Author’s Accepted Manuscript

PREPARATION AND PROPERTIES OF

COBALT-BASED SOFT MAGNETIC
MATERIAL PREPARED BY NOVEL POWDER
METALLURGY

Yogesh Srivastava, Sanjay Srivastava

www.elsevier.com/locate/jmmm

PII: S0304-8853(16)30493-0
DOI: http://dx.doi.org/10.1016/j.jmmm.2016.07.067
Reference: MAGMA61679
To appear in: Journal of Magnetism and Magnetic Materials
Received date: 30 April 2016
Revised date: 23 July 2016
Accepted date: 30 July 2016
Cite this article as: Yogesh Srivastava and Sanjay Srivastava, PREPARATION
AND PROPERTIES OF COBALT-BASED SOFT MAGNETIC MATERIAL
PREPARED BY NOVEL POWDER METALLURGY, Journal of Magnetism
and Magnetic Materials, http://dx.doi.org/10.1016/j.jmmm.2016.07.067
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 PREPARATION AND PROPERTIES OF COBALT-BASED SOFT MAGNETIC
MATERIAL PREPARED BY NOVEL POWDER METALLURGY
Yogesh Srivastava*1 and Sanjay Srivastava
Department of Material Science & Metallurgical Engineering, Ceramic & Powder Metallurgy Laboratory, Maulana
Azad National Institute of Technology, Bhopal, Madhya Pradesh, India (462003)

123209001_yogesh@manit.ac.in

Abstract
The present work deals with the development of nanocrystalline 60Co–26Fe-14Al (wt%)
soft magnetic materials via mechanical milling of elemental powders. The evolution of solid
solution during milling proceeded with continuous decrease in atomic order and the crystallite
size, and an introduction of internal strain and dislocations. The milling-induced lattice defects,
crystallite size reduction, and atomic disorder exhibited a decrease in saturation magnetization,
remanence magnetization, squareness ratio, and blocking temperature with increasing milling
time. It has been demonstrated that, at subzero temperatures, the magnetization decreases with
increasing temperature due to the development of an effective anisotropy caused by an evolution
of canted spin structure owing to the introduction of lattice defects during milling.
Keywords: Powder metallurgy; Nanocrystalline; Cobalt-Iron-Aluminium; Magnetism;
Dislocation density.

1. Introduction
Recently spin-electronics based industries have attracted scientific interest. But spin-
polarized current and electron transfer be the major challenges. To overcome this problem, Half-
metallic ferromagnet’s (HMF’s) be the potential candidate [1]. These HMF’s were first predicted
by de-Groot [2-5]. They exhibit strongly metallic in one spin and semiconducting in other spin at
the fermi energy (EF) level, that results in 100% spin polarization [6]. On the atomic level
heusler compounds, half-metallicity directly related to the structural disorderness. According to
band structure calculation, disordering in atomic position would reduce the spin polarization [1,
7]. Reduction of size to nano-scale would increase the disorder. So, nanostructured materials are
proven to be perfect for developing relation between magnetic nature and structural disorder [8,
9]. Cobalt-based heusler compounds have attracted primary interest due to high curie
temperature (Tc) and low atomic disordering [10]. Galanakis et al., theoretically predicted 84%

