Journal of Alloys and Compounds 350 (2003) 232–245 L

www.elsevier.com / locate / jallcom

Glass-forming ability and magnetic properties of mechanically solid-state

reacted Co 1002x Ti x alloy powders
a, a b
M. Sherif El-Eskandarany *, Wei Zhang , A. Inoue
a
Inoue Superliquid Glass Project, Exploratory Research for Advanced Technology, Japanese Science and Technology Corporation, Yagiyama-minami,
2 -1 -1, Sendai 982 -0807, Japan
b
Institute for Materials Research, Tohoku University, Katahira 2 -1 -1, Sendai 980 -8577, Japan
Received 19 June 2002; received in revised form 12 July 2002; accepted 12 July 2002

Abstract

A high-energy ball milling technique using the mechanical alloying method has been employed for fabrication of glassy Co 1002x Tix
(25#x#67) alloy powders at room temperature. The fabricated glassy alloys in the Co-rich (33$x) side exhibit good soft magnetic
properties. The binary glassy alloys for which the glass transition temperatures (T g ) have rather high temperatures (above 800 K), show
large supercooled liquid regions before crystallization (DT x larger than 50 K). The reduced glass transition temperature (ratio between T g
and liquidus temperatures, T l (T g /T l )) was found to be larger than 0.56. We have also performed post-annealing experiments on the
mechanically deformed Co / Ti multilayered composite powders. The results show that annealing of the powders at 710 K leads to the
formation of a glassy phase (thermally enhanced glass formation reaction), of which the heat of formation was measured directly. The
similarity in the crystallization and magnetization behaviors between the two classes of as-annealed and as-mechanically alloyed glassy
powders implies the formation of the same glass state.
 2002 Elsevier Science B.V. All rights reserved.

Keywords: Amorphous materials; Transition metal alloys; Mechanical alloying; Magnetic measurements

1. Introduction tions [23–25]. Since the pioneering investigation of Koch

For more than 5000 years, most metallic alloys have
been fabricated by melting and casting techniques [1]. The
mechanical alloying (MA) [2,3] process is a rather new
comer to the world of metallurgy and materials science.
Whether it can be called a revolution or simple evolution,
the MA method has been successfully employed for
producing wide varieties of advanced materials, including
metal nitrides [4,5], carbides [6,7], hydrides [8,9], silicates
[10], equilibrium [11] and nonequilibrium [12] phases,
composite and nanocomposite materials [13–16], and
nanocrystalline materials [17,18]. Amongst these useful
materials, metallic glassy alloys, with their unique short-
range atomic order, have attracted research by many MA
scientists [19–22] due to the desirable properties that make
them pioneering materials for several industrial applica-
*Corresponding author. Present address: Faculty of Engineering, Al-
Azhur University, Nasr City 11371, Cairo, Egypt.
E-mail address: msherif@mst1.mist.com.eg (M. Sherif El-Eskan-
darany).
et al. [3] in 1983, numerous numbers of amorphous alloys
and metallic glasses were fabricated by the MA method
[26–42]. Accordingly, the term MA is becoming increas-
ingly common in both metal science and glass science.
In the recent years, metallic glassy soft magnetic
materials (see, for example, Refs. [43–45]) have received
much attention due to their unique properties and their
promising applications. These materials offer the oppor-
tunity to decrease transformer core losses. In particular a
large elastic flexibility guarantees excellent insensitivity
with respect to plastic deformations and a small electrical
conductivity reduces the eddy-current losses. Co-based
glassy / amorphous alloys, with their non-magnetorestric-
tion, possess excellent soft magnetic properties that pro-
pose them as core and sensor materials for inductive
applications. Binary Co–Ti glassy alloys, which do not
show any deep eutectic compositions in the equilibrium
phase diagram [46] have not received much attention
because of the difficulties of preparation by the conven-
tional melt-spinning method. The only report for the
formation of an ordinary amorphous Co 78 Ti 22 alloy by the

