 22.8 14.8 16.6 45.8

A1 9.6 31.9 17.8 40.8b

B2 22.2 14.1 17.1 46.6

A1 9.7 29.3 17.9 43.1b

B2 21.8 13.7 17.2 47.3

A1 9.7 25.0 18.0 47.3b

B2 21.4 12.1 17.6 48.9

A1 9.9 20.0 18.7 51.4b

B2 20.9 10.2 18.1 50.8

A1 10.5 17.7 18.4 53.4b

B2 20.7 9.3 18.6 51.4

a
Second-order transition, hence equal compositions.
b
Different positions in the two-phase region connected to a range of tie-lines.

5. Thermodynamic modelling AxByCz, the Gibbs energy G Ax By Cz was modeled as:

G Ax By Cz = f G Ax By Cz (T ) + xGHSERA + yGHSERB + zGHSERC

The thermodynamic descriptions of the pure elements were ac-
cepted from Dinsdale [52]. For a ternary stoichiometric compound (1)

6
A. Walnsch, et al. Calphad 66 (2019) 101621

Fig. 5. SEM/BSE micrographs of the cross-sectional polished diffusion couples D1 and D2 annealed at 1000 °C for 168 h and subsequently quenched in ice water, as
well as the micrograph of the cross-sectional polished diffusion couple D3 annealed at 1175 °C for 72 h. (a) Overview of the area near the bonding plane of sample D1
with an overlay of the measured EDS line profile along the single-phase regions. (b) Detailed view of the marked section b in (a) showing the two-phase area (A1 +
B2). (c) Overview of the area near the bonding plane of sample D2 with an overlay of the measured EDS line profile along the single-phase regions. (d) Detailed view
of the marked section d in (c) showing the two-phase area (A1 + B2). (e) Overview of the area near the bonding plane of sample D3 with an overlay of the measured
EDS line profile along the single-phase A1 regions. (f) Detailed view of the marked section f in (e) showing a two-phase area (A1 + B2). The labels indicate the
present phases (Table 1).

n
where f G Ax B y Cz (T ) is the Gibbs energy of formation of the stoichio- with the surface of reference term Gm, srf = i x i Gi , the contribution to
metric compound from pure elements and GHSERi is the Gibbs energy the Gibbs energy from the configurational entropy of mixing
n
of a pure element i referred to the enthalpy of its stable state at Gm, conf = RT i xi · lnx i and the excess Gibbs energy Gm, E which is
298.15 K. Substitutional solutions were modeled as: modeled as:

Gm = Gm, srf + Gm, conf + Gm, E

n n
= xG
i=1 i i
+ RT x
i=1 i
· lnx i + Gm, E (2)

7
A. Walnsch, et al. Calphad 66 (2019) 101621

Gm, E = Gm, bin . E + Gm, tern . E + Gm, quat . E and Liu [63], respectively.
n 1 n n 2 n 1 n At first, the thermodynamic interaction parameters of the phases at
= x x L + i=1
j = i + 1 i j ij
xxx L
k = j + 1 i j k ijk
+ x i xj xk xl0 Lijkl
i=1 j=i+1
the Fe–Mn side of the ternary Al–Fe–Mn system were assessed.
(3) Therefore, the experimental data of Umino et al. [34], Liu et al. [26,27],
where Gm, bin . E , and represent all binary, ternary and
Gm, tern . E Gm, quat . E Sato et al. [33], as well as the experimental investigations of the present
quaternary interaction parameters, respectively. The binary interaction work were used to describe the solubility of the A1, A2, B2 and β-Mn
parameters Lij were modeled using the Redlich-Kister polynomials phases. In a second step, the solubility of the Al–Fe and Al–Mn phases,
[53], which were expressed as: as well as the three ternary phases (φ, κ, D3) were modeled according to
m the experimental data of Balanetskyy et al. [19] and Priputen et al.
Lij = v
Lij (x i xj) . [31].
=0 (4) After the thermodynamic optimization of the ternary Al–Fe–Mn
system, the quaternary interaction parameters for the A1, A2 and B2
The ternary interaction parameters Lijk were modeled as [54]:
phases were modeled according to the experimental data of He and
i
Lijk = x i Lijk + xj Lijk + xk Lijk
j k
Zhou [49] and the heat-treated samples and diffusion couples of the
(5)
present work. The data of Kaputkina et al. [50] was not included in the
0
and for the quaternary interactions, only the parameters Lijkl were optimization of the parameters, since it was not considered as reliable
used. experimental data.
Solution phases with more than one sublattice, in which the com-
position of at least one of the constituent sublattices is allowed to vary, 6. Discussion of the thermodynamic optimization
were modeled using the compound energy formalism (CEF) [55]. The
Gibbs energy of such a phase is expressed as: 6.1. Al–Fe–Mn system

