Calphad 64 (2019) 78–89

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

Thermodynamic assessment and experimental investigation of the T

Al–Mn–Ni system
⁎
Alexander Walnsch, Mario J. Kriegel , Martin Rudolph, Mykhaylo Motylenko, Olga Fabrichnaya,
Andreas Leineweber
TU Bergakademie Freiberg, Institute of Materials Science, Gustav-Zeuner Str. 5, 09599 Freiberg, Germany

A B S T R A C T

The ternary Al–Mn–Ni system plays an important role in the development of several structural and functional materials. To accomplish a purposeful development of
alloys related to this system, an assessment of the thermodynamic parameters was performed. The assessment is based on literature data, as well as experimental
investigations regarding the phase equilibria at 800 and 1000 °C. Moreover, the decomposition of the disordered A2 phase in the Mn-rich corner of the Al–Mn–Ni
system was investigated by means of transmission electron microscopy and in-situ X-ray diffraction. Calculations based on the present description are in excellent
agreement with the experimental data available in literature and reproduce the experimental results of the present work.

1. Introduction extrapolations and a valid and target-oriented alloy design.

Materials based on the ternary Al–Mn–Ni system possess a wide
variety of excellent properties, leading to the possibility of utilizing
these alloys for structural and functional applications. Al-rich and
Al–Ni-based alloys were investigated due to their promising specific or
high-temperature strengths [1–5]. In addition to these structural ma-
terials, the magnetic Al–Mn–Ni alloys are of remarkable interest and
were investigated extensively in the last decades [3,6–11]. Due to their
complex magnetic properties and crystallographic ordering phe-
nomena, magnetic Heusler alloys of the Al–Mn–Ni system attracted the
attention of many research groups which studied these alloys theore-
tically [12–17], as well as experimentally [18–23].
Besides the magnetic shape memory alloys, based on the Ni2MnAl
Heusler phase, the Al–Mn–Ni system plays an important role in the
development of several different classes of shape memory alloys
(SMAs). Since Al, Mn and Ni are main alloying elements in many Cu-
based [24–32] and Fe-based [33–45] SMAs, it is necessary to in-
vestigate the influence of these elements on the phase stabilities in the
corresponding alloy systems.
To achieve this goal, comprehensive experimental investigations
were conducted by means of EPMA, XRD and DTA analyses of several
heat-treated and quenched samples of the ternary Al–Mn–Ni system. A
thermodynamic assessment, using the CalPhaD (Calculation of Phase
Diagrams) approach [46], was developed (i) to allow the adjustment of
the chemical composition of Al–Mn–Ni alloys, as well as (ii) the in-
corporation in thermodynamic descriptions of higher order systems
(e.g. Fe–Mn–Al–Ni for SMA applications), to perform reliable
2. Experimental procedure
Six ternary Al–Mn–Ni alloys were prepared by arc melting of high
purity metal mixtures (Al: 99.9995%, Mn: 99.95%, Ni: 99.995%). These
alloys will be denoted in the following by the nominal compositions as
oAl-nMn-mNi with o, n and m indicating the Al, Mn and Ni contents in
at%, respectively. According to this denotation, the nominal composi-
tions of the observed samples were 22Al-55Mn-23Ni, 15Al-58Mn-27Ni,
10Al-78Mn-12Ni, 11Al-60Mn-29Ni, 14Al-62Mn-24Ni and 11Al-68Mn-
21Ni. 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-treat-
ment process, the samples were sealed in fused silica ampoules under a
controlled argon atmosphere with Ar pressures between 250 and 300
mbar, depending on the subsequent heat-treatment temperature. The
heat treatments of the samples were conducted in a horizontal tube
furnace at 800 and 1000 °C for 504 and 72 h, respectively, and subse-
quently quenched in ice water.
The chemical composition of each phase and the overall composi-
tion of the alloys were determined using electron-probe microanalysis
with wavelength-dispersive X-ray spectroscopy (EPMA/WDS). The
chemical compositions of the individual phases were measured locally
whereas the overall chemical compositions were obtained from aver-
aged EPMA line-scans over 1 mm with a step size of 1 µm. The mea-
surements were performed using a JEOL JXA-8900 RL microprobe at

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

https://doi.org/10.1016/j.calphad.2018.11.003
Received 14 September 2018; Received in revised form 2 November 2018; Accepted 8 November 2018
0364-5916/ © 2018 Elsevier Ltd. All rights reserved.
A. Walnsch et al. Calphad 64 (2019) 78–89

20 kV accelerating voltage. Table 1

Phase identification was performed using X-ray diffraction (XRD). Stable solid phases in the Al–Mn–Ni system.
XRD pattern were measured on polished cross sections using a URD6 Phase Prototype Pearson symbol Space group
diffractometer (Seifert/FPM Freiberg, Germany). The goniometer
working in conventional Bragg-Brentano geometry used CuKα radiation Al12Mn Al12W cI26 Im3̅
(wavelengths: 0.154056 and 0.154437 nm) and was equipped with a Al3Ni CF3 oP16 Pnma
Al3Ni2 Al3Ni2 hP5 P3̅ m1
curved graphite monochromator in the diffracted beam. Whole pattern-
Al3Ni5 CdPt3 oC8 Cmmm
based refinements using the Rietveld method [47,48] with the software Al4Mn µ-Al4Mn hP563 P63 /mmc
TOPAS [49] were used to verify the phase compositions and to de- Al6Mn CrB oC8 Cmcm
termine respective lattice parameters. Al8Mn5 R-Al8Cr5 hR26 R3̅ m
In-situ X-ray diffraction at high temperatures (HT) was performed A2 W cI2 Im3̅ m
with a Bruker D8 Advance (Bruker AXS, Karlsruhe, Germany) dif- B2 CsCl cP2 Pm3̅ m
α-Mn α-Mn cI58 I4̅ 3m
fractometer in θ-θ-geometry. The diffractometer was equipped with a
β-Mn β-Mn cP20 P41 32
sealed X-ray tube with Cu anode. Photons were detected using a A1 Cu cF4 Fm3̅ m
LynxEye XE 1D detector. The high temperature stage at the dif- ε Mg hP2 P63 /mmc
fractometer was a MTC HighTemp+, in which the sample was placed HT-Al11Mn4 Al3Mn oP156 Pnma
on a resistively heated Ta strip. In order to decrease the temperature L10 AuCu tP2 P4/mmm
gradient in the chamber, the sample was additionally surrounded by a L12 AuCu3 cP4 Pm3̅ m
LT-Al11Mn4 Al11Mn4 aP30 P1̅
Ta strip radiation heater. The temperature is recorded by a type D (W-
MnNi2 – – –
Re3/W-Re25) thermocouple directly in contact with the Ta heater strip. R-Al4Mn NbSe2 hP6 P63 /m
The sample was not placed directly on the Ta strip due to possible re- φ Al5Co2 hP26 P63 /mmc
actions between the sample and the Ta heater, but was placed on a κ κ-Al14,4Cr3,4Ni1,1 hP227 P63 /m
piece of a {100}-oriented sapphire single crystal. The thermal shielding O O-Al77Cr14Pd9 oP650 Pmmn