1
Contact No.: +91-9407256417/ 0755-2902318
spin polarization for Co2CrAl type full heusler alloy [11]. Kelekar et al., predicted the increase in
atomic disordering on Co2FexCr1-xAl films grown on MgO substrate [12, 13]. Also observed the
spin polarization increase at fermi energy by increasing the Fe concentration [14-17]. Further,
Wurmehl et al., predicted the properties of compounds using arc-melting suggested by Kelekar et
al [18]. Umetsu et al., synthesized Co2MnAl full heusler alloy by following induction melting
technique under protective atmosphere and studied its magnetic properties [19]. Furthermore,
Vinesh et al., showed the effect of mechanical alloying on Fe2MnAl type heusler alloy [20].
Mikami et al., suggested the preparation of Fe2VAl by ball milling [21].
The magnetic properties of cobalt based materials are size dependent [22, 23]. In these
magnetic materials, to achieve improved functional properties nano-sized grain diameters is
crucial. Since mechanically alloyed powder was carried out in a tungsten carbide vial, the
process became expensive and complex. Dube and co-workers successfully prepared powder
preforms in protective atmosphere [24-26].
Moreover, for the preparation of bulk samples, two noble processes are generally suggested ie.,
either by arc-melting or mechanical alloying. Both the processes have their own importance. Due
to limitations of product formation in arc-melting, mechanical alloying is one of the powerful
technique for production of high performance and low cost materials. In this work, mechanical
alloying is followed to obtain the physical features, microstructures and milling effect were
thoroughly studied.
2. Experimental procedure
In the present study, commercial available elemental powders of Cobalt (median particle
size 10.0 µm, > 99.9 % purity), Iron (median particle size 89.0 µm, > 99.9 % purity) and
Aluminium (median particle size 15.0 µm > 99.9 % purity), supplied by Alfa Aesar, USA used
as the starting material constituents. Before mixing the powders mixed in 60% wt.% Co, 26
wt.% Cr and 14 wt.% Al stoichiometric ratio. The composition obtained allowed for mechanical
alloying in high energy planetary ball mill (Pulverisette-5) supplied by Fritsch GmbH, Germany.
During mechanical alloying tungsten carbide balls (10 mm) used as the grinding medium. The
milling jars having capacity of 250 ml and internally lined with tungsten carbide. The process
carried out at a speed of 250 rpm. For this, the powder mixture mixed in balls-to-powder ratio
(BPR) of 10:1. A schematic diagram of the process carried out arrangement is shown in Fig. 1.
To avoid contamination and agglomeration of system, wet milling performed using excess
amount of process control agent (PCA). To limit the process and avoid the welding between the
vials and the balls, the milling paused periodically at every 20 minutes. The powder samples
collected at various stages of milling for their morphological analysis. The approach used to
calculate crystallite size and lattice strain based on the procedure discussed elsewhere [27, 28]. In
this approach, three most intense peaks in the X-ray Diffraction (XRD) spectra used for
calculations. The instrumental broadening corrected using standard silicon powder as the
reference material. Phase evolution in the milled powder samples studied using monochromatic
XRD, Pananalytical, X’Pert Pro equipped with copper target. The microstructural
characterization, structural formation, evolution of phase and average grain size was calculated
from X-ray diffraction (XRD) (Pananalytical, X’Pert Pro)of the milled, Scanning Electron
Microscopy (SEM) (JEOL, JSM-6390A, Japan) with accelerating voltage 10 kV and
Transmission Electron Microscopy (TEM). Electron Microscopy (EM) used to examine the
morphological feature and distribution of particle size of the powder particles.
2.1 Morphological analysis
The MAed powders produced after milling examined by using Scanning Electron
Microscopy (SEM) (JEOL, JSM-6390A, Japan) equipped with EDS, with accelerating voltage
10 kV and Transmission Electron Microscopy (TEM). Electron Microscopy (EM) used to
examine the morphological feature and distribution of particle size for the powder particles.
2.2 Structural evolutions phase
The structural formation, evolution phase and average grain size was envisage from XRD
using Cu kα radiation ranging 2θ from 300 to 900 taking the step size as 0.020 with the integration
time 4seconds. The X-ray broadening formation due to grain size can explained by Voigt and
Gaussian function [29]. The instrumental broadening corrected using the standard silicon as
reference material. The average crystallite size and the induced lattice strain estimated by using
the relation:

0.9
( t  o ) cos    4( )(sin  ) (1)
D

where, λ is the Cukα radiation wavelength

( t  o ) is FWHM of the milled powders
and,  is the lattice strain induced during milling.
2.3 Magnetic properties
Magnetic properties were determined by measuring M–H hysteresis loop using a
vibrating sample magnetometer VSM 3900 PMC under an applied field of 20 kOe at 300 K.
3. Results and discussions
3.1. Morphology
The micro structural and morphological variations at different milling intervals shown in
Fig. 2 (a-e). Fig. 2 (f) shows the particle size distribution of the powders with average particle
sizes used in the present study. At the early stage, the powder particles were deformed by
compression forces showing characteristic of ductile to ductile transition. The SEM results
reveals the presence of two kinds of phases ie., the phase with spherical morphology and other
flaky. During milling, the constitutents with brittle nature converted into angular or subangular
or spherical nature. While the ductile phases had resulted in flaky morphology. A Certain form
of agglomeration in the milled particles can be clearly seen. This agglomeration is due to the
predominance of welding mechanism and increase the inter-diffusion of Al and Fe in Cobalt.
After certain hours, a steady state condition arises and the smaller particles undergo to bear more
deformation without any further decrease in size.