Gm = Gm, srf + Gm, conf + Gm, E
= 0
f Gend yis + RT s i
nsyis lnyis + Gm, E
where 0f Gend is the Gibbs energy of formation of the end-members, yis is
the site fraction of the species i on the sublattice s, n is the stoichio-
metric coefficient for each sublattice and Gm, E is the contribution of the
excess Gibbs energy. The excess Gibbs energy in the case of two sub-
lattices was modeled as:
Gm, E = yis yAr yBr vL A, B :C
P s r
where P represents the condition of an additional constituent on sub-
lattice r while all other sublattices are singularly occupied.
In the quaternary Al–Fe–Mn–Ni system, the disordered phases A1
and A2 form the ordered phases L12 and B2 respectively. In the present
description a single Gibbs energy function was used to describe the
disordered and the ordered version of the respective phases. The Gibbs
energy of mixing using the formalism as described in the work of Dupin
and Ansara [56,57], which is:
Gm = Gmdis + Gmord
where Gmdis is the (substitutional solution modeled) Gibbs energy of the
disordered phase and Gmord is the additional contribution to the Gibbs
free energy due to ordering. This additional contribution is described
as:
Gmord = Gmord (yis ) Gmord (yis = x i )
where Gmord (yis ) is the Gibbs energy of the ordered phase, expressed using
CEF, with the site fractions yis of component i on sublattice s and
Gmord (yis = x i ) is the Gibbs energy contribution of the disordered phase
to the ordered phase, calculated when the site fractions of each com-
ponent on each sublattice is the same and equal to the overall com-
position of the phase. The CalPhaD-based thermodynamic assessment
[58] of the Al–Fe–Mn–Ni system was performed using the PARROT
module [59] of the Thermo-Calc Software [60] for the optimization of
the thermodynamic parameters. Phase diagrams were calculated using
the Thermo-Calc Software.
5.1. Thermodynamic optimization of the Al–Fe–Mn and Al–Fe–Mn–Ni
systems
The binary descriptions of the Al–Fe, Al–Mn, Al–Ni, Fe–Mn, Fe–Ni
and Mn–Ni systems were taken from Zienert and Fabrichnaya [16], Du
et al. [18], Ansara et al. [61], Huang [17], Servant and Sundman [62]
The calculated isothermal sections of the Al–Fe–Mn system in
(6) comparison with the experimental data used for the description of the
ternary interaction parameters are illustrated in Fig. 6. For the Al-rich
portion, Fig. 6(c–g) and Fig. 7(e, f) show that the experimentally ob-
served solubility ranges of the intermetallic phases were reproduced
very well. Especially the phase equilibria involving the ternary phases
(φ, κ, D3), as well as the large solubility of the Al8Mn5 and the Al6Mn
phase were reproduced with high accuracy by the thermodynamic
calculations. Only the large solubility range of the Al13Fe4 phase could
(7) not be reproduced, since otherwise the interaction parameters would
exhibit uncommonly large values leading to incorrect calculations in
other parts of the phase diagram.
The calculated solubility ranges of the phases in the Fe–Mn side of
the phase diagram are in excellent agreement with the experimental
data, especially for the phases which are important for the further de-
velopment of SMAs in the Al–Fe–Mn–Ni system, as illustrated in the
isothermal sections in Fig. 6(a, b) and Fig. 7(a–d).
6.2. Al–Fe–Mn–Ni system
(8)
The calculated isoconcentration section at 1100 °C for 15 at.% Mn,
based on the present description of the Al–Fe–Mn–Ni system, is shown
in Fig. 8. Even though the actual manganese contents of the A1 and B2
phases in equilibrium (15.2 at.% for A1 and 15.1 at.% for B2, respec-
tively) are not exactly located in the illustrated plane of the quaternary
(9) tetrahedron the deviations are small and thus, this section can be used
for the illustration of the experimental phase equilibrium. The calcu-
lated phase diagram is in good agreement with the experimental data of
He and Zhou [49].
Regarding the heat-treated quaternary alloys of the present work,
two isoconcentration sections of the phase diagram are illustrated in
Fig. 9. The isoconcentration section at 1000 °C for 7.5 at.% Ni, together
with the experimentally determined tie-lines of the samples 15Al-
43.5Fe-34Mn-7.5Ni and 13.5Al-65Fe-14Mn-7.5Ni is shown in Fig. 9 (a).
The calculations show a good agreement with the experiments. The
isoconcentration section at 1175 °C for 20 at.% Mn, together with the
measured chemical compositions of the individual phases in the sam-
ples 12Al-61Fe-19Mn-8Ni, 15Al-36Fe-18Mn-31Ni and 14Al-14Fe-
20Mn-52Ni is given in Fig. 9 (b), showing a very good agreement be-
tween the experiments and the calculations. Especially the change of
the length of the tie-lines related to the transition from the disordered
A2 to the ordered B2 phase is reproduced very well by the present
thermodynamic description.
The isoconcentration sections used to illustrate the phase equilibria