by sapphire was found to be less than 100 K due to their transparency

for heat radiation. The temperature calibration of the HTXRD data was
Fig. 1.
based on the DTA data. To limit oxidation of the samples and to avoid
A few experimental investigations on the constitution of the ternary
the evaporation of Mn during the HTXRD measurements, the chamber
Al–Mn–Ni system are available in literature [9,11,53–60]. The present
was purged by Ar gas and simultaneously evacuated by a vacuum
assessment is based mainly on two major works [53,56]. The first one
pump. The resulting pressure inside the chamber was adjusted to 0.3
by Balanetskyy et al. [53] deals with the Al-rich part of the phase
mbar. X-ray pattern were recorded in a limited 2θ − range to reduce
diagram and the second one by Kainuma et al. [56] investigated the
measurement time and therefore reduce the temperature difference
Mn–Ni side of the ternary Al–Mn–Ni system. Since the solubility of the
between the measured diffraction pattern. For HTXRD measurements a
phases was investigated almost in the whole composition range, it is
heating rate 5–20 K/min was used, while XRD pattern were recorded
possible to assess the thermodynamic parameters of the phases in the
continuously. Reference scans for phase identification were taken be-
Al–Mn–Ni system. There is no information in literature concerning the
fore and after the heating runs.
solubility of Ni and Mn in Al12Mn and Al3Ni5, but Balanetskyy et al.
The spatial distribution of the individual phases in the alloys was
[53] showed limited solubility for the other Al-rich intermetallic phases
obtained from scanning electron micrographs. These micrographs were
(Al3Ni, Al3Ni2, Al4Mn, Al6Mn, Al8Mn5 and HT/LT-Al11Mn4) depending
taken using back-scattered electrons (SEM/BSE) with a FEG-SEM LEO
on temperature [53,61]. For example, in the alloys, which were heat
1530 GEMINI that was operated at an acceleration voltage of 20 kV. In
treated at 1000 °C, Al8Mn5 and HT-Al11Mn4 were found to dissolve up
order to correlate the SEM/BSE contrast with local chemical composi-
to 3.0 at% and 1.7 at% Ni, respectively, and the solubility of Al3Ni2 was
tions measured with EPMA, energy-dispersive X-ray spectroscopy (EDS)
determined to be 3.3 at% Mn. Moreover, Balanetskyy et al. [61] iden-
point measurements were performed on the respective grains using a
tified three different ternary phases, which form at different tempera-
Bruker EDS system.
tures and exhibit large homogeneity ranges [53,61]. The ternary φ
Transmission electron microscopy (TEM) investigations were per-
phase is stable below 993 °C and possesses a hexagonal crystal struc-
formed with a JEOL JEM-2200FS, operating at 200 kV, to investigate
ture, based on the Al5Co2 type. Its compositional limits vary with
the eutectoid decomposition of the high temperature A2 phase by
temperature and range from 69–74 at% Al and 15–23 at% Mn at 950 °C
means of Fourrier transformation analyses (FFT) on high resolution
to 70–77 at% Al and 14–22 at% Mn at 750 °C. Additionally, at 867 °C
TEM (HRTEM) images. The TEM lamella was prepared by the lift-out
the hexagonal ternary κ phase forms by a peritectic reaction. This phase
technique using the focused ion beam (FIB) FEI Helios NanoLab 600i.
has a narrow homogeneity range at almost constant Al contents of 80 at
In order to determine the temperature of transition reactions,
% and vary between 1 and 6 at% of Ni, as a function of temperature.
thermal analyses were performed on as-solidified samples using dif-
The third ternary phase, which was observed by Balanetskyy et al. [61]
ferential thermal analysis (DTA) with the SetSys Evolution 1750
is the orthorhombic O phase, which forms peritectically below 757 °C.
(SETARAM, France) device. The samples were placed in Al2O3 crucibles
The O phase exhibits a very small homogeneity range around the
and heated/cooled in inert He-atmosphere (99.999%) using heating/
chemical composition of 78Al-13Mn-9Ni, which doesn’t vary with
cooling rates of 20 and 30 K/min respectively. The device was cali-
temperature [53,61].
brated to the melting temperatures of pure elements (Al, Au, Ni). The
In the Ni-rich area of the phase diagram, Jia et al. [55] and Kainuma
transition temperatures of solid state reactions were determined using
et al. [56] investigated the phase equilibria between the A1, B2 and L12
the onset point of the DTA signal.
phases in the temperature range between 800 and 1300 °C. At 1000 °C,
Kainuma et al. [56] were able to determine the A1 + B2 + L12 tie-tri-
3. Phase equilibria in the Al–Mn–Ni system
angle, revealing the maximum solubility of the L12 phase for Mn at
15.2 at% Mn. The EPMA measurements of the quenched samples
3.1. Literature review
showed that the homogeneity range of the L12 phase extends towards
lower temperatures, until up to approximately 20 at% Mn at 800 °C
The crystallographic data of the solid phases in the Al–Mn–Ni
[55,56]. Moreover, the data of Kainuma et al. [56] showed the de-
system are given in Table 1 and phase diagrams of the binary sub-
creasing solubility of Al in the disordered A1 phase upon cooling, which
systems Al–Mn [50], Mn–Ni [51] and Ni–Al [52] are illustrated in