The deformation occurs between the powder particles is due to the stacking fault energy
which results in the slip dislocation and dominates it. The refinement in the particle size
observed in 30-50 hours of milling assigned to increased deformation in the particles which
separates the agglomerated powders into various sections. Due to prolonged milling, crystallite
size decreases which results in increase of surface area. The milled powder particles were
electron transparent and close to the edges. The structure of finally MAed powders examined by
TEM as represented in Fig.3 (a) and (b) shows the fraction number of particles representing the
mean particle size. Clearly, it noticed that only some regions with ordered crystalline structure
viewed. But prolonging the milling time, these regions developed and the mean crystallite size
measured nearly to be ~20 nm.
3.2. Structural phase analysis
Fig.4 shows the XRD pattern of Co2FeAl powder prepared at different milling times.
From the figure, it clearly shows that in the early stage all the peaks consist of Co, Fe and Al
reflections. It provides a comparison with mechanically alloyed powders at various stages. No
oxide peaks are visible in the XRD profile. The continuous use of PCA helped in preventing any
oxide formation. According to XRD profiles, there shows an increase in the peaks broadening
with the increase in milling period, which result in the lattice strain development and grain
refinement as well. Another noticeable fact from XRD pattern, shifting peak towards the lower
angle. It shows the formation of major phase Co2FeAl with the minute possibility of small phases
formation in CoFe and FeAl.
The evolution of average crystallite size (L), and the strain (σ) of powders mixture shown in
Fig.5 and 6. It clearly seen rapid decrease in crystallite size in various stages of milling followed
by a sluggish decrease up to 50 hours. Average crystallite size of mixture powder after 50 hours
approximately found to be 20 nm. In early stage, Al peak get dissolved after 7 hours forming
solid solution. During the beginning stage, it is noticeable that owing to severe distortions
introduced in lattice which results in severe plastic deformation during mechanical alloying of
powder particles. As the milling time exceeds above 7 hours of milling, the crystalline phase
varied accordingly.
From Figure, the appearance of peak at 44.620 is clearly visible. The peak around 820 not much
clearly visible but there still exist a phase. As per the standards, the phase of prepared samples
are as follows. The peaks associated at 44.68, 65.58 and 82.42 correspond to Co2FeAl
respectively. While, the peaks at 41.579, 47.39 and 75.85 Fe signifies the existence of Fe,
Co4Al13 and Co2Al5 phase. Thus, the phases can be identified to Co2FeAl, Fe, Co4Al13 and
Co2Al5 according to the peak position as shown in Fig.4. Furthermore, we can see that the width
and the intensity of the diffraction peaks from Co2FeAl gradually increases and strong
respectively indicating the crystallinity of Co2FeAl. The appearence of super lattice peak (220)
indicates that the B2 phase structure, in which neither Co atoms go into the Fe or Al and vice-
versa. According to Scherrer’s equation and FWHM of the (220) peak, the grain size is
determined.
3.3 Lattice constant
The lattice constant also shows a variation in respect to milling as shown Fig.7. The lattice
constant continuously decreasing during milling process and attains a minimum value of about
0.71292 nm. The decrease of lattice parameter can be due to inter-diffusion of Al and Fe in Co
lattice [30] and the difference in the atomic radii of the solute atoms (rFe = 0.156 nm and rAl =
0.118 nm). The decrease of lattice constant could lead to the formation of solid solution and the
nanostructured phase [15]. It is clear from Fig. 4 that milling after longer duration, some of the
Al content is not completely dissolved. However, it may be suggested that addition of element
with a lower atomic radius (rAl= 0.118 nm) had dissolved in the Co lattice and formed a phase
consists of Co and Al. This may be attributed due to: (a) the lattice distortion because of severe
plastic deformation (b) temperature increment during the diffusion process and (c) structural
grain refinement as well.
3.4 Crystallinity
Crystallinity denotes to the degree of structural order in a solid and could be quantified as a
volume percentage of the material which is crystalline. The deviation in crystallinity leads to a
broadening of the diffraction peaks in XRD. By analyzing the peak broadening it is conceivable
to reveal information about the level of crystallinity. Broadening may be caused by instrumental,
crystallite size and the strain broadening. In the present investigation, the percentage crystallinity
was calculated based on pseudo–voigt function at the peak heights of various milling times. The
decrease in crystallinity with milling time is shown in inset of Fig. 7. This decrease was observed
upto 30% for 50 hours MAed powder. However, prolonged milling process decreases the
crystallinity with the increase in specific surface area that my favors the generation of Vander
Waal’s interactions.
3.5 Dislocation density
The crystallite size and dislocation density results indicated that the fracturing of particles
dominating till 30 hours indicating the constitutents are elastic in nature. The dislocations density
can be represented by the following equation [30, 31]:

( )1/2
D  2 3 (2)
( L)b
where b is the Burgers vector of dislocations and is equal to 0.3420 nm for Co and 0.2484 nm for
Fe; L is the crystallite size and σ is the micro strain. Two sections of density dislocation clearly
observed in Fig. 8. During the first 15 hrs of milling, the dislocation density slightly increases
from 0.09*1016/m2 to about 0.35*1016/m2 for Co, 0.04*1016/m2 to about 1.72*1016/m2 for Fe and
from 15 and 50 h, the dislocation density shows a considerable increase and reaches a maximum
value of about 1.15*1016/m2 in case of Co, 2.8*1016/m2 for Fe and 3.44*1016/m2 resectively for
the major phase formed. This explained by the fact collision between the balls will give rise to
temperature so the dislocations may undergo climb. So diffusivity increased by reduction of
crystallite size.
3.6 Magnetic property measurement
Since Co2FeAl is a half-metallic ferromagnet in nature, thus its saturation magnetization
can be calculated according Slater-Pauling rule which is given by [32-34]:
M = NV – 24 (3)
According to this rule, magnetic moment of 5.19 µB/f.u. is observed. The result is in
good agreement with the theoretical value.
Generally, soft magnetic materials involve frequent reversal of magnetization. Therefore,
it is necessary to kept hysteresis losses as low as possible by controlling its microstructural
features to get desired hysteresis loop [22, 23, 35-37]. Room temperature magnetic hysteresis
(M–H) loops of 60 Co–26 Fe-14 Al powder samples milled for various milling times using VSM
magnetometer is shown in Fig. 9.
These sigmoidal hysteresis loops are observed in samples due to the presence of structural
defects developed inside the grains. The unsaturated hysteresis loops can be related to the large
demagnetizing effect of the powders at higher milling times and disordered structure of the
powders.
The saturation magnetization and average magnetic moment at applied field gradually
decreases as milling proceeds. Further an increase in inter-atomic distances between Fe
neighbours atoms will contribute in lowering the saturation magnetization. Progressively during
milling process partial filling of d–d interactions take place is induced which results in the
decrease of average magnetic moment [38-44].
Since cubic symmetry of the crystal structure is existed for Co2FeAl in this phase. According to
this, the existence of five-fold degenerate d-orbitals spilts into t2g and eg orbitals. Therefore, only
two states still retain their degeneracy as a sign of the planar symmetry.
3.6.1. Saturation magnetization
From Fig. 10 (a), the saturation magnetization continuously increases with milling time
These variations can be explained under three categories:
3.6.1.1. Lower milling duration
It is observed that the decrease in magnetization can be attributed by lattice constant and
the grain size refinement, anti-site disorder and the stacking faults. Since the density of states is
sensitive to change in volume than exchange interaction, therefore the magnetic interaction is
expected to decrease with interatomic distances at the Fermi level.
3.6.1.2. Medium milling duration
The decrease in saturation magnetization can be explained by the presence of non-
ferromagnetic elements, effect of disordered grain boundary and the surface effects.
3.6.1.3. Higher milling duration
At higher milling interval all alloying elements were completely dissolved into the Co
matrix which forms the associated phase. The dissolution process was completed which is clear
from the XRD patterns. Though some amount of Al remains undissolved which forms B2 phase.
This Al might be responsible for the decrease in saturation magnetization. The resulting narrow
hysteresis loop implies a very small hysteresis loss under cyclic magnetization field. The
saturation magnetization of the bulk powder were approximately 140.79 emu/g at 20 kOe which
are almost similar to the values reported.
3.6.2 Remanence magnetization (Mr)
The magnetic remanent magnetization (Mr) values were extracted from the hysteresis
loops and their evolution with milling time plotted in Fig. 10 (b). This sharp decrease remanent
magnetization after 50 hours of milling might be attributed due to the particle size reduction and
the formation of grain boundaries inside the material. The remanent magnetization showed a
decrease in values from 37.5 emu/g to 17.8 emu/g due to the formation of cluster size pa rtices
and the increase in density of defects formed during milling.
3.6.3. Magnetic coercivity (HC)
Magnetic coercivity is plotted versus milling time in Fig. 10 (c). From the figure, it can be
perceived that up to 15 hours of milling, the coercivity increase from 23.88 emu/g to 25.27
emu/g and can be attributed to the effect of plastic deformation and internal strain introduced.
And above 15 hours, HC shows a monotonically decreases upto 23.71 emu/g. The reduction in
coercivity upto 30 hours of milling is the result of deviation of inter-atomic spacing in interfacial
regions. On further increasing the milling from 30 hours to 50 hours, HC holds a constant level
and achieve a final value of 17.8 emu/g.
3.7 FC-ZFC measurement
Fig. 11 shows the field-cooled (FC) and zero-field-cooled (ZFC) magnetic measurement as a
function of temperature for the samples milled at various durations. The ZFC magnetization was
recorded by lowering the temperature in zero magnetic field and then applying the magnetic field
by increasing the temperature. FC magnetization were obtained by cooling the sample to low
temperature in external field and then raising the temperature. FC and ZFC measurement curve
represents the change from ferromagnetic to paramagnetic transformation. From ZFC
magnetization measurement, there exhibits blocking temperature (TB) at around 425 K for final
mechanically milled sample.
In large external field, field dependence is attributed by ferromagnetic contribution that
dominates the reversal behavior. The superparamagnetic behavior can be described by the
relation:
EA
  0( ) (4)
k BT
where,  is the superparamagnetic relaxation time
 0 is the relaxation time constant
T is the temperature