8
A. Walnsch, et al. Calphad 66 (2019) 101621

Fig. 6. Calculated isothermal sections of the Al–Fe–Mn system based on the present thermodynamic assessment, together with the experimental data of Umino et al.
[34] (the indicated temperatures for the second-order transition A2/B2 display the measured transition temperatures of the DSC samples), Liu et al. [27], Balanetskyy
et al. [19], Liu et al. [37], Sato et al. [33], Liu and Hao [26], Priputen et al. [31] and the experimental investigations of the present work (the marked three-phase
equilibria indicate the overall chemical composition of the three-phase alloys). (a) T = 1200 °C, xAl < 0.2 (b) T = 1100 °C, xAl < 0.2 (c) T = 1070 °C, xAl > 0.4
(d) T = 1020 °C, xAl > 0.4 (e) T = 1000 °C (f) T = 950 °C, xAl > 0.5 (g) T = 875 °C, xAl > 0.5. The dashed lines mark the second-order transition between the
phases A2 and B2.

in the diffusion couples D1 and D2 of the present work are shown in
Fig. 10. Thereby, it was possible to show the whole diffusion path of
sample D1 in the isoconcentration section at 1000 °C for 8 at.% Mn (see
Fig. 10 (a)) since the manganese concentration along the diffusion
couple varies only to a small extent around 8 at.%. On the Ni-poor side
of the isoconcentration section the diffusion path (red line) starts in the
single-phase A2 region at the Al content of approximately 20 at.%. At
the chemical composition of 20.5Al-64.8Fe-7.7Mn-7.0Ni, indicated by
the asterisk inside the single-phase region, the direction of the diffusion
path suddenly changes, implying an effect related to the second-order

9
A. Walnsch, et al. Calphad 66 (2019) 101621

Fig. 7. Calculated isothermal sections of the Al–Fe–Mn system based on the present thermodynamic assessment, together with the experimental data of Umino et al.
[34] (the indicated temperatures for the second-order transition A2/B2 display the measured transition temperatures of the DSC samples), Liu et al. [27], Balanetskyy
et al. [19] and the experimental investigations of the present work (the marked three-phase equilibria indicate the overall chemical composition of the three-phase
alloys). (a) T = 900 °C, xAl < 0.5 (b) T = 850 °C, xAl < 0.5 (c) T = 800 °C, xAl < 0.5 (d) T = 725 °C, xAl < 0.5 (e) T = 695 °C, xAl > 0.5 (f) T = 650 °C, xAl > 0.5.
The dashed lines mark the second-order transition between the phases A2 and B2.