79
A. Walnsch et al.
Fig. 1. Calculated phase diagrams of the binary subsystems: (a) Al–Mn system [50], (b) Mn–Ni system [51], (c) Ni–Al system [52].
is also indicated by the DTA investigations of Mishima et al. [58].
Kainuma et al. [56] also investigated the equilibria involving the
A2, ε and β-Mn phases in the temperature range between 850 and
1100 °C. As compared to higher temperatures, a remarkable expansion
of the B2 + β-Mn two-phase field was observed at 850 °C, which almost
reaches the binary Al–Ni system. Moreover, it was stated that at tem-
peratures above 1000 °C a first-order as well as second-order transitions
between the disordered A2 and the ordered B2 phase should occur,
depending on the chemical composition [56].
Besides the EPMA measurements of the heat-treated and quenched
samples, Wachtel et al. [11] and Henninger [54] investigated two dif-
ferent isopleths using susceptibility measurements. Wachtel et al. [11]
examined 15 samples in the isopleth between Ni3Al and Ni3Mn, con-
cerning the phase equilibria between L12, A1 and Liquid, which is in
good agreement with the investigations by Masahashi et al. in the same
isoplethal section [11,57]. The other isopleth, between NiAl and NiMn,
was investigated by Henninger [54]. This section shows the equilibria
between B2 and Liquid. Besides the eight samples, which were used to
construct the NiAl–NiMn isopleth, Henninger also investigated five
other samples in the ternary Al–Mn–Ni system with Al concentrations
up to 50 at% to determine a partial liquidus surface [54].
3.2. Experimental investigations
In order to investigate the extension of the B2 + β-Mn two-phase
field at lower temperatures, the samples with the nominal compositions
22Al-55Mn-23Ni, 15Al-58Mn-27Ni and 10Al-78Mn-12Ni were heat
treated at 800 °C for 504 h and subsequently quenched in ice water.
Exemplarly, the SEM/BSE micrograph of 15Al-58Mn-27Ni (Fig. 2)
Fig. 2. SEM/BSE micrograph of the crosssectionally polished 15Al-58Mn-27Ni
alloy annealed at 800 °C for 504 h and subsequently quenched in ice water
exhibiting B2 and β-Mn phases (Table 1).
80
Calphad 64 (2019) 78–89
shows a B2 + β-Mn two-phase microstructure which formed during the
heat treatment at 800 °C. The chemical compositions (EPMA) of the
phases, as well as their lattice parameters (XRD) are summarized in
Table 2.
In order to refine the isothermal section at 1000 °C and to verify the
observations of Kainuma et al. [56], samples with nominal chemical
compositions of 11Al-60Mn-29Ni, 14Al-62Mn-24Ni and 11Al-68Mn-
21Ni were heat treated at 1000 °C for 72 h and subsequently quenched
in ice water. The microstructures of the heat-treated samples are illu-
strated in Fig. 3. The microstructural investigations show a (A1 + B2)
two-phase microstructure for the sample 11Al-60Mn-29Ni, which is in
agreement with the proposed isothermal section of Kainuma et al. [56].
The samples with the nominal chemical composition of 14Al-62Mn-
24Ni and 11Al-68Mn-21Ni show two microstructural components: a
very fine microstructure plus B2 (14Al-62Mn-24Ni) or plus A1 (11Al-
68Mn-21Ni). The fine microstructure was analysed by TEM (see Fig. 4)
and consist of B2 + A1, the latter being heavily faulted. The presence of
such a very fine microstructure after annealing at 1000 °C implies its
formation upon quenching. At the annealing temperature of 1000 °C
likely a two-phase microstructure was present, where one of these
phases could not be retained. The high-temperature XRD data (see
below) imply that this phase has the A2 structure, which decomposes
by eutectoid reaction to B2 + A1 upon quenching. Notably, the (aver-
aged) compositions of the fine microstructure measured by EPMA is
very close for the alloys 14Al-62Mn-24Ni and 11Al-68Mn-21Ni quen-
ched from 1000 °C: 13.6Al-62.7Mn-23.7Ni and 13.4Al-63.2Mn-23.4Ni.
The chemical compositions of the other phases and their corresponding
lattice parameters are summarized in Table 2.
The sample 11Al-68Mn-21Ni was additionally analysed by DTA
measurements, as well as in-situ XRD measurements during heating in
order to investigate the transition temperature of the eutectoid reaction
and the participating phases in the eutectoid reaction. Fig. 5 shows the
combined results of both, the in-situ XRD (a,b) and the DTA in-
vestigations. The DTA curve illustrated in Fig. 5 shows three en-
dothermic effects upon heating, which were marked with the dashed
lines 1, 2 and 3. The first one at 856 °C is associated with the trans-
formation of β-Mn into A1, as it can be seen in both Fig. 5(a) and (b)
due to the disappearing of the 201, 221, 310 and 311 reflections of β-
Mn and the increase of the intensity of the 111 and 200 reflections of
A1. The temperature difference between both methods arising upon
heating is related to the experimental setup of the in-situ XRD, since the
thermal barrier caused by the sample carrier, the actual temperature at
the sample differs from the recorded temperature of the heating tape.
The second endothermic effect at 977 °C in the DTA signal describes
the eutectoid decomposition of A2 into A1 and B2, since the intensities
of the A1 reflections, as well as the B2 reflections in Fig. 5(b) decrease
as the intensity of the 110 A2 reflection increases upon heating.
A. Walnsch et al. Calphad 64 (2019) 78–89

Table 2
Chemical compositions (EPMA) and lattice parameters (XRD) of the samples heat treated at 800 °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 Lattice parameter a [nm] Phase composition [at%]

Al Mn Ni Al Mn Ni

22Al- 55Mn-23Ni 800 22.4 54.7 22.9 B2 0.2919 34.0 22.1 43.9
β-Mn 0.6382 13.6 80.5 5.9
15Al- 58Mn-27Ni 800 15.3 57.6 27.1 B2 0.2929 25.7 31.3 43.0
β-Mn 0.6374 8.8 74.2 17.0
10Al- 78Mn-12Ni 800 10.1 78.0 11.9 B2 -* 28.8 27.7 43.5
β-Mn 0.6363 9.4 79.7 10.9
11Al- 60Mn-29Ni 1000 10.6 59.5 29.9 A1 0.3708 6.1 70.0 23.9
B2 0.2934 14.1 51.2 34.7
14Al- 62Mn-24Ni 1000 14.2 61.9 23.9 B2 0.2919 15.1 59.0 25.9
A2 -** 13.6 62.7 23.7
11Al- 68Mn-21Ni 1000 11.1 68.4 20.5 A1 0.3717 8.5 73.6 17.8
A2 -** 13.4 63.2 23.4

* insufficient amount of the phase for accurate lattice parameter determination with XRD.
** phase decomposed into A1 and B2 upon quenching.