0925-8388 / 02 / $ – see front matter  2002 Elsevier Science B.V. All rights reserved.
PII: S0925-8388( 02 )00929-5
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245 233

way of rapid solidification from the molten metallic alloy
is that of Inoue et al. in 1980 [47].
In the present study, the glass-forming ability of me-
chanically alloyed Co 1002x Ti x has been investigated. The
effect of annealing on the structure and stability of the
multilayered Co / Ti composite powders, which are ob-
tained during the early stage of ball milling, has been
studied. For the purpose of the present work, X-ray
diffraction, scanning and transmission electron micro-
scopy, magnetic measurements, differential scanning
calorimetry and differential thermal analysis have been
employed to monitor the effect of MA time on the
structural changes and the thermal stabilities of the fabri-
cated glassy alloy powders.
contamination contents in the final product (86 ks) of MA
powders are 0.14–0.22 wt% and 0.34–0.60 wt%, respec-
tively. Annealing the multilayered composite MA powders
was performed at the desired temperatures in well-sealed
DSC Al-cells under continuous flow (2.5 ml s 21 ) of
purified argon flow. As soon as the annealing procedure
was achieved, the DSC was rapidly cooled and the samples
were subsequently removed from the DSC heating
chamber. The as-annealed samples were structurally ana-
lyzed by means of XRD, TEM / EDS and VSM techniques.
SEM / EDS technique was employed to observe the metal-
lographical and compositional changes of the as-annealed
MA particles.

3. Results

2. Experimental procedure 3.1. Structural changes with the MA time

Pure elemental powders (99.9% or better) of Co (25 The XRD patterns of mechanically alloyed Co 1002x Ti x
mm) and Ti (50 mm) were used as the starting reactant powders are shown in Fig. 1 after 86 ks of MA time (final
materials of MA. The powders were firstly balanced to product). Clearly visible haloes are obtained, especially in
give the nominal composition of Co 1002x Ti x (x525, 31, the Co-rich side (x,50 at%), indicating the completion of
33, 50 and 67 at%), mixed, charged into tempered chrome
steel vials (250 ml in volume) and then sealed together
with 50 tempered chrome steel balls (10 mm in diameter)
in an argon atmosphere glove-box. The ball-to-powder
weight ratio was maintained as 14:1. The MA experiments
were performed in a planetary ball mill (Fritsch P5) at a
rotation speed of 2.1 s 21 . In order to avoid an increase in
the vial temperature, the milling procedure was period-
ically interrupted every 1.8 ks and then halted for 3.6 ks
under a continuous flow of air. The later process was
necessary to eliminate the buildup of unprocessed powder
deposits at dead or abandoned spots inside the vials. The
ball milling was stopped after selected milling times and a
small amount (about 500 mg) of the MA samples were
taken from the vials in the glove box. The as-milled
samples were characterized by means of X-ray diffraction
(XRD) employing Cu Ka radiation, transmission electron
microscopy (TEM), using a 300-kV field emission micro-
scope, scanning electron microscopy (SEM) using 15-kV
field emission electron microscope, differential scanning
calorimetry (DSC) and differential thermal analysis (DTA)
at a constant heating rate of 0.67 K s 21 and under flow of a
purified argon gas (99.999 wt%). The magnetic polariza-
tion (Js ) of the ball-milled powders was measured at room
temperature, using a vibrating sample magnetometer
(VSM) with a maximum applied magnetic field of 670
kA m 21 . The coercive force was measured with a B–H
loop tracer. Energy dispersive spectroscopy (EDS), using
an electron beam of |5 nm has been used for analyzing
the concentration of the alloying elements, and the degree
of Fe contamination in the milled powders. In addition, the
oxygen content was determined by the helium carrier Fig. 1. XRD patterns of mechanically alloyed Co 1002x Ti x powders after
fusion–thermal conductivity method. The iron and oxygen 86 ks of the ball milling time.
234 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
the solid-state reaction and the formation of amorphous