phase transition from the disordered A2 to the ordered B2 phase. This

Fig. 8. Calculated partial isoconcentration section at 1100 °C for xMn = 0.15 of
the Al–Fe–Mn–Ni system based on the present thermodynamic assessment, to-
gether with the experimental data of He and Zhou [49]. The indicated numbers
at the experimental data points display the molar fractions xMn of the individual
phases.
second-order transition is well described by the calculations, as in-
dicated by the dashed line in the phase diagram. With increasing Al
content in the single-phase B2 region, the diffusion path enters the
A1 + B2 two-phase field, indicated by the red area in Fig. 10 (a). The
experimentally observed tie-lines in the two-phase area of the diffusion
couple D1, shown in the marked two-phase field (A1 + B2) in Fig. 10
(a), are in very good agreement with the calculations. After passing the
two-phase region, the diffusion path continues until reaching the che-
mical composition of the end-member of the diffusion couple, being
located in the single-phase A1 region. Even though the diffusion path in
Fig. 10 (a) does not seem to cross the mass-balance line [51], the
conservation of mass is fulfilled, since in the single-phase A2 region, the
Al concentration is slightly reduced from 20 to 19 at.% across a very
large area in the diffusion couple. This long-range depletion of Al
compensates the enrichment of Al in the narrow B2 region, after the
second-order transition, preserving the mass balance in the diffusion
couple D1. For sample D2, the whole diffusion path could not be dis-
played in a single isoconcentration section, since the concentration of
all elements along the diffusion path are varying too much. Never-
theless, the experimentally observed tie-lines in the two-phase region of
diffusion couple D2 exhibit almost constant Mn concentrations of

10
A. Walnsch, et al. Calphad 66 (2019) 101621

Fig. 10. Calculated partial isoconcentration sections of the Al–Fe–Mn–Ni

Fig. 9. Calculated partial isoconcentration sections of the Al–Fe–Mn–Ni system system based on the present thermodynamic assessment, together with the
based on the present thermodynamic assessment, together with the experi- experimental data of the diffusion couples (D1 and D2) of the present work. (a)
mental data of the heat treated and quenched samples of the present work. (a) T = 1000 °C, xMn = 0.08, together with the diffusion path of sample D1 given
T = 1000 °C, xNi = 0.075 (b) T = 1175 °C, xMn = 0.2. The dashed line refers to as the red line and the two-phase field (A1 + B2) covered by the diffusion
the second-order transition between the phases A2 and B2. The indicated couple illustrated with the red marked area. (b) T = 1000 °C, xMn = 0.1, to-
numbers at the experimental data points display the molar fractions xNi and xMn gether with the tie-lines extracted from the two-phase area of diffusion couple
of the individual phases in (a) and (b), respectively. D2. The dashed lines mark the second-order transition between the phases A2
and B2. The indicated numbers at the experimental data points display the
approximately 10 at.%. Therefore, Fig. 10 (b) illustrates the iso- molar fractions xMn of the individual phases. (For interpretation of the refer-
concentration section at 1000 °C for 10 at.% Mn, together with the tie- ences to colour in this figure legend, the reader is referred to the Web version of
lines between the phases A1 and B2 in the two-phase region of diffusion this article.)
couple D2, showing a very good agreement between the experiment
and the calculations based on the present assessment.
The phase equilibria, determined in diffusion couple D3, are shown
in the isoconcentration sections illustrated in Fig. 11. The two-phase
equilibrium of the quaternary end-member of the diffusion couple D3
(12.5Al-47Fe-32Mn-7.5Ni) is shown in the isoconcentration section at
1175 °C for 7.5 at.% Ni given in Fig. 11 (a). For the region of isolated
precipitates in diffusion couple D3 (A1 + B2), the experimental data is
shown in the isoconcentration section at 1175 °C for 17.5 at.% Mn in
Fig. 11 (b). Both calculated sections show a very good agreement with
the experimentally determined tie-lines of diffusion couple D3.

7. Conclusions

New insights on the phase relations at 725 and 1000 °C of the

ternary Al–Fe–Mn and at 1000 and 1175 °C of the quaternary
Al–Fe–Mn–Ni systems were gained, regarding the phase equilibria in-
volving the relevant phases for SMA applications (A1, A2, B2 and β-
Mn). For the ternary Al–Fe–Mn system, the two-phase equilibria be-
tween A1 and β-Mn were refined by several heat-treated samples and
can be reproduced by calculations using the thermodynamic database
developed in the present assessment. Fig. 11. Calculated partial isoconcentration sections of the Al–Fe–Mn–Ni
Moreover, a thermodynamic description of the quaternary system based on the present thermodynamic assessment, together with the
experimental data of the diffusion couple D3 obtained in the present work. Due
Al–Fe–Mn–Ni system was established for the first time. The quaternary
to clarity reasons, only every second measured tie-line in (b) was marked with
interaction parameters of the A1, A2 and B2 phases were optimized
the respective Ni-concentration). (a) T = 1175 °C, xNi = 0.075 (b) T = 1175 °C,
based on experimental data measured by conventional equilibration of xMn = 0.175. The dashed line refers to the second-order transition between the
alloys and diffusion couples. For both methods, the calculations based phases A2 and B2. The indicated numbers at the experimental data points
on the present database are in excellent agreement with the experi- display the molar fractions xNi and xMn of the individual phases in (a) and (b),
mentally observed phase equilibria. Therefore, extrapolating calcula- respectively.
tions using the present thermodynamic description enable a further