Moreover Fig. 5(a) shows the complete disappearance of the super-

structure reflection of B2, indicating the disorder of the high tem-
perature A2 phase. The third endothermic effect, located slightly above
1000 °C, indicates the transition from the A1 + A2 two-phase field into
a single-phase A2 field, since the intensities of the 111 and 200 A1
reflections decrease, as the intensity of the 110 A2 reflection increases
upon heating. To verify this single-phase region, an additional heat
treatment of sample 11Al-68Mn-21Ni was carried out at 1050 °C for
72 h. The obtained microstructure is illustrated in Fig. 6. A eutectoidly
decomposed microstructure containing A1 and B2 was observed, con-
firming the single phased A2 sample at the heat-treatment temperature,
as indicated by the in-situ XRD measurements.
Furthermore, to investigate the stability range of the disordered A2
phase at higher Mn-contents, as proposed by the experimental in-
vestigations of Kainuma et al. [56], the sample 9Al-82Mn-9Ni was also
investigated by means of DTA and in-situ XRD. Fig. 7(a) and (b) show
the results of the in-situ XRD, whereas Fig. 7(c) shows the DTA curve
during heating, indicating two endothermic effects at temperatures
above 900 °C, marked by the dashed lines 1 and 2. The first effect at
943 °C is related to the formation of A1, due to the appearance of the
111 and 200 A1 reflections, shown in Fig. 7(b). The sharpness of this
effect indicates the occurrence of a four-phase transition reaction
(A1 + A2 ⇄ B2 + β-Mn) near the nominal chemical composition of the
sample at the given temperature. Therefore, due to slight in-
homogeneities, this effect occurs upon heating, as indicated by the
occurrence of the B2 110 reflection illustrated in the isothermal XRD
measurement at 1000 °C in Fig. 7(d). However, since the nominal
chemical composition is located near the A1 + β-Mn two-phase field,
the reflections related to these phases show much higher intensities.
The second endothermic effect at 1086 °C in the DTA curve is connected
to the transformation of β-Mn into disordered A2, due to the dis-
appearance of the β-Mn reflections, shown in Fig. 7(a) and (b) and the
appearance of the 110 A2 reflection, without an increase in the in-
tensity at the position of the B2 100 superstructure reflection.

4. Thermodynamic modeling

The thermodynamic descriptions of the pure elements were taken

from Dinsdale [62]. For a ternary stoichiometric compound AxByCz, the
Fig. 3. SEM/BSE micrographs of crossectionally polished 11Al-60Mn-29Ni, Gibbs energy G Ax B y Cz was modelled as:
14Al-62Mn-24Ni and 11Al-68Mn-21Ni alloys annealed at 1000 °C for 72 h and
subsequently quenched in ice water. The labels indicate the present phases G Ax B y Cz − xHAθ − yHBθ − zHCθ
(Table 1). The mixture (A1 + B2) describes a eutectoid microstructure. = Δf G Ax B y Cz (T ) + xGHSERA
+ yGHSERB + zGHSER C (1)
where Hiθ is the enthalpy of a pure element i in the phase θ at 298.15 K,

81
A. Walnsch et al. Calphad 64 (2019) 78–89

Fig. 4. (a) TEM image of the eutectoid

microstructure of sample 11Al-68Mn-
21Ni annealed at 1000 °C for 72 h. (b)
HRTEM image of a characteristic area
of (a). (c) FFT of the marked region c in
the HRTEM image (b) showing an or-
dered B2 structure. (d) FFT of the
marked region d in the HRTEM image
(b) showing an A1 structure with ad-
ditional reflections due to periodic
faulting.

Δf G Ax B y Cz (T ) is the Gibbs energy of formation of the stoichiometric Gmθ = Gmθ,srf + Gmθ,conf + Gmθ,E
compound from pure elements and GHSERi is the Gibbs energy of a =
n n
∑i = 1 x i Giθ + RT ∑i = 1 x i ln x i + Gmθ,E (2)
pure element i referred to the enthalpy of its stable state at 298.15 K.
Substitutional solutions were modelled as: n
with the surface of reference term Gmθ,srf = ∑i x i Giθ , the contribution to
the Gibbs energy from the configurational entropy of mixing
n
Gmθ,conf = RT ∑i x i⋅ln x i and the excess Gibbs energy Gmθ,E which is

Fig. 5. In-situ XRD measurement of sample 11Al-68Mn-21Ni upon heating from 700 to 1170°C in the 2θ-range from (a) 29 to 31.5° and (b) 39 to 49° (the dashed lines
1, 2 and 3 refer to the three endothermic effects in the DTA curve in (c)) (c) DTA curve of the sample 11Al-68Mn-21Ni in the temperature range from 650 to 1050 °C.
The asterisk symbols indicate the uncorrected temperatures derived from the HTXRD measurements.

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A. Walnsch et al. Calphad 64 (2019) 78–89

θ
Lijk = x i iLijk
θ
+ x j jLijk
θ
+ xk kLijk
θ
(5)
Solution phases with more than one sublattice, in which the com-
position of at least one of the constituent sublattices is allowed to vary,
were modelled using the compound energy formalism (CEF) [65]. The
Gibbs energy of such a phase is expressed as:

Gmθ = Gmθ,srf + Gmθ,conf + Gmθ,E

= ∑ Δ0f Gend ∏ yis
+ RT ∑s ∑i nsyis ln yis + Gmθ,E (6)
where Δ0f 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 Gmθ,E is the contribution of the
Fig. 6. SEM/BSE micrograph of the crosssectionally polished 11Al-68Mn-21Ni excess Gibbs energy. The excess Gibbs energy in the case of two sub-
alloy annealed at 1050 °C for 72 h and subsequently quenched in ice water. lattices was modelled as:

