Materials Today Communications 37 (2023) 107288

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Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

Study on the composition effect upon the microstructure development in

Cu-Fe alloys prepared using Aerodynamic Levitation
Debaraj Sahoo a, *, Manas Paliwal b, Atul Srivastava a, Sushil Mishra a
a
Department of Mechanical Engineering, Indian Institute of Technology, Bombay, Maharashtra 400076, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur, West Bengal 721302, India

A R T I C L E I N F O A B S T R A C T

Keywords: The current study primarily focuses on the development of microstructure in Cu-Fe alloys (with varying Cu
Cu-Fe alloy concentration) solidified using the Aerodynamic Levitation (ADL) method. The solidified microstructure analysis
Undercooling is performed using different characterization techniques such as Scanning Electron Microscopy (SEM), X-ray
Immiscible alloy
Tomography, Energy Dispersive Spectroscopy (EDS), and Electron Backscatter Diffraction (EBSD). In addition,
Aerodynamic Levitation
the total undercooling in the alloys is calculated as a function of Cu composition and is found to increase with Cu
content in the alloys. The surface morphology of the sample changes from planer front in pure Cu and Cu75Fe25
alloy to cellular in Cu50Fe50, Cu25Fe75 and pure Fe. The sample tomography and SEM analysis reveal that pure
Fe and Cu exhibit a single-phase structure and a distinct phase separated microstructure is observed in the case of
Cu75Fe25, Cu50Fe50 and Cu25Fe75 compositions. The grain orientation mapping of the solidified sample using
EBSD reveals a core shell structure of Cu-Fe alloys. In the case of pure Fe and Cu, the grain structure is influenced
by undercooling level. The orientation relationship analysis of the phase separated Cu and Fe in the alloy does
not provides any orientation relationship between the grains of Fe and Cu.

1. Introduction
The presence of a metastable miscibility gap in Cu-Fe alloy system
distinguishes it as a one-of-a-kind material for developing electrical
contacts [1], electrical switches [2], sensors [3], magnetic recording
materials [4], and energy storage materials [5]. The phase separation is
possible when the alloy melt is undercooled below the metastable
miscibility gap. The container less solidification method has the poten­
tial to facilitate the required undercooling, which is difficult to achieve
in the standard solidification process. This solidification technique is
characterized by the absence of any interaction between the mould and
the solidifying sample. Out of several contactless solidification tech­
niques like Aerodynamic levitation (ADL) [6], Electromagnetic levita­
tion (EML)[7,8], Electrostatic levitation (ESL) [9], and Acoustic
levitation (AL)[10], ADL and EML are the most widely employed due to
their simple operational control. Likewise, controlling the cooling rate is
an essential solidification process parameter. In the EML method, the
alternate current flowing through the water-cooled levitating coil de­
velops an electromagnetic field. The Lorentz force of the induced eddy
current levitates the electrically conducting sample positioned in the
electromagnetic field, while the induced eddy current heats and melts
the sample. The sample is cooled by introducing an external gas into the
process chamber [7]. Whereas, in the ADL process, the gas flow used to
levitate the sample also functions as a cooling medium, eliminating the
need for additional gas flow arrangements to cool the sample. In addi­
tion, the use of laser power to heat the sample also enables the ADL to
melt non-conducting samples, whereas EML is mostly applied for con­
ducting or semiconducting samples and necessitates additional modifi­
cation for non-conducting samples. Therefore, ADL provides easier
operational control in comparison to EML.
The high cooling rate in the ADL method allows the Cu-Fe system to
undercool at a desired degree in order to obtain a phase separated
structure. Ma et al. [11] used Aerodynamic Levitation with changing Cu
percentages to develop a core-shell microstructure in the Cu-Fe alloy
system. According to Luo et al. [12], phase separation of the Fe50Cu50
alloy in electromagnetic levitation can occur with an undercooling (ΔT)
of 7 ◦ C. They reported that Fe phase appears to have a finely branched
morphology in low undercool melts, but a coarse grain morphology is
seen in high undercool melts. As per Huang et al. [13], a Cu-Fe alloy
core-shell structure can be made via a solid-state reaction technique,
with Fe and Cu forms a core and shell structure respectively. Lu et al.
[14] examined the Cu50Fe50 alloy using both gas fluxing and drop tube

* Corresponding author.
E-mail address: debaraj92@iitb.ac.in (D. Sahoo).