alloys (Fig. 1a–c). The rather irregularity for the position
of the first halo maximum may be attributed to the surface
oxidation of the amorphous powders that occurred during
handling the powders outside the glove-box. For x550 and
67, the end-products are mixtures of an amorphous phase
coexisting with a small volume fraction of unprocessed
h.c.p.-Ti nanocrystalline powders (Fig. 1d and e). It can
then be concluded that the mechanically alloyed Co–Ti
binary system exhibits a considerably wide amorphization
range, extending from 25 to 67 at%.
In order to understand the amorphization process and the
structural changes that take place upon ball milling the
alloying elements of Co and Ti powders, some samples
were taken after different MA times. The XRD patterns of
mechanically alloyed Co 75 Ti 25 (selected here as a typical
example) powders are shown in Fig. 2 after selected MA
times. In contrast to the powders at the early stage of MA
(0–7.2 ks), which are a mixture of polycrystalline h.c.p.-
Co and h.c.p.-Ti (Fig. 1a,b), a broad diffuse and smooth
halo appears after 32 ks of MA time (Fig. 2c), indicating
the formation of an amorphous phase. This amorphous
Fig. 2. XRD patterns of mechanically alloyed Co 75 Ti 25 powders after (a)
0, (b) 7.2, (c) 32, and (d) 86 ks of ball milling time.
phase maintains its unique structure and does not transform
into any other metastable / stable phase even after longer
MA time (86 ks), as displayed in Fig. 2d.
The bright field images (BFIs) of Co 75 Ti 25 powders at
the early stage of milling are shown in Fig. 3. After a few
kiloseconds of MA time (1.8 ks), the metallic Co and Ti
powders tend to agglomerate and form large-grained
composite powders (Fig. 3a). These agglomerated particles
are continuously subjected to impact and shear forces upon
increasing the MA time. The existence of numerous faults
with grain boundary fringes and heavy dislocations in the
boundary is the general feature for the sample, which was
ball-milled for 7.2 ks (Fig. 3b).
The image of a high-resolution transmission electron
microscope (HRTEM) of mechanically alloyed Co 75 Ti 25
powders that was ball milled for 86 ks is shown together
with the corresponding selected area diffraction pattern
(SADP) in Fig. 4. The image shows maze pattern contrast
(Fig. 4a) with a typical halo-diffraction pattern of an
amorphous phase (Fig. 4b).
In order to assess the distribution of the alloying
elements (Co and Ti) in the powders of the final product
(86 ks), the local composition and the degree of homo-
geneity of the ball-milled sample have been examined by
the TEM / EDS technique. Some selected examined regions
for this sample are indexed in Fig. 4a and the corre-
sponding EDS analyses are listed in Table 1. Obviously,
the compositions do not fluctuate drastically from region to
region and the constituent elements of Co and Ti are
uniformly distributed in the powders, being rather close to
the starting nominal composition of Co 75 Ti 25 . The same
information could be obtained for the other compositions
of mechanically alloyed Co 1002x Ti x amorphous alloy
powders.
3.2. Metallographic changes with the MA time
Detailed SEM examinations were performed to under-
stand the metallography of mechanically alloyed
Co 1002x Ti x powders after different stages of MA. Fig. 5
shows the micrographs of the cross-sectional views of
Co 75 Ti 25 powders after selected MA times. After a few
kiloseconds of milling (1.8 ks), the starting ductile pow-
ders tend to agglomerate and form composite particles with
a thick multilayered structure (Fig. 5a). However, after 7.2
ks of MA time, the powders manifest a much finer
‘lamellar’ structure of the two constituents (Fig. 5b). In
addition, the layers are arranged in one orientation direc-
tion. Further milling (11 ks) enhances the shear and impact
forces generated by the balls and this leads to drastic
reduction of the layer thickness (Fig. 5c) so as to be hardly
visible after 86 ks of the MA time (Fig. 5e). The
disappearance of the layered-structure morphology implies
the completion of the solid-state reaction and the formation
of a single phase.
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245 235