11
A. Walnsch, et al. Calphad 66 (2019) 101621

improvement of materials properties and heat-treatment procedures of Acknowledgements

these innovative Fe-based SMAs.
Data availability statement
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
This work was financially supported by the German Research
Foundation (DFG) [grant number KR 4855/1-1]. The authors would
like to thank Dr.-Ing. Anton Salomon for his support with the SPS
bonding of the diffusion couples.

Appendix A. Summary of the obtained thermodynamic parameters for the Al–Mn–Ni system

Parameter Function [J·mol−1, J·mol−1·K−1]

Liquid: (Al,Fe,Mn)
0 LIQUID −27349.27618
LAl, Fe,Mn
1 LIQUID −25105.97318
LAl, Fe,Mn
2 LIQUID −19863.37915
LAl, Fe, Mn
A1: (Al,Fe,Mn,Ni)(VA)
0 A1 −479308.058 + 282.591257 T
LAl, Fe,Mn : VA
1 A1 −54144.7454
LAl, Fe, Mn: VA
2 A1 −25068.59713
LAl, Fe, Mn : VA
0 A1 309860.284–315.170412 T
LAl, Fe,Mn, Ni : VA
A2: (Al,Fe,Mn,Ni,VA)(VA)3
0 A2 −852.165191 + 24.2454212 T
LAl, Fe,Mn : VA
1 A2 −6003.44368
LAl, Fe, Mn: VA
2 A2 −19845.673194
LAl, Fe, Mn : VA
0 A2 −462425.797 + 197.784337 T
LAl, Fe,Mn, Ni : VA
B2: (Al,Fe,Mn,Ni,VA)0.5(Al,Fe,Mn,Ni,VA)0.5(VA)3
0 B2 0 11660.3861
LAl, Mn: Fe : VA = LFe
B2
: Al, Mn : VA
0 B2 0 3362.77542
LAl, Fe : Mn : VA = LMn
B2
: Al, Fe : VA
0 B2 0 B2 333.045267
LFe, Mn : Al : VA = LAl : Fe, Mn : VA
0 B2 0 B2 −12986.5448
LFe, Mn,Ni : Al : VA = LAl : Fe, Mn, Ni : VA
0 B2 0 B2 −93502.9745
LAl, Mn, Ni : Fe : VA = LFe : Al, Mn, Ni : VA
0 B2 0 B2 −19856.2315
LAl, Fe,Ni : Mn : VA = LMn : Al, Fe, Ni : VA
0 B2 0 B2 30105.9874
LAl, Fe,Mn : Ni : VA = LNi : Al, Fe, Mn : VA
β-Mn: (Al,Mn,Ni)(VA)
0 Mn −117139.263 + 31.2472641 T
LAl, Fe : VA
1 Mn 41675.5801
LAl, Fe : VA
0 Mn −133271.266
LAl, Fe , Mn : VA
1 Mn 54046.8534
LAl, Fe , Mn : VA
2 Mn −26383.2251
LAl, Fe , Mn : VA
ε: (Al,Mn,Ni)(VA)0.5
0
LAl, Ni : VA −125498.432

Al2Fe: (Al)12(Fe,Mn)5(Al,Fe)2
0 Al Fe −29859.397654 + 14·GHSERAL + 5·GHSERMN
GAl :2Mn : Al
0 Al Fe −26942.5 + 12·GHSERAL + 5·GHSERMN + 2·GHSERFE
GAl :2Mn : Fe
0 Al Fe −305465.322
LAl :2Fe, Mn : Al
0 Al Fe −466965
LAl :2Fe, Mn : Fe
Al5Fe2: (Al)8(Fe,Mn)4(Al,VA)4
0 Al Fe −109287.8263 + 8·GHSERAL + 4·GHSERMN
GAl :5Mn2: VA
0 Al Fe −150068.7138 + 12·GHSERAL + 4·GHSERMN
GAl :5Mn2: Al
0 Al Fe −592288.263 + 292.896741 T
LAl :5Fe, Mn
2
: Al
0 Al Fe −290493.733
LAl :5Fe, Mn
2
: VA
Al13Fe4: (Al)0.6275(Fe,Mn)0.235(Al,VA)0.1375
0 Al Fe −5986.37945 + 0.6275·GHSERAL + 0.235·GHSERMN
GAl :13 4
Mn : VA