https://doi.org/10.1016/j.mtcomm.2023.107288
Received 18 August 2023; Received in revised form 26 September 2023; Accepted 7 October 2023
Available online 10 October 2023
2352-4928/© 2023 Elsevier Ltd. All rights reserved.
D. Sahoo et al.
solidification techniques. Phase separation was seen during the glass
fluxing process, producing a phase that was rich in Fe and Cu. The alloy
also showed secondary phase separation, with Cu-rich particles
appearing in the Fe-rich phase and vice versa. The drop tube approach
showed a structural change from a fully dendritic to a mixed micro­
structure, with Fe and Cu phases partially and completely phase sepa­
rated. Chen et al. [15] discovered metastable phase separation in the
Cu70Fe30 composition when the temperature of undercooling surpasses
56 ◦ C. The favorable nucleation of the Fe-rich phase is induced through
cyclic superheating and undercooling within a high-frequency induction
boiler. For undercooling temperatures falling within the range of
56–79 ◦ C, coarsening of Fe nuclei takes place as a result of Ostwald
ripening. However, undercooling beyond 79 ◦ C leads to coarsening
caused by the coagulation effect of Fe droplets. In our previous research,
Sahoo et a. [16] investigated various compositions in Cu-Fe alloy sys­
tem, solidified using W-wire method and reported an increase in
undercooling of the melt with increasing Cu concentration. Although the
samples are highly undercooled, an incomplete phase separation is
observed in most of the samples. A thorough literature analysis reveals
that the composition significantly affects the undercooling and phase
separation in the contactless solidification process. However, there are
not many studies that provide a detailed examination of the final
microstructure formed as a function of composition in terms of phase
distribution and grain orientation obtained through container less so­
lidification techniques.
In this work, various Cu-Fe alloy (with varying Cu concentrations)
samples are prepared using the ADL method, and the solidification
process is examined using a high-speed camera (HSC). In these experi­
ments, the lack of interaction between the sample and mould enables the
system to achieve significantly high degree of undercooling. SEM-EDS
and X-ray tomography was used to determine the microstructural
characteristics of the solidified alloys, and EBSD was employed to map
the grain orientation of the sample. In addition, using the experimen­
tally obtained solidification growth velocity, the undercooling is
calculated as a function of composition.
2. Experimental details
In this study, high-purity powders of Fe (99.56%) and Cu (99.56%)
were utilized. Inductively Coupled Plasma-Atomic Emission Spectrom­
etry (ICP-AES) was utilized in order to ascertain the powder composi­
tion. As a part of the sample preparation process, the powders were
mixed in a planetary ball mill for ten minutes with a composition of Cu x:
Fe 100− x (x: 0, 25, 50, 75 and 100 wt%). The combined powder was then
Fig. 1. The aerodynamic levitation with different important components used to capture different parameters during the experiment.
2
Materials Today Communications 37 (2023) 107288
subjected to a compaction force of 30 kN, which resulted in the pro­
duction of pellets with a diameter of 10 mm and a thickness that ranged
from 2 to 3 mm. After that, the pellets were sliced into smaller rectan­
gular samples of varying weights, ranging anywhere from 30 to 40 mg
each. Following the sample preparation, the solidification experiments
were performed using the ADL technique which is discussed below.
2.1. Experimental technique
The solidification study was carried out in an environment that was
completely non-contact throughout the experiment, and the molten
sample was levitated using the ADL principle, as can be seen in Fig. 1.
The ADL system consists of a process chamber that has a conical nozzle
with a cone angle of 60 ◦ and an orifice size of 1 mm housed inside it. The
attainment of a stable levitation state can be accomplished by modifying
the Ar gas flow rate through the conical nozzle. This adjustment is made
in response to the size and weight of the sample. As part of the process of
solidification testing, a high-power continuous wave CO2 laser (Synrad
i401 400 W) with a beam diameter of 6 mm ± 0.6 mm emits with a
wavelength of 10.6 µm was used in the process chamber to convert the
prepared sample into its molten form.
Once the sample is levitated, it can be maintained in a condition of
complete non-contact throughout the duration of the solidification
phenomenon. Through careful regulation of the output power of the
laser, it is possible to exert the necessary degree of control over the level
of undercooling achieve by the non-contact condition. An optical py­
rometer (Chino IR-CAS series) with a working range of 600–3000 ◦ C and
operating wavelength of 900 nm is used to monitor the surface tem­
perature of the sample in a continuous manner. The pyrometer provides
a temperature-time history that can be used to measure the undercooling
before solidification and the extent of recalescence. The real-time so­
lidification phenomenon was captured by a high-speed camera based on
CMOS that is capable of operating at a maximum frame rate capacity of
40000. The rate at which images are acquired is sufficient to capture the
important stages of solidification.
2.2. Characterization of solidified samples
The SEM analysis was performed using a FEG Zeiss SEM Gemini 300
model microscope equipped with EDS, to investigate the internal
structures, surface morphology, and compositional analysis of solidified
samples. The samples were dipped in epoxy and polished on silicon
carbide sheets with grit sizes ranging from 120 to 2500 mesh, followed
by 8 h of vibratory polishing in colloidal silica solution. EBSD analysis
D. Sahoo et al.
was performed utilizing an Oxford HKL attachment integrated with the
SEM system. The EBSD data was analyzed and the Inverse Pole
Figure (IPF) was generated using the TLS OIM software. The EBSD ex­
periments were conducted using a 300 mm aperture size, under high
current conditions, and with a step size of 0.2 mm. The Kikuchi pattern
was optimized using a Binning mode of 2 × 2 and a gain of 5. The
voltage used by EBSD and SEM was maintained at 20 KV. TSL software