and, EA  ln( )k T  25k BT (5)
0 B
Therefore, the blocking temperature (TB) can be given by the relation
TB = KV/25kB (6)
According to eq. (6), we can conclude that if the size of the particle increases TB increases and
vice-versa.
3.8 Squareness ratio
For determining the magnetic energy, squareness ratio (Mr/MS) is plotted against milling time in
Fig. 12. The squareness ratio shows a continuous decrease due to domain wall pinning because
of induced defects. This continuous decreased in Mr/MS with increasing milling time indicating
the existence of single domains in magnetic powder.
3.9 Milling impact on compensation temperature (Tcomp)
The magnetic contribution arises from the antiparallel alignment of magnetic moments in the
resultant of the coupled magnetic moments. The net magnetization direction is determined by the
sublattice magnetization at low temperatures, i.e. at sub-zero temperatures. However, at high
temperatures, the magnetization of the sub-lattice decreases rapidly due to the weak coupling
between the magnetic moments. Interestingly, at the compensation temperature (Tcomp), the
magnetization of one of the sublattice becomes equal and opposite to the resultant of the other
sublattices. The compensation temperature can be defined according to the following relation
[45]:
N A ( S  1)
Tcomp  g B2 (aa  ad ) M a (0)
3k
with (aa  ad )M a (0)  (dd  ad ) M d (0)
where, λaa, λad, λdd are the molecular field coefficients of sublattice aa, ad, dd, respectively at low
temperatures. Also the super-exchange interaction between various sites is determined by the
bond angle in the sub-lattices [46]. Since the defects are introduced during the mechanical
alloying, it will change the bond angle, resulting in altering the nature of super-exchange
interaction between various sites. As a result, the molecular field coefficients and compensation
temperature are changed accordingly. Fig. 13 represents the magnetization variation with
temperature and inset shows the differential change (dM/dT) and its slope leads to the
compensation temperature. The compensation temperature for the present system was found to
be 881.92 K.
3.10 Effect on canted spin structure
Fig. 14 shows the magnetization for milled sample at various temperatures. We could observe
that at 300 K, the saturation is obtained a value of 140.79 emu/g and on decreasing the
temperature saturation magnetization value increases to 215 emu/g. The loops suggested the
presence of canted spin structure in mechanically milled samples which is due to the super-
exchange interaction weakening and the structural defects introduced during the process. The
canted spin structure is responsible for the development of effective anisotropy (Keff).
4. Conclusion
A new powder metallurgy processing route, based on mechanical milling of elemental
powders, for preparing L21/B2 60Co–26Fe-14Al (wt%) alloy powder has been proposed, and
the existing changes in structural and magnetic properties have been studied. The prepared
nanocrystalline powder formed non-equilibrium solid solution with dislocation density about
1016/m2. The atomic order, lattice parameters, and magnetic properties changed with increasing
milling time. During milling, the dislocation defects are introduced which reduced the crystallite
size of powders, leading to decreased magnetism as observed. A very narrow hysteresis loop was
obtained under cyclic magnetization environment which is attributed to the disordered structure.
The coercivity first increased and then rapidly decreased with milling time, attaining a constant
value after 50 hours. Moreover, the saturation magnetization, remanence magnetization,
squareness ratio, and blocking temperature were found to decrease continuously with increasing
milling time. These changes were attributed to the decrease in lattice order, crystallite size, and
incorporation of lattice defects in the powder due to milling. The compensation temperature
(Tcomp) was estimated approximately 881.92 K for the present system. It was also observed that
the structural defects are responsible for canted spin structure, which may lead to the
development of effective anisotropy resulting in a decrease in the magnetization with increasing
temperature in the sub-zero temperature regime.
Acknowledgement
The authors wish to express their gratitude to the MANIT for providing financial support
to carry out this work through TEQIP-II grant no. 1823/MSME/MANIT/8/9/2015. Permission
from Central Instruments Facility, IISER Bhopal (M.P.), India for the use of VSM is gratefully
acknowledged.
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Fig 1.Process flow diagram for alloy formation