Gmθ, E = ∑ ∏ yis y rA yBr νLA,B:C

modelled as: P s≠r (7)

Gmθ,E = Gmθ,binE + Gmθ,ternE where P represents the condition of an additional constituent on sub-
n−1 n n−2 n−1 n lattice r while all other sublattices are singularly occupied.
= ∑i = 1 ∑ j = i + 1 x i x j Lijθ + ∑i = 1 θ
∑ j = i + 1 ∑k = j + 1 x i x j xk Lijk (3) In the ternary Al–Mn–Ni system, the disordered phases A1 and A2
form the ordered phases L12 and B2 respectively. In the present de-
where Gmθ,binE and Gmθ,ternE represent all binary and ternary interaction scription a single Gibbs energy function was used to describe the dis-
parameters, respectively. The binary interaction parameters Lijθ were ordered and the ordered version of the respective phases. The Gibbs
modelled using the Redlich-Kister polynomals [63], which were ex- energy of mixing using the formalism as described in the work of Dupin
pressed as: and Ansara [52,66], which is:
m Gm = Gmdis + ΔGmord (8)
Lijθ = ∑ νLijθ (xi − xj) ν
ν=0 (4) where Gmdis
is the (substitutional solution modelled) Gibbs energy of the
disordered phase and Gmord is the additional contribution to the Gibbs
θ
and the ternary interaction parameters Lijk were modelled as [64]: free energy due to ordering. This additional contribution is described

Fig. 7. (a) In-situ XRD measurement of sample 9Al-82Mn-9Ni in the 2θ-range from 29.5 to 31.5° and the temperature range from 1200 to 1350°C (the dashed line 2
refers to the second endothermic effect in the DTA curve in (c)) (b) In-situ XRD measurement of sample 9Al-82Mn-9Ni in the 2θ-range from 39 to 49° and the
temperature range from 900 to 1350°C, the white areas at approximately 1000 and 1200 °C indicate changes of the heating rate and measuring time in the in-situ
XRD experiment (the dashed lines 1 and 2 refer to the two endothermic effects in the DTA curve in (c)) (c) DTA curve of the sample 9Al-82Mn-9Ni in the temperature
range from 900 to 1150°C (d) XRD measurement of sample 9Al-82Mn-9Ni in the 2θ-range from 40.75 to 46.75° at 1000 °C. The asterisk symbols indicate the
uncorrected temperatures of the HTXRD measurements.

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A. Walnsch et al. Calphad 64 (2019) 78–89

as: formalism, the ternary ordering parameters can be described as:

ΔGmord = ΔGmord (yis ) − Gmord (yis = xi) (9) L12 2 L12 2 L12 1 L12
G Al2MnNi
= G + G Al + GMnNi + α Al2MnNi
3 Al3Mn 3 3Ni
3 3 (10)
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 L12 2 L12 1 L12 2 L12
G AlMn2 Ni
= G + G Al + GMnNi + α AlMn2Ni
Gmord (yis = x i ) is the Gibbs free energy contribution of the disordered 3 Al3Mn 3 3Ni
3 3 (11)
phase to the ordered phase, calculated when the site fractions of each L12 1 L12 2 L12 2 L12
component on each sublattice is the same and equal to the overall G AlMnNi = G + G Al + GMnNi + α AlMnNi2
2
3 Al3Mn 3 3Ni
3 3 (12)
composition of the phase. The CalPhaD-based thermodynamic assess- L12 L12 L12
with the binary interaction parameters G Al3Mn
, G Al3Ni
and GMnNi ,
as well
ment [46] of the Al–Mn–Ni system was performed using the PARROT 3
as the adjustable parameters α Al2MnNi , αAlMn2Ni and αAlMnNi2 .
module [67] of the Thermo-Calc Software [68]. Phase diagrams were
The Al-rich intermetallic phases were modelled using CEF For the
calculated using the Thermo-Calc Software. Due to the sensitive or-
intermetallic phases of the Al–Ni system, the descriptions were adopted
dering phenomena the isothermal and isoplethal sections were cross
from Zhang et al. [70] to ensure a possible combination of the ther-
checked using PANDAT [69].
modynamic descriptions for a database, which is capable of describing
higher order systems like the Al–Fe–Mn–Ni system.
5. Thermodynamic optimization of the Al–Mn–Ni system The ternary phases φ and κ were modelled using CEF, taking into
account the available information about their crystal structures and the
The binary descriptions of the Al–Mn, Mn–Ni and Al–Ni systems experimentally observed homogeneity ranges. The O phase was mod-
were taken from Du et al. [50], Liu [51] and Ansara et al. [52], re- elled as a stoichiometric compound, since in the experimental ob-
spectively. In the first step of the thermodynamic optimization, the servations of Balanetskyy et al. [53] no significant solubility was ob-
thermodynamic parameters of the phases on the Mn–Ni side of the served. The thermodynamic models and the assessed parameters were
phase diagram were optimized, taking into account the experimentally summarized in Appendix A, the ternary parameters which are not in-
observed equilibria between the phases A1, A2, B2, L12, β-Mn and ε by cluded in the appendix are equal to zero.
Kainuma et al. [56], Jia et al. [55] and He and Zhou [59], as well as the
experimental results, observed in this work. Since the experimental
6. Discussion of the thermodynamic optimization
data of Müller et al. [9] show significant deviations to the data of
Kainuma et al. [56], it was not considered for the thermodynamic
The calculated isothermal section at 1000 °C, based on the present
modeling. In the second step of the assessment, the thermodynamic
description of the Al–Mn–Ni system is shown in Fig. 8. The calculations
parameters of the phases in the Al-rich corner of the Al–Mn–Ni system
are in a good agreement with the experimental investigations. Espe-
were optimized, considering mainly the experimental investigations of
cially, the experimentally determined A1 + B2 + L12 tie-triangle by
Balanetskyy et al. [53]. In this optimization step, the solubilities of the
Kainuma et al. [56] and the A2 + B2 region on the Mn-rich side of the
intermetallic binary phases were modelled. Afterwards, the ternary
isothermal section were reproduced very well by the thermodynamic
phases (φ, κ, O) were considered and their thermodynamic parameters
calculations.
were optimized together with those of the binary Al-rich intermetallic
The partial isothermal section (xAl > 50 at%) at 950 °C, including
phases. In the final step of the assessment, the parameters of the liquid
the experimental data of Balanetskyy et al. [53] is illustrated in Fig. 9.
phase were modelled, taking into account the experimental data from
The isothermal section shows, together with the isothermal section at
the isoplethal sections of Wachtel et al. [11] and Henninger [54], as
1000 °C (Fig. 8), that the solubilities of the Al-rich intermetallic phases
well as the phase stabilities obtained in the present work and the DTA
(Al3Ni2, Al8Mn5 and HT-Al11Mn4) reproduce the experimental data.
results.
Moreover, the solubility range of the ternary φ phase is in good
agreement with the experimental data. Besides the φ phase, the ternary
5.1. Selection of the optimizing parameters