was used to measure the Inverse pole figure (IPF), Inverse pole figure
(IPF) map, Image Quality (IQ) map, and phase map from EBSD data. The
sample tomography was performed using a TESCAN UniTOM HR system
with a spatial resolution of 600 nm and voxels between 1.1 and 1.4 mm.
2.3. Undercooling calculations
The total undercooling during solidification is calculated using the
Lipton-Kurz-Trivedi (LKT) model using the experimentally obtained
solidification growth velocity (V) data [17]. The sum of the solutal
undercooling (ΔTc), thermal undercooling (ΔTt), curvature under­
cooling (ΔTr) and kinetics undercooling (ΔTk) can be used to define the
total undercooling (ΔT) as:
ΔT = ΔTc + ΔTt + ΔTr + ΔTk
(1 − k0 )Iv (Pc )
ΔTc = ml c0
1 − (1 − k0 )Iv (Pc )
ΔTt =
H
× Iv (Pt )
Cp
ΔTr =
2Γ
R current investigation delays the nucleation event, resulting in more
V undercooling than the sample prepared using the W-wire method
ΔTk =
μ
Here ml is liquidus slop, c0 is initial alloy concentration, k0 is the actual
partition coefficient, Iv (Pc ) is the Ivantsov function of the solutal Peclet
number, Iv (Pt ) is the Ivantsov function of thermal Peclet number, H is
the heat of fusion, Cp is the specific heat of liquid, Г is the Gibbs-
Thompson coefficient and µ is the kinetic coefficient of γFe phase. As
ΔTt contribution is very small compared to the other terms, it is
neglected in the undercooling calculations. The dendritic tip radius is
related to the undercooling terms using the equation below:
R=
Γ/σ∗
(ΔH/CPL )Pt ξt − {2m′l C0 (1 − kv )Pc /[1 − (1 − kv )Iv (Pc ) ] }ξt
In Eqn. 6, Pt and Pc are the thermal and solutal Peclet numbers,
respectively, given by VR/2α and VR/2Dl while σ ∗ is the stability
constant (1/4π2), Dl stands for diffusion coefficient. The liquid thermal
gradient at the tip is given by Mullis and Cochrane [18]:
Gl =
θPt
R morphology is evident, indicating a planar solidification front.
The hyper cooling limit known as θ is (H/Cp). Boettinger et al. [19]
provide a modification in the liquidus slop given by Eq. (8) based on the
impact of the solidus and liquidus line on the solidification velocity.
{ }
m′l = ml 1 +
k0 − kv [1 − ln(kv /k0 ) ]
(8)
1 − k0
Where kv is velocity dependence partition coefficient given by Aziz [20]:
k0 + aV/Dl
kv =
1 + aV/Dl
where a denotes the characteristic diffusion length. The sample’s growth
velocity, denoted as V, is ascertained through the utilization of a high-
speed camera. Employing the Phantom CV3.5 software, the sample’s
Materials Today Communications 37 (2023) 107288
dimensions are calibrated with the pixel. Subsequently, the average
growth velocity is determined by dividing the pixel distance traveled by
the solidifying front by the time taken to cover said distance. The
thermophysical parameters employed for the undercooling calculations
are outlined in Table 1. By utilizing these thermophysical parameters in
conjunction with the experimentally derived growth velocity, the
dendrite tip radius (R) can be computed using Eq. (6). The total
undercooling is then evaluated based on Eqs. 1–5, utilizing the calcu­
lated R-value
3. Results and discussion
3.1. Cooling curve and phase formation
The undercooling estimated using the LKT model is superimposed on
the Cu-Fe phase diagram and shown in Fig. 2. As seen, the degree of
undercooling increases with increasing Cu concentration in the alloy.
The growth velocity used to calculate undercooling is derived from the
ADL-prepared sample during solidification. In the case of pure Fe, the
calculated undercooling is close to 20 ◦ C, however as the Cu content
rises to 25 wt%, the calculated undercooling rises to around 60 ◦ C. The
(1) calculated undercooling for Cu50Fe50 composition is close to 90 ◦ C.
When the Cu content is increased to 75%, the predicted undercooling is
close to 250 ◦ C. The calculated undercooling is close to 230 ◦ C in the
(2)
case of pure Cu. The authors in their previous work reported the
increasing trend in undercooling with the composition in the samples
(3) prepared using W-wire method[16]. The results of the undercooling
obtained using the W-wire method is superimposed in Fig. 2 as well. The
undercooling obtained in this study is 20–30 ◦ C higher than the previ­
(4) ously obtained values. This is because the ADL method used in the
(5) employed in the previously reported work [16].
The HSC pictures of the solidifying samples obtained at different
time steps are shown in Fig. 3. Pure Cu exhibits a recalescence event at
about 90 ms. In the Cu75Fe25 composition, the nucleation event occurs
around 25 ms, and with further decrease in Cu content in the alloys,
nucleation event is found to begin relatively early (Cu50Fe50: 10 ms and
Cu25Fe75: 7 ms). Because of the low undercooling, nucleation occurs
instantly in the case of pure Fe. A growth front emanating from the
bottom of the sample and ascending towards the top is clearly visible in
the alloy case (Cu75Fe25: 30 ms, Cu50Fe50: 20 ms, and Cu25Fe75:
7 ms). It is noted that nucleation event during the ADL is a clear function
(6) of Cu content and the related undercooling. A high degree of under­
cooling in pure Cu and Cu75Fe25 delays the nucleation event compared
to Cu50Fe50 and Cu25Fe75 samples.
3.2. Surface morphology
Fig. 4 depicts the surface morphology of the samples shortly after
(7) solidification. In the pure Cu example (Fig. 4A), distinct surface
The high undercooling attained in this sample leads to the devel­
opment of a planar front during solidification. The surface morphology
of Cu75Fe25 also shows a planner morphology with facets like structure
in the magnified views of the surface. The undercooling obtained in this
composition resulted in the planar faceted like surface morphology
(Fig. 4B). In the case of Cu50Fe50 composition, a cellular growth front
was observed due to decrease in the undercooling. In the case of
Cu50Fe50 and Cu25Fe75 and pure Fe samples, the appearance of cell-
like structures on the surface (Fig. 4C and D) suggests a cellular
(9)
growth front morphology. As seen in Fig. 4A1-E1, in the case of the W-
wire sample, the solidification front is dependent upon the degree of
undercooling. At higher concentrations of Cu (in both Pure Cu and
Cu75Fe25), a planar solidification front is observed. However, as the
concentration of Fe increases, the solidification front transitions to a
3
D. Sahoo et al. Materials Today Communications 37 (2023) 107288