Fig. 3. BFI of mechanically alloyed Co 75 Ti 25 powders after (a) 1.8 and (b) 7.2 ks of ball milling time. The SADP that corresponds to the BFI in (b) is
presented in Fig. 3c.
236 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245

Fig. 4. (a) HRTEM and (b) the corresponding SADP of the final product (86 ks) of mechanically alloyed Co 75 Ti 25 powders. The EDS analyses of some
selected regions are listed in Table 1.

3.3. Magnetic measurements 3.4. Thermal stability

The typical hysteresis loops of the end-product (86 ks of
MA time) of mechanically alloyed Co 1002x Ti x alloy pow-
ders are shown in Fig. 6a. In spite of the samples of x550
and 67, the amorphous alloy powders in the Co-rich side
(x,50) exhibit typical soft magnetic-type hysteresis loops.
Fig. 6b summarizes the magnetic properties of me-
chanically alloyed Co 1002x Ti x powders, indexed by Js of
the end-products with respect to the Ti content, x. The Js
values of amorphous Co 75 Ti 25 , Co 69 Ti 31 and Co 67 Ti 33
alloy powders are 0.64, 0.61, and 0.42 T, respectively.
Contrary to these rather high values, the Js values of the
amorphous Co 50 Ti 50 and Co 33 Ti 67 powders are 0.06 and
0.02 T, respectively. Obviously, Js is roughly decreasing
linearly with increasing Ti content, x.
Table 1
Local compositional EDS analysis of mechanically alloyed Co 75 Ti 25
powders that were obtained after 86 ks of milling time
Region Co (at%) Ti (at%)
1 75.7 24.3
2 76.3 23.7
3 75.2 24.8
4 74.7 25.3
5 75.8 24.2
The selected analytical zones are indexed in Fig. 4 (see the main text).
The DSC scans of mechanically alloyed Co 1002x Ti x
powders that were ball-milled for 86 ks (end-product) are
displayed in Fig. 7. For all alloys in the composition range
(Fig. 7a–c) two separate reactions are taking place. The
first reactions, which are endothermic, are due to the glass
transition of the formed glassy phase, whereas the second
sharp exothermic reaction is attributed to the crystallization
of the glassy phase. It is worth mentioning that the
appearance of the endothermic reactions during the DSC
scans, indicates the formation of glassy phase. In addition,
the crystallization of the glassy phase takes place through a
single sharp exothermic reaction (Fig. 7a–c), suggesting
that the formed glassy phase is single in structure and
homogeneous in composition. We will define the onset
temperature of the first and second reactions as glass
transition, T g and crystallization, T x temperatures, respec-
tively. In addition, the supercooled liquid region before
crystallization, will be denoted as DT x (DT x 5 T x 2 T g ).
Contrary to these glassy powders, the DSC scan for
Co 33 Ti 67 (Fig. 7d) reveals a broad exothermic reaction,
which lies at a relatively lower temperature (|727 K),
suggesting that the obtained amorphous phase is rather
heterogeneous. The absence of T g implies that the formed
metastable phase is an ordinary amorphous alloy.
In order to get more information about the progress of
the solid-state reaction during the several stages of MA,
selected ball-milled Co 1002x Ti x powders at the early,
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
Fig. 5. SEM micrographs of the cross-sectional view for mechanically alloyed Co 75 Ti 25 powders after ball milling for (a) 1.8, (b) 7.2, (c) 11, and (d) 86 ks.
intermediate and final stages of MA were thermally
analyzed. The DSC scans of the ball-milled powders,
exemplified by Co 75 Ti 25 powders are presented in Figs. 8
and 9 after different MA times. Fig. 8 displays the DSC
scan of Co 75 Ti 25 powders after 11 ks of MA time. The
scan reveals three separate reactions that take place: at 661
K (peak temperature of the first broad exothermic re-
action), at 765 K (onset temperature of the endothermic
reaction) and at 833 K (onset temperature of the second
sharp exothermic reaction). We should emphasise that the
first exothermic peak is a temporary reaction and com-
pletely disappeared during the second heating run of the
sample, which was previously annealed at 710 K. Contrary
to this low temperature reaction, the last two peaks
permanently remain during the second DSC scan. This low
temperature peak does not appear anymore in the DSC
scans of the samples at the intermediate (22–43 ks) and
final (65–86 ks) stages of MA, as shown in Fig. 9.
237
Surprisingly, the endothermic reaction, which is clearly
visible in the DSC scan of Fig. 8, disappears during the
intermediate stage of the MA processing time (Fig. 9a,b).
Moreover, the second exothermic reaction, which takes
place sharply in the DSC run of the 11 ks sample (Fig. 8),
tends to be broadened with remarkable shift to the high
temperature side (857 K) upon MA for 22 ks (Fig. 9a).
This crystallization reaction, however, becomes rather
pronounced after 43 ks of MA time (Fig. 9b) and main-
tains its tendency for shifting to the higher crystallization
temperature (T x ) side (876 K). The endothermic reaction
corresponding to the glass transition temperature, T g ,
appears at 833 K after 65 ks of MA time (Fig. 9c) and
becomes more visible upon ball milling for 86 ks, when