Fig 2. SEM micrographs of Elemental powders of (a) Co, (b) Fe (c) Al, (d) 7 hrs milled (e) 15
hrs milled (f) 30 hrs milled (g) 50 hrs milled powder and (h) shows particle size distribution

Fig 3. (a) TEM micrograph of 50 hr MAed powder and (b) mean particle size distribution
Fig 4. XRD profile pattern of MAed powders at different time intervals (a) Premix, (b) 7 hr, (c)
15 hr, (d) 30 hr and (e) 50 hr
Fig 5. Crystallite size variation with milling duration
Fig 6. Variation of microstrain with milling time
Fig 7. Variation of lattice constant with milling time and inset shows the crystallinity
Fig 8. Variation of dislocation density with milling time
Fig 9. Variation of magnetization with milling time
Fig 10. Variation of Ms, Mr and Hc with milling duration
Fig 11. Variation of magnetization with temperature for (a) 30 hrs and (b) 50 hrs milled
Fig 12. Dependence of room temperature squareness ratio on milling duration
Fig 13. Variation of magnetization with respect to temperature. Inset shows dM/ dT with
temperature
 Fig 14. First quadrant hysteresis loops for 15 hrs mechanically milled at various temperatures

Highlights

 Co-based HA have been fabricated by mechanical alloying.

 The effect of milling time was investigated.
 The saturation magnetization can be reached up to 140.79 emu/g.