Table 1
Thermos-physical parameters of Cu-Fe alloy at different compositions.
Parameters Unit Cu Fe Fe25Cu75 Fe50Cu50 Fe75Cu25 Ref.

Specific heat (Cp) Solid J/kg K 420 450 647.2 589.3 641.7 [21]
Specific heat (Cp) Liquid J/kg K 495 795 580.14 655.87 725.47 [21]
Heat of fusion (H) J/Kg 206,000 247,000 232,616 231,673 253,800 [21]
Liquidus Temperature (TL) K 1356 1809 1688 1698 1725 [21]
Prefactor of diffusion co. efficient (D0) m2/s 1.46 × 10− 7
4.3 × 10− 7
2.17 × 10− 7
2.88 × 10− 7
3.59 × 10− 7
[22]
Activation energy (Q) J/Kg 637,000 920,000 707,000 778,000 850,000 [22]
Characteristic diffusion length (a) m 2 × 10− 10 3 × 10− 10 5 × 10− 10 4.1 × 10− 10
3.1 × 10− 10

Equilibrium liquidus slop (ml ) K/wt% 0 0 -0.86 -0.61 -1.63

[21]
Interface energy (γ) J/m2 0.223 0.381 0.28 0.32 0.36 [12,23]
Actual partition co. efficient (K0) 0 0 0.19 0.28 0.434 [21]
Diffusion Co. efficient (Dl) m2/s 3.9 × 10− 9
5.5 × 10− 9
8.18 × 10− 9
7.23 × 10− 9
5.86 × 10− 9
[22]
Velocity (V) m/s 4.5 0.028 2.79 2.46 1.26
Liquid Thermal gradient (Gl) K/m 2.23 × 108 6.19 × 105 1.52 × 107 1.93 × 107 1.72 × 107