In the present assessment, the phases Liquid, A1, A2, β-Mn and ε
were modelled as substitutional solutions, where the 0L θ , 1L θ and 2L θ
parameters were used to describe the interactions of the atoms in the
ternary system. To describe the solubilities of the phases properly for
different isothermal sections, the i L θ parameters were described as a
linear function of the temperature. In order to avoid artefacts in the
calculations, the amount of parameters was kept as low as possible. The
B2 and L12 phases were modelled as the ordered versions of the phases
A2 and A1, respectively, according to the formalism described by Dupin
and Ansara [52,66]. Therefore, B2 is described as (Al, Mn, Ni,
VA)0.5(Al, Mn, Ni, VA)0.5(VA)3 and L12 is described as (Al, Mn,
Ni)0.75(Al, Mn, Ni)0.25(VA)1. For B2, the parameters
i B2 B2 i B2 i B2
LAl,Mn:Ni:VA = iLNi:Al,Mn:VA , L Ni:Al,Mn:VA = L Mn:Al,Ni:VA and
i B2
B2
L Mn,Ni:Al:VA = iL Al:Mn,Ni:VA were modelled as constant temperature in-
dependent values. Since the ordering connected to the Heusler phase is
usually taking place at lower temperatures, which were not covered by
the experimental investigation in this work, these ordering phenomena
were not modelled in the present database. For the disorder/order
transition A1/L12, a modified formalism proposed by Zhang et al. [70]
was used in order to allow an extrapolation into higher order systems. Fig. 8. Isothermal section at 1000 °C, calculated using the present description
Therefore, a series of binary order parameters (taken from binary de- for the Al–Mn–Ni system. The experimental datapoints obtained in this work, as
L12 well as the data of Kainuma et al. [56], Jia et al. [55], He and Zhou [59] and
scriptions), as well as three ternary ordering parameters (GAlMnNi 2
,
L12 L12
GAlMn2Ni and G Al2MnNi ), were evaluated. According to this modified Balanetskyy et al. [53] are included (right top side of the diagram).

84
A. Walnsch et al.
Fig. 9. Partial isothermal section (xAl > 50 at%) at 950 °C, calculated using the
present description for the Al–Mn–Ni system. The experimental datapoints of
Balanetskyy et al. [53] are included (right top side of the diagram).
Fig. 10. Isothermal section at 850 °C, calculated using the present description
for the Al–Mn–Ni system. The experimental datapoints of Kainuma et al. [56],
Jia et al. [55] and Balanetskyy et al. [53] are included (right top side of the
diagram).
κ phase is stable in the isothermal section at 850 °C, which is illustrated
in Fig. 10. The experimental data of Balanetskyy et al. [53] were re-
produced, even though the κ phase was modelled as a line compound.
Moreover, the wide extension of the B2 + β-Mn two-phase field, ac-
cording to Kainuma et al. [56] is also in a good agreement with the
present calculations.
The ternary extension of the B2 + β-Mn two-phase field at 850 °C
pursues even to lower temperatures, exemplary illustrated in the partial
isothermal section (xAl < 50 at%) at 800 °C in Fig. 11 (a). This con-
tinuation of the two-phase field was also confirmed by EPMA mea-
surements of the heat-treated samples, which are presented in the
partial isothermal section. The origin of this unusual wide extension of
the B2 + β-Mn two-phase area is even more visible in the metastable
phase diagram shown in Fig. 11 (b), where only the transition between
A2 and B2 were considered. It shows a two-phase field between A2 and
B2, which expands to lower temperatures. This feature of the phase
diagram has already been postulated in the experimental work of
85
Calphad 64 (2019) 78–89
Fig. 11. (a) Partial isothermal section (xAl < 50 at%) at 800 °C, calculated
using the present assessment for the Al–Mn–Ni system. The experimental da-
tapoints of Jia et al. [55] and the present investigations are included (right top
side of the diagram). (b) Calculated metastable ternary section (xAl < 50 at%,
only A2 and B2 were considered for calculation) at 800 °C using the present
thermodynamic description.
Fig. 12. Partial isothermal section (xAl > 50 at%) at 750 °C, calculated using
the present description for the Al–Mn–Ni system. The experimental datapoints
of Balanetskyy et al. [53] are included (right top side of the diagram). The
datapoints of Balanetskyy et al. [53] indicate either two-phase or three-phase
microstructures.
Kainuma et al. [56] and is reproduced by the established thermo-
dynamic database.
The partial isothermal section (xAl > 50 at%), which is presented in
Fig. 12, shows the phase equilibria involving the ternary O phase.
Moreover, the position of the different tie triangles, indicated by Ba-
lanetskyy et al. [53], were reproduced very well.
The interaction parameters of the liquid phase were assessed using
magnetic measurements by Henninger [54] and Wachtel et al. [11].
Exemplary, the isoplethal section between Ni3Al and Ni3Mn is illu-
strated in Fig. 13, including the experimental data of Wachtel et al.
[11]. The calculated isoplethal section shows a good agreement with
the experimental data. The calculated liquidus projection of the ternary
A. Walnsch et al. Calphad 64 (2019) 78–89

Al–Mn–Ni system, together with isothermal lines ranging from 800 to

1600 °C, is shown in Fig. 14 and a summary of the reactions involving
the liquid is given in Table 3.