the crystallization reaction becomes sharp (Fig. 9d). It is
worth mentioning that the DT x of the end-product (86 ks)
exhibits an extraordinary large value of 57 K for a binary
metallic glassy alloy. The T g was confirmed by heating the
238 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
Fig. 6. (a) Hysteresis loops of as-mechanically alloyed Co 1002x Ti x
powders of (i) Co 75 Ti 25 , (ii) Co 69 Ti 31 , (iii) Co 67 Ti 33 , (iv) Co 50 Ti 50 , and
(v) Co 33 Ti 67 amorphous alloys. (b) Magnetic polarization of the end-
product of MA as a function of Ti concentration (x).
samples to a temperature just above T g and then cooling
down to about 320 K. Then, the second and third heating
runs were performed to confirm the reproducibility of T g
and to establish a base line. The T g always appears at the
same temperature (832.8–833.2 K) for all the three heating
runs.
We shall go back to the scan in Fig. 8, with its puzzling
low-temperature exothermic peak and thermal stability. In
order to explore and interpret the roots of the fully
separated exothermic reactions, three separate samples
(denoted as [I, [II and [III), which had been originally
ball-milled for 11 ks, were independently heated to the
desired temperatures for several investigations. The XRD
pattern reveals sharp Bragg-peak reflections that corre-
spond to elemental Co and Ti crystals, with no indication
Fig. 7. DSC curves of the end-product (86 ks) of as-mechanically alloyed
Co 1002x Ti x powders for (a) Co 75 Ti 25 , (b) Co 67 Ti 33 , (c) Co 50 Ti 50 , and (d)
Co 33 Ti 67 glassy alloys.
of the existence of a glassy phase (Fig. 10a). In addition,
its hysteresis B–H loop (Fig. 11a) shows rather high
values of Js and coercive Hc , being very close to those
values for the powders at the early stage of MA, implying
the absence of any glassy phase.
The XRD pattern of the sample that was taken after the
completion of the first exothermic reaction (Fig. 8) reveals
a typical halo-diffuse pattern of an amorphous phase (Fig.
10b). In addition, the hysteresis B–H loop of this sample
(Fig. 11b) shows lower values (in comparison with sample
[I) of Js (0.68 T) and coercive Hc (3.13 kA m 21 ), being
slightly higher than those of the glassy Co 75 Ti 25 sample
obtained after 86 ks of MA time (see Fig. 6a(i)). This may
be attributed to the existence of unreacted elemental fine
particles of Co in the as-annealed sample. The local
compositional analysis of this annealed sample has been
examined by the TEM / EDS technique. Aside from the
featureless fine structure (Fig. 12a) and its correlated halo-
diffuse SADP (Fig. 12b) of an amorphous phase, the
compositions of some selected regions (see the table in
Fig. 12) have close values, being very close to the starting
nominal composition.
The XRD pattern of the sample heated to 993 K (Fig.
10c) reveals an f.c.c. structure with a lattice parameter (a 0 )
of 0.36175 nm, in good agreement with the reported value
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
Fig. 8. Typical DSC curve of as-mechanically alloyed Co 75 Ti 25 powders
for 11 ks of the ball milling time. Points [I, [II and [III refer to the
samples that are taken for SEP/ EDS, XRD, VSM and TEM investigations
(see Figs. 10–13). Whereas T TEGFR is the peak temperature of the
amorphization peak, T g and T x are the onset temperatures of glass
transition and crystallization temperatures, respectively. The shaded area
under the DSC scan displays the structural changes that take place upon
heating these multilayered composite powders in the DSC. The crystalline
composite Co 75 Ti 25 powders, which cover a temperature range extending
from room temperature up to 696 K, are transformed into solid–amor-
phous upon annealing at temperature II (710 K) which melts (glass
transition) and transforms into liquid–amorphous in an area which
extended from 768 to 831 K. It then gradually transforms into the most
stable phase of f.c.c.-Co 3 Ti upon heating through a single exothermic
reaction that extends from 981 K.
of the ordered phase of f.c.c.-Co 3 Ti [48]. Furthermore, the
hysteresis B–H loop (Fig. 11c) does not imply any soft
magnetic properties, with a low value of Js (0.23 T).
In addition to the above analyses, the melting (T m ) and
liquidus (T l ) temperatures of the as-annealed sample at 710
K have been examined, using the DTA technique. The
typical DTA curve of the annealed sample is placed in Fig.
13a together with the DTA scan of the glassy powders that
were obtained after 86 ks of MA time (Fig. 13b). The
curve a shows a single endothermic reaction which starts at
1425 K (T m ) and ends at 1480 K (T l ), in excellent
agreement with the reported values of f.c.c.-Co 3 Ti [46].
These values are close to those of the final product (1431
and 1476 K, respectively) (Fig. 13b). However, the T g /T l
value of the as-annealed sample (0.52) is considerably
lower than that of the final product (0.56). Therefore, it
can be concluded that when pure multilayered Co / Ti
composite particles are subjected to isothermal annealing
239