Fig. 2. (A) The amount of undercooling superimposed on the phase diagram for various compositions of ADL samples, as represented by (a-e), (B) Comparison of
ADL and W wire [16] sample undercooling by composition.

cellular morphology in the Cu50Fe50 alloy. Furthermore, with a further
increase in Fe concentration, the solidification front takes a dendritic
structure in both Cu25Fe75 and pure Fe.
3.3. X-ray tomography
The cross-sectional examination of the sample at the positions
denoted as a-a and b-b are shown in Fig. 5. In the case of pure Cu, a single
phase is seen throughout the sample, with the existence of small voids at
the top cross section signifying volumetric contraction at the end of
solidification (Row-I). In the case of Cu75Fe25, the cross section (a-a) is
composed of a two-phase area with a void at the phase separation
interface. Fe has a higher area proportion in the two-phase region than
Cu. As Fe has a lower density than Cu, during phase separation, low
density Fe floats on top of liquid Cu, and takes up the top part of the
sample. Cu and Fe are placed in a core-shell configuration at the cross
section (b-b), with Cu at the core and Fe as the shell, as seen in Row III.
The small, spherical Cu particles may be seen in the Fe-rich region close
to the interface in the enlarged image. However, no Fe particles were
found in the Cu-rich region (Row II and IV). The cross sections of the
Cu50Fe50 and Cu25Fe75 samples show a comparable core shell struc­
ture, and the Cu droplets are entrapped in the Fe rich region of the
Cu25Fe75, Cu50Fe50 and Cu75Fe25 samples. This is because the
amount of undercooling affects the degree of phase separation in the
alloys [24]. When the undercooling of Cu-Fe alloys is compared, the
undercooling decreases with decreasing Cu content in the alloys. It is
noted that once the alloy is undercooled, Fe and Cu rich liquid phase
start to separate because of surface tension difference between liquid Cu
and Fe. The minute droplets then collide with each other and eventually,
phase separate. In the meantime, the nucleation of Fe starts from the
phase separated liquid Fe. The undercooling in liquid Fe enables the Fe
nuclei to grow at a faster rate by entrapping the Cu droplets within it
before they can be rejected into the bulk separated Cu ruck liquid. This
leads to the entrapment of Cu droplets in the Fe rich region, as seen in
the Cu25Fe75, Cu50Fe50 and Cu75Fe25 compositions. Pure Fe has a
phase distribution that is equivalent to pure Cu. At the top cross section,
it reveals a single phase in the center and volumetric contraction in the
shape of a void. (Row-I and III). The microstructure development in
these alloys is explained in the subsequent section.
3.4. Internal structure and composition analysis
Fig. 6 shows the SEM analysis of the sample at the selected cross
section and the corresponding EDS analysis. A single phase is shown in
the case of pure Cu and Fe (Fig. 6 A and E), and the EDS mapping reveals
that the phase is composed of Cu and Fe, respectively. Cu75Fe25,
Cu50Fe50, and Cu25Fe75 compositions exhibit a two-phase structure in
the form of a core and shell. The shell is composed of Fe, whereas Cu
phase is formed at the center. The EDS mapping confirms the core shell
arrangement, which is in line with the structure observed in tomography
analysis. In the above three alloys, Fe rich phase contains spherical Cu
particles, whereas no such Fe entrapment is observed in Cu rich area of
Cu50Fe50 and Cu75Fe25 composition. But, in the Cu25Fe75 composi­
tion, the entrapment of the Fe particles in the Cu rich area is observed
from the EDS mapping. Meanwhile, a distinct phase separation interface
is observed in case of the above three alloys.

4
D. Sahoo et al. Materials Today Communications 37 (2023) 107288

Fig. 3. HSC images of solidifying samples of various compositions taken at various time intervals. It has been found that the time needed for nucleation reduces with
increasing Fe content, ranging from t = 90 ms for pure Cu to t = 7 ms for Cu25Fe75. Due to the low level of undercooling, the nucleation of pure Fe occurs
instantly (t = 0 ms).