7. Conclusions

New insights on the phase relations in the Mn-rich corner of the

Fig. 13. Calculated isoplethal section Ni3Al–Ni3Mn using the present thermo-
dynamic description. The experimental data of Wachtel et al. [11] is marked by
squares and triangles, depending on the type of transition.
ternary Al–Mn–Ni system were obtained regarding the phase equilibria
and the stability of the disordered A2 phase. The A2 phase was found to
decompose by a eutectoid type of reaction (A2 ⇄ A1 + B2) using
complementary methods (TEM, DTA, HTXRD). Moreover, the wide
extension of the B2 + β-Mn two-phase field at low temperatures was
found to be connected with a metastable miscibility gap between A2
and B2, which was confirmed by the thermodynamic calculations based
on the present assessment.
The thermodynamic database is in very good agreement with the
experimental data available in literature, as well as the investigations of
the present work. The present assessment includes the descriptions for
the ternary phases and the solubilities of the intermetallic compounds
in the Al-rich corner. Furthermore, based on the present assessment, a
liquidus projection of the whole ternary system was calculated.

Acknowledgements

This work was financially supported by the German Research

foundation (DFG) [Grant number KR 4855/1-1]. The authors would
like to thank Dipl.-Ing. Galina Savinykh and Dr.-Ing. Christian Schimpf
for their support with the DTA and XRD analyses. Moreover, Martin
Rudolph would like to thank the DFG for the financial support in the
subproject A05 within the framework of the CRC 920.

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,Mn,Ni)
0 LIQUID –69465.3466 – 20.1192731 T
LAl,Mn,Ni
1 LIQUID –14248.0017
LAl,Mn,Ni
Fig. 14. Calculated liquidus projection together with isothermal lines ranging 2 LIQUID –33964.4585
LAl,Mn,Ni
from 800 to 1600 °C using the present assessment. A1: (AI,Mn,Ni)(VA)
0 Al
LAl,Mn,Ni:VA 172051.001 – 87.136094 T

Table 3
Reactions with the liquid phase in the Al–Mn–Ni system, calculated based on the present database.
Reaction Temperature [°C] Liquid Composition [at%]

Al Mn Ni

T1 Liquid + L12 ⇄ A1 + B2 1363.59 24.23 0.78 74.99

T2 Liquid + B2 ⇄ Al8Mn5 + φ 968.89 67.71 21.84 10.45
T3 Liquid + Al8Mn5 ⇄ HT-Al11Mn4 + φ 965.76 72.96 19.54 7.51
T4 Liquid + B2 ⇄ Al3Ni2 + φ 944.54 70.45 11.05 18.50
T5 Liquid + HT-Al11Mn4 ⇄ Al4Mn + κ 909.90 85.73 12.89 1.38
T6 Liquid + HT-Al11Mn4 ⇄ φ + κ 900.30 84.42 11.51 4.07
T7 Liquid + Al3Ni2 ⇄ Al3Ni + φ 845.36 80.73 2.90 16.37
P1 Liquid +φ+κ ⇄ O 786.73 90.20 2.70 7.10
T8 Liquid + φ ⇄ Al3Ni + O 776.27 87.74 1.84 10.42
T9 Liquid + Al4Mn ⇄ R-Al4Mn + κ 720.90 97.54 2.43 0.03
T10 Liquid + R-Al4Mn ⇄ Al6Mn + κ 702.46 97.96 2.02 0.02
T11 Liquid + Al6Mn ⇄ A1 + κ 655.85 98.90 1.08 0.02
T12 Liquid + κ ⇄ A1 + O 653.18 98.73 1.39 0.08
E1 Liquid ⇄ A1 + Al3Ni + O 641.34 97.00 0.10 2.90
p1 Liquid + ε ⇄ B2 1156.76 45.02 51.93 3.05
e1 Liquid ⇄ A1 + B2 1030.62 9.55 61.84 28.61
p2 Liquid + B2 ⇄ φ 970.41 68.21 21.25 10.54
p3 Liquid + HT-Al11Mn4 ⇄ κ 909.63 86.09 12.89 1.02

86
A. Walnsch et al. Calphad 64 (2019) 78–89

1 Al
LAl,Mn,Ni:VA 201726.532 – 161.29596 T
2 A1
LAl,Mn,Ni:VA –64827.8

L12: (Al,Mn,Ni)0.75(Al,Mn,Ni)0.25(VA)
Ll2 2 Ll2 1 Ll2 2
Ll2
G AlMn2Ni
= ⋅G Al3Mn
+ ⋅G Al3Ni
+ ⋅G MnNi3
+ αAlMn2Ni
3 3 3
Ll2 2 Ll2 2 Ll2 1 Ll2
G AlMn2Ni
= ⋅G Al3Mn+ ⋅G Al3Ni+ ⋅G MnNi3
+ αAlMn2Ni
3 3 3
Ll2 2 Ll2 2 Ll2 1 Ll2
G AlMn2Ni
= ⋅G Al +
3Mn 3
⋅G Al +
3Ni 3
⋅G MnNi3
+ αAlMn2Ni
3
α Al2MnNi –15672.698
αAlMn2Ni –3555.8348
αAlMnNi2 –88.313008
0 Ll Ll2 Ll2 Ll2 Ll2
2
LAl,Mn,Ni:VA –3/2·G Al3Ni
– 3/2·G Mn 3Ni
+ 3/2·GAlMn2Ni
+ 3/2·G Al2MnNi
1 Ll2 Ll2
–1/2·G Al Ll2
+ 1/2·G Mn Ll2
3/2·GAlMn Ll2
+ 3/2·G Al
L Al,Mn:Ni:VA 3Ni 3Ni 2Ni 2MnNi
0 Ll Ll2 Ll2 Ll2 Ll2
2
LAl,Ni:Mn:VA –3/2·G Al3Mn
– 3/2·G MnNi3
+ 3/2·GAlMnNi2
+ 3/2·G Al2MnNi
1 Ll Ll2 Ll2 Ll2 Ll2
2
LAl,Ni:Mn:VA –1/2·G Al3Mn
+ 1/2·G MnNi3
– 3/2·GAlMnNi2
+ 3/2·G Al2MnNi
0 Ll Ll2 Ll2 Ll2 Ll2
2
LMn,Ni:Al:VA –3/2·G AlMn3
– 3/2·G AlNi3
+ 3/2·GAlMnNi2
+ 3/2·GAlMn2Ni
1 Ll Ll2 Ll2 Ll2 Ll2
2
LMn,Ni:Al:VA –1/2·G AlMn3
+ 1/2·G AlNi3
– 3/2·GAlMnNi2
+ 3/2·GAlMn2Ni
0 Ll Ll2 Ll2 Ll2 Ll2 Ll2
2
LAl,Mn,Ni:Al:VA G AlMn3
– 3/2⋅G Al2Mn2
– 3/2·G Al3Mn
+ G AlNi3
– 3/2·G Al2Ni2
Ll2 Ll2 Ll2 Ll2
– 3/2·G Al3Ni
– 3/2·GAlMnNi2
– 3/2·GAlMn2Ni
+ 6·G Al2MnNi
0 Ll Ll2 Ll2 Ll2 Ll2
2
LAl,Mn,Ni:Mn:VA –3/2·G AlMn3
– 3/2·G Al2Mn2
+ G Al3Mn
+ GMnNi3
– 3/
Ll2 Ll2 Ll2 Ll2
2·GMn 2Ni2
– 3/2·GMn 3Ni
– 3/2·G AlMnNi2
+ 6·G AlMn2Ni
– 3/
Ll2
2·G Al2MnNi
0 Ll Ll2 Ll2 Ll2 Ll2
2
LAl,Mn,Ni:Ni:VA –3/2·G AlNi3
– 3/2·G Al2Ni2
+ G Al3Ni
– 3/2·GMnNi3
– 3/
Ll2 Ll2 Ll2 Ll2
2·GMn 2Ni2
+ GMn 3Ni
+ 6·G AlMnNi2
– 3/2·G AlMn2Ni
– 3/
Ll2
2·G Al2MnNi
β-Mn: (Al,Mn,Ni)(VA)
0 β − Mn –143774.787 + 10.9723954 T
LAl,Ni:VA
A2: (Al,Mn,Ni,VA)(VA)3
0 A2
LAl,Mn,Ni:VA 187015.112 – 106.259674 T
1 A2
LAl,Mn,Ni:VA 45897.4784 – 81.0680065 T
2 A2
LAl,Mn,Ni:VA 110124.134 – 163.650192 T