Fig. 9. DSC thermograms of mechanically alloyed Co 75 Ti 25 powders
after (a) 22, (b) 43, (c) 65, and (d) 86 ks of the ball milling time.
at 710 K for 1.8 ks, a solid-state diffusion reaction is
taking place and a glassy phase is yielded. We shall call
this process a thermally enhanced glass formation reaction
(TEGFR).
The thermal stability of mechanically alloyed Co 75 Ti 25
powders, indexed by the T g , and crystallization tempera-
ture, T x are presented as a function of MA time in Fig. 14a.
In the figure, the T TEGFR (peak temperature of the low
exothermic temperature reaction in Fig. 8), which takes
place during the early stage of milling, is independent of
MA time and disappears after 11 ks of the MA time. At
this early stage of milling, T g appears in a temperature
range of 763–766 K and surprisingly disappeared as soon
as T TEGFR disappears. The T x of the glassy phase obtained
at the early stage of milling slightly changes with increas-
ing MA time. It, however, changes dramatically during the
intermediate stage, indicating continuous compositional
changes of the mechanically alloyed powders. At the end
of the final stage of milling (65–86 ks), T x tends to reach a
value of 889 K, implying the completion of the me-
chanically induced glass formation reaction (MIGFR) and
the formation of a single homogeneous glassy phase.
Moreover, T g which disappeared during the intermediate
and the mid final stages of milling, appears during the end
of this final stage (76–86 ks). DT x of the glassy phase
obtained at the final stage of milling has a rather large
240 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
Fig. 10. XRD patterns of previously mechanically alloyed Co 75 Ti 25
powders for 11 ks and then heated to (a) 473, (b) 710, and (d) 993 K (see
Fig. 6).
value of 56 K. This value is considerably lower than that
of the glassy phase, which is obtained by annealing the
powders of the early stage of milling (63 K). This may be
attributed to the introduction of oxygen and iron contami-
nations into the powders (0.14 and 0.60 wt%, respectively)
upon longer ball milling (86 ks).
The T g , T x , T m and T l of the end-product of me-
chanically alloyed Co 1002x Ti x powders are presented in
Fig. 14b as a function of Ti content, x. The mechanically
alloyed glassy powders in the composition range 25$x#
50 exhibit large values of DT x (over 50 K), especially in
the Co-rich side (x#25). Both T g and T x depend on T m
and T l , which change markedly with changing Ti con-
centrations.
Further information on the amorphization and crys-
tallization reactions is given by the enthalpy change of
glass formation (DHTEGFR ) via thermally enhanced glass
formation reaction TEGFR and enthalpy change of crys-
tallization (DHx ) and presented as a function of MA time
in Fig. 15a and b, respectively. For all compositions
(25#x#50) the values of DHTEGFR were directly mea-
sured from the area under the low temperature exothermic
Fig. 11. Hysteresis loops of previously mechanically alloyed Co 75 Ti 25
powders for 11 ks and then heated to (a) 473, (b) 710, and (d) 993 K (see
Fig. 6).
reaction during DSC measurements of the powders at the
early stage of milling, which is previously shown in the
DSC scan of x525 (see Fig. 8). DHTEGFR tends to decrease
monotonically during the first few kiloseconds of milling
and approaches minimum values, ranging from 20.39
kJ mol 21 (x550) to 20.56 kJ mol 21 (x525). However, it
increases with increasing MA time and completely van-
ished towards the end of the MA time (Fig. 15a). In
contrast to the DHTEGFR at the Co rich side (x#31),
DHTEGFR at the Ti rich side (x$31), has lower values and
it takes longer MA time to disappear. It is worth mention-
ing that the low temperature peak due to the TEGFR does
not appear during DSC scans of the composite powders at
the Ti-rich side, which already have formed thick layers
(.500 mm). Increasing the MA time does not improve the
metallographical characterizations, and the powders still
contain many thick layers even after longer MA time, as
long as 86 ks. Accordingly, DHTEGFR for Co 33 Ti 67 (x567)
multilayered powders has zero value and does not change
with increasing MA time, as displayed in Fig. 15a.
During the early stage of MA (11 ks) the DHx slightly
changed with changing MA time (Fig. 15b). However, it
drastically decreased to 22.19 kJ mol 21 (x525) to 20.68
kJ / mol (x567) upon further ball milling time (11–43 ks),
indicating an increase in the volume fraction of the formed
glassy phase. During the last stage of MA (65–86 ks) DHx
tends to reach saturation values, ranging from 22.35
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245 241

Fig. 12. (a) HRTEM, and (b) the correlated SADP of previously mechanically alloyed Co 75 Ti 25 powders for 11 ks and then heated to 710 K. The
corresponding EDS analyses are listed in a table inside the figure.

kJ mol 21 (x525) to 20.96 kJ mol 21 (x50.67), indicating
the completion of the MA processing time.
4. Discussion
In contrast to the Co–Zr binary system, with its several
deep eutectic compositions [49] which allows a