12
A. Walnsch, et al. Calphad 66 (2019) 101621

0 Al Fe −20172.6016 + 7.912288 T + 0.765·GHSERAL + 0.235·GHSERMN

GAl :13 4
Mn : Al
0 Al Fe −5584.64295
LAl :13 4
Fe, Mn : Al
0 Al Fe −9918.80007
LAl :13 4
Fe, Mn : VA
Al8Mn5: (Al)12(Mn,Fe)5(Al,Mn,Fe)9
0 Al Mn −348687.512 + 21·GHSERAL + 5·GHSERMN
GAl :8Fe : Al5
0 Al Mn −619984.705 + 12·GHSERAL + 14·GHSERMN
GAl :8Fe : Fe5
0 Al Mn −654576.268 + 12·GHSERAL + 5·GHSERMN + 9·GHSERFE
GAl :8Mn :5Fe
0 Al Mn −314379.184
LAl :8Mn :5Al, Fe
0 Al Mn 119335.5
LAl :8Mn :5Fe, Mn
0 Al Mn −288460.9 + 107.71326 T
LAl :8Fe : Al5 , Fe
HT-Al11Mn4: (Al,Mn)29(Mn,Fe)10
0 HT Al11 Mn 4 698428.182–320.52 T + 29·GHSERMN + 10·GHSERFE
GMn : Fe
0 HT Al Mn −656539.1–103.8 T + 29·GHSERAL + 10·GHSERFE
GAl : Fe 11 4
0 HT Al Mn
11 4 −3129944.45 + 1436.64717 T
LAl, Mn: Fe
0 HT Al Mn
11 4 −273797.005 + 197.07 T
LAl : Fe, Mn
1 HT Al Mn
11 4 1.75908082–114.370329 T
LAl: Fe,Mn
0 HT Al Mn
11 4 −1147591.71 + 862.07 T
LAl, Mn: Mn , Fe
LT-Al11Mn4: (Al,Mn)11(Mn,Fe)4
0 LT Al Mn −74967.654 + 11·GHSERMN + 4·GHSERFE
GAl : Fe 11 4
0 LT Al Mn
11 4 −251268.68
LAl : Fe, Mn
Al6Mn: (Al)6(Mn,Fe)
0 Al Mn −60439.3279 + 6·GHSERMN + GHSERFE
GAl :6Fe
0 Al Mn −729443 + 671.29 T
LAl :6Fe, Mn
φ: (Al)0.7(Al,Mn)0.15(Mn,Fe)0.15
0
GAl : Al : Fe −3478.641913 + 5.12394 T + 0.85·GHSERAL + 0.15·GHSERFE
0
GAl : Al : Mn −7892.135498 + 0.85·GHSERAL + 0.15·GHSERMN
0
GAl : Mn : Fe −11802.97388–6.985235 T + 0.7·GHSERAL + 0.15·GHSERFE + 0.15·GHSERMN
0
GAl : Mn : Mn −25381.18638 + 10.34109 T + 0.7·GHSERAL + 0.3·GHSERMN
0
LAl : Al, Mn : Mn −9503.9539

0
LAl : Al, Mn : Fe −6987.9687

0
LAl : Mn : Fe, Mn −4015.5869

0
LAl : Al: Fe, Mn −19867.689 + 12.896348 T

0
LAl : Al, Mn : Fe, Mn −65195.3659 + 58.876489 T

κ: (Al)4(Al,Mn)
0
GAl : Fe −27896.37948 + 4·GHSERAL + GHSERFE
0
GAl : Mn −96306.27943 + 26.496 T + 4·GHSERAL + GHSERMN
0
LAl : Fe, Mn −254298.7461 + 147.44 T

D3: (Al)0.72(Mn)0.19(Fe)0.09
0 D −22809.34921 + 2.4042 T 0.72·GHSERAL + 0.19·GHSERMN + 0.09·GHSERFE
GAl3: Mn: Fe

Appendix B. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.calphad.2019.04.006.

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