The observed microstructure can be explained as follows: The Ar gas
which is used to levitate the sample takes away the extra heat from the
samples in addition to the heat loss by radiation, causing it to undercool.
The high thermal conductivity of Cu helps it to dissipate the thermal
heat more quickly resulting in a higher level of undercooling in the case
of Cu rich composition (pure Cu and Cu75Fe25). As the Cu concentra­
tion decreases in the alloys, the undercooling decreases as well. The
consequence of decreased undercooling can be seen clearly in surface
morphology, as morphology transforms from planner to cellular (Fig. 4).
When the sample is undercooled, the nucleation process begins by
releasing the latent heat, as this is the case in pure Cu and Fe samples. On
the other hand, liquid-liquid phase separation takes place before the
nucleation in the Cu75Fe25, Cu50Fe50, and Cu25Fe75 compositions. As
seen from Fig. 2 the undercooling of the compositions Cu75Fe25 and
Cu50Fe50 is well below the miscibility gap.
Whereas, the undercooling of Cu25Fe75 is close to miscibility gap. In
Cu75Fe25 and Cu50Fe50 alloys, the nucleation of the Fe phase begins in
the undercooled Fe-rich liquid phase, and solidification proceeds in a
planar manner. Due to extremely high solidification velocities, the Cu
droplets in the Fe rich phase are unable to merge with the Cu rich bulk
phase and are confined to the Fe rich side of the solidified samples as
spherical globules. In the Cu25Fe75 composition, the nucleation of Fe is
initiated as soon as the liquid phase separation is achieved. The Fe rich
liquid phase is instantly transformed to solid Fe whereas the Cu rich
liquid phase is still in the undercooled condition. It is to be noted that
during solidification, Cu rich liquid continuously rejects Fe due to high

5
D. Sahoo et al.
Fig. 4. Different magnifications reveal the surface morphology of solidified materials (A1-E1) of the W- wire sample and (A-E) ADL sample. The distinctive surface
morphology observed in A) pure Cu and B) Cu75Fe25 is attributable to the front of planned solidification. The amount of undercooling in C) Cu50Fe50 D) Cu25Fe75
and E) pure Fe promotes the development of a cellular growth front.
solidification velocity, Fe does not have sufficient time to reach the two-
phase interphase and therefore becomes entrapped within the Cu melt.
This is confirmed by the EDS mapping of the Cu75Fe25 composition,
which reveals Fe particles trapped in the Cu rich side.
3.5. Crystallographic texture
The effect of composition on phase separation and microstructure
development during the solidification was analyzed using SEM-EDS and
X-ray tomography. SEM study on the cross-section (b-b) of the sample
shows the contrast between the two phases (Fig. 6). Further, an EBSD
study was performed on the same sections to understand the grain
structure and its crystallographic orientation. To capture the complete
cross-section, multiple scans were performed and the montage of EBSD
maps was created. Image quality (IQ) map, phase map and Inverse Pole
6
Materials Today Communications 37 (2023) 107288
Figure (IPF) map along with the IPF are shown in Fig. 7. As expected,
pure Fe and Cu samples show a single phase as observed from IQ and
phase maps. The pure Fe sample shows a very large grain compared to
the pure Cu sample. Very few points are observed in the IPF of Fe sample
due to the presence of very few grains in the cross-section, whereas the
Cu sample shows complete distribution of the points in the IPF. The
crystallographic texture of both Fe and Cu samples is mostly random.
Both the samples, pure Fe and Cu, have an area of very small grains, as
marked by the arrow in the figure. The fine grain size region is the site of
nucleation, during the solidification, from which the grains grow to­
wards the opposite side of the sample. The nucleation of grains releases
latent heat, which raises the melt temperature and reduces the under­
cooling level, leading to a drop in growth velocity. The combined effect
of an increase in melt temperature and a decrease in growth velocity
causes the increase in grain size of the sample at locations far from the
D. Sahoo et al. Materials Today Communications 37 (2023) 107288

Fig. 5. X-ray tomography was used to create 3D representations of (A) pure Cu, (B) Cu75Fe25, (C) Cu50Fe50, (D) Cu25Fe75 and (E) pure Fe samples. Rows (I) and
(III) display their cross-sectional views at sample cross-sections (a-a and b-b). The magnified image of a selected cross-section (a-a and b-b) of the sample in Rows (I
and III) is depicted in Rows (II and IV), which reveals the entrapped Cu droplets (light brown color) in the Fe-rich area (light grey color).