B2: (Al,Mn,Ni,VA)0.5(Al,Mn,Ni,VA)0.5(VA)3
0 B2
L 10000
Al,Mn:Ni:VA
0B2
= LNi:Al,Mn:VA
1 B2
LAl,Mn:Ni:VA − 3000
1 B2
= LNi:Al,Mn:VA
2 B2
LAl,Mn:Ni:VA − 1000
2 B2
= LNi:Al,Mn:VA
0 B2
LAl,Ni:Mn:VA 4000
0 B2
= LMn:Al,Ni:VA
1 B2
LAl,Ni:Mn:VA − 22000
1 B2
= LMn:Al,Ni:VA
2 B2
LAl,Ni:Mn:VA − 1500
2 B2
= LMn:Al,Ni:VA
0 B2
LMn,Ni:Al:VA 1500
0 B2
= LAl:Mn,Ni:VA
1 B2
LMn,Ni:Al:VA − 5250
1 B2
= LAl:Mn,Ni:VA
2 B2
LMn,Ni:Al:VA − 4750
2 B2
= LAl:Mn,Ni:VA
ε: (Al,Mn,Ni)(VA)0.5
0 ε
LAl,Ni:VA –43768.365
0 ε
LAl,Mn,Ni:VA –284684.12
Al8Mn5: (Al)12(Mn)5(Al,Mn,Ni)9
0 Al Mn
8 5 –544370.553 + 12·GHSERAL + 5·GHSERMN + 9·GHSERNI
G Al:Mn:Ni
0 Al Mn
8 5 –792214.891
LAl:Mn:Mn,Ni
0 Al Mn
8 5 –1475486.61 + 748.585504 T
LAl:Mn:Al,Ni

87
A. Walnsch et al. Calphad 64 (2019) 78–89

1 Al Mn
8 5 –3117414.4 + 1914.60908 T
LAl:Mn:Al,Ni
HT-Al11Mn4: (Al,Mn)29(Mn,Ni)10
0 HT-Al Mn –1568998.27 + 627.4561 T + 29·GHSERAL
G Al:Ni 11 4
+ 10·GHSERNI
0 HT-Al Mn
11 4 –773141.554
LAl,Mn:Ni
0 HT-Al Mn
11 4 –781886.537
LAl:Mn,Ni
Al3Ni: (Al)0.75(Mn,Ni)0.25
0G Al3Ni –7067.978 + 2.14239 T + 0.75·GHSERAL
Al:Mn
+ 0.25·GHSERMN
0LAl3Ni –9689.53789
Al:Mn,Ni
Al3Ni2: (Al)3(Al,Mn,Ni)2(Ni,VA)
0 Al Ni
3 2 –86978.757 + 3·GHSERAL + 2·GHSERMN + GHSERNI
G Al:Mn:Ni
0 Al Ni
3 2 –50252.068 + 3·GHSERAL + 2·GHSERMN
G Al:Mn:VA
0 Al Ni
3 2 –463276.488 + 246.240710 T
LAl:Al,Mn:VA
φ: (Al,Mn,Ni)5(Al,Mn,Ni)2
0 φ
GAl:Mn –187635.274 + 111.502213 T + 5·GHSERAL
+ 2·GHSERMN
0 φ
GAl:Ni –140514.764 + 5·GHSERAL + 2·GHSERNI
0 φ
LAl:Al,Mn –61590.1368
0 φ
LAl:Al,Ni –76556.3009
0 φ
LAl:Mn,Ni –397845.313
0 φ
LAl,Mn:Mn,Ni 211812 – 898.4126 T

κ: (Al)4(Mn,Ni)
0 κ
GAl:Mn –77729.5448 + 11.0953755 T + 4·GHSERAL + GHSERMN
0 κ
GAl:Ni –28965.4137 + 4·GHSERAL + GHSERNI
0 κ
LAl:Mn,Ni –501902.461 + 300.307353 T
O: (Al)0.78(Mn)0.13(Ni)0.09
0 O
GAl:Mn:Ni –39345.1489 + 15.0077609 T + 0.78·GHSERAL
+ 0.13·GHSERMN + 0.09·GHSERNI

8. Data availability statement

The raw/processed data required to reproduce these findings cannot be shared at this time due to technical or time limitations.

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