nucleation point. The smaller grain size of pure Cu can be attributed to
the significant level of undercooling experienced by the liquid melt
before nucleation (Fig. 2) and the possibility of multiple nucleation sites.
Similarly, the larger grains in pure Fe samples are the result of low
undercooling level which promote grain growth and less nucleation site.
Based on the phase map, it is apparent that the outer surface of all
alloys consists predominantly of Fe, while the core is primarily
composed of Cu, also confirmed by EDS and X-ray tomography. The
EBSD analysis at b-b section of Cu75Fe25 composition reveals that the
Fe phase is present at the shell and Cu phase in the core. The Cu50Fe50
sample shows a very large Cu grain at the core, whereas Fe shell grain
shows a grain size variation. Very small grains are present at the
nucleation site and large grains are present away from the nucleation
site. It has to be noted that the nucleation point is not present at the b-b
section of Cu75Fe25 sample. The Cu25Fe75 sample shows a slight grain
size variation of Fe phase. The cross-section area of Fe phase is very
small at b-b section, which constrains the grain growth of Fe phase.
Unlike the other two systems Cu75Fe25 and Cu50Fe50, the Cu phase
shows a smaller grain size in Cu25Fe75 sample.
The phenomenon of formation of coarse grain structure of phase
separated Cu of Cu75Fe25 and Cu50Fe50 can be attributed to the
exothermic release of latent heat during the nucleation and growth of
solid Fe in the Fe-rich liquid phase and reduction in heat transfer rate
due to formation of solid Fe shell. The transfer of released latent heat to
the still-liquid Cu decreases its undercooling threshold. At the same
time, the reduced heat transfer rate of the liquid Cu present at the core
due to solidified Fe phase at the shell gets sufficient time for grain
growth. The combined contribution of above factors results in a coarse
grain structure of Cu75Fe25 and Cu50Fe50 samples. In contrast, the
phenomenon of fine grain structure formation Cu25Fe75 sample can be
attributed to the presence of Fe dendrites (Fig. 6) in the Cu rich area of
Cu25Fe75 sample. The entrapped Fe dendrites in the Cu liquid phase

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D. Sahoo et al. Materials Today Communications 37 (2023) 107288

Fig. 6. The internal area of (A) pure Cu, (B) Cu75Fe25, (C) Cu50Fe50, (D) Cu25Fe75 and (E) pure Fe samples at the cross-section (b-b) marked in the 3D sample. Row
(I) shows the overall internal cross section of the sample, Row (II) shows the magnified view of the selected cross-section (b-b), Row (III) represent the composition
mapping of the selected cross-section (b-b) of the sample, and rows (IV and V) depict the distribution of Fe (red color) and Cu (green color) in that area respectively.

provide additional nucleation sites and the probability of growth for
each Cu nucleus is consistent across all nucleation sites offered by Fe
dendrites. This uniform growth pattern hinders the individual nucleus
growth, leading to a decrease in the grain size of phase-separated Cu.
The IPF of all the samples corroborates the presence of different grain
sizes in Cu and Fe phases. The larger grains in the sample give very few
points in the IPF, whereas smaller grain size fills up the entire IPF.
It can be argued that a higher degree of undercooling in pure Cu
leads to the formation of a fine grain structure, while a lower degree of
undercooling in pure Fe results in a coarse grain structure. In all of the
alloy compositions, the phase map shows a distinct phase separated
interface. The Cu75Fe25 composition results a coarse grain structure for
both phases with a higher orientation spread. The observed heteroge­
neity in grain size within the Fe-rich region of the Cu50Fe50 and
Cu25Fe75 samples can be attributed to the existence of potential
nucleation sites. The Cu50Fe50 compositions exhibit a coarse grain
structure of Cu phase. In contrast, the Cu25Fe75 composition displays Fe
dendrites in the Cu-rich region, this leads to the formation and growth of
multiple Cu grains, resulting in a reduced grain size of the Cu phase. The
orientation relationship analysis of the phase separated Fe and Cu does
not provide any orientation relationship between the grains of Fe and
Cu. This observation implies that while the presence of solidified Fe
serves as a nucleation site for Cu to nucleate and grow, it does not exert
any influence on the crystallographic orientation of the Cu grains.
3.6. Comparison between the sample prepared by ADL and W-wire
method
Upon comparison of the observed surface morphology of the samples
solidified using ADL technique to that of samples solidified using the W-
wire method reveals that an increase in Cu content increases the level of
undercooling in both the solidification techniques [16]. The higher level
of undercooling achieved in the ADL technique allows the sample to
form a planner growth front in the high Cu compositions (Pure Cu and
Cu75Fe25), whereas all other compositions exhibit a cellular solidifi­
cation front. While in the W-wire case, depending on the level of
undercooling, a planner solidification front is observed at high Cu
concentrations (Pure Cu and Cu75Fe25), and as the Fe concentration
increases, the solidification front becomes cellular (Cu50Fe50), with
further increase in Fe concentration, the solidification front becomes

8
D. Sahoo et al. Materials Today Communications 37 (2023) 107288

Fig. 7. The EBSD analysis of pure Cu, Cu75Fe25, Cu50Fe50, Cu25Fe75 and pure Fe samples at the cross-section (b-b). Column (I) displays the image quality (IQ) map
of the selected areas. The phase distribution at the selected area is represented by Column (II). The red color represents Cu, while the blue colour represents Fe. The
IPF map of the selected area of the samples is represented by Column (III), and the varying colors represent the varying orientation of grains in the selected area. In
Columns (IV and V), the orientation spread of individual components (Cu and Fe) is shown.

dendritic (Cu25Fe75 and pure Fe). Thus, depending on the Cu concen­
tration, the solidification front in the ADL process changes from planner
to cellular, but in the W-wire process the solidification front changes
from planner to cellular and finally to dendritic.
When the internal surface morphology of ADL and W-wire samples is
compared, it is observed that the existence of liquid-liquid phase sepa­
ration in the high undercooled melt of the ADL sample creates a distinct
phase separated interface between the Fe rich and Cu rich areas. In
contrast, the phase separation in the alloys prepared using W-wire
technique varies from a sharp phase separated interface in the Cu75Fe25
composition to diffusive in the Cu50Fe50 and Cu25Fe75 compositions.
In the above two alloys, the interface serves as a transition zone between
the Fe-rich and Cu-rich phases. The use of the ADL technique allows the
sample to create a core shell structure, which is not present in samples
prepared using the W-wire method. Upon comparing the EBSD analysis
of ADL and W-wire samples, it is observed that the W-wire provides
many nucleation sites, resulting in a fine grain structure with random
grain orientation. In contrast, the degree of undercooling influences the
grain structure of pure Cu and Fe samples prepared by ADL method. In
the case of alloys, the grain structure depends on the undercooling and
the existence or absence of a nucleation site at the cross section. The
nucleation site in Fe rich area gives a significantly varied grain structure.
While partial phase separated Cu produces a fine grain structure, the
complete phase separated Cu produces a coarse grain structure. No

9
D. Sahoo et al.
orientation relationship between grains formed in the phase separated
Fe and Cu region is to be observed.
4. Summary
Based on the above observations following points can be summarized
from the present study:
a. The increase in Cu concentration in the Cu-Fe system increases the
total undercooling in the alloys prepared using ADL method. The
higher level of undercooling in the Cu rich composition is responsible
for the planner growth front and planar surface morphology in pure
Cu and Cu75Fe25 samples. In the case of Fe-rich compositions,
relatively lower undercooling promotes cellular surface morphology
in pure Fe and Cu25Fe75 samples.
b. In the case of pure Cu and Fe, a single phase is observed with a void
formed by volumetric contraction at the sample’s top surface. A core
shell structure is observed in all other compositions, with Fe present
in the shell and Cu in the core.
c. The SEM-EDS and X-ray tomography analyses support the formation
of the core-shell structure, and small Cu droplets were found
entrapped in the Fe rich region.
d. EBSD study of the solidified sample confirms the formation of core
shell structure in Cu-Fe alloys with Fe rich phase acts as shell and Cu
as core. In the pure Cu and Fe case, the degree of undercooling before
solidification influences the grain size distribution. Meanwhile,
depending on whether a nucleation site is present or not, the alloy’s
Fe phase will either create a coarse grain or a varied grain structure,
whereas the degree of phase separation determines the structure in
Cu phase. The IPF of phase separated Fe and Cu grains shows that
there is no orientation relationship between them.
Credit authorship contribution statement
Debaraj Sahoo: Formal analysis, Writing – original draft prepara­
tion, Investigation, Visualization, Software, Methodology. Prof. Manas
Paliwal: Supervision, Investigation, Validation, Formal analysis,
Methodology, Prof. Atul Srivastava: Methodology, Conceptualization,
Supervision, review Writing, Prof. Sushil Mishra: Supervision,
Conceptualization, Project administration, Funding acquisition, Meth­
odology, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
Acknowledgement
This work was supported by the Department of Science and Tech­
nology (DST), India under the Swarnajayanti Fellowship scheme (Grant
ID: RD/0115-DSTFL80-005). AS acknowledges the support received
from DST, India. Also, thankful to MMMF lab, IIT Bombay for providing
all the facilities for sample characterization and TESCAN XRE Demolab
Ghent, Belgium for the support to perform four-dimensional X-ray mi­
croscope (FDXM) analysis.
10
Materials Today Communications 37 (2023) 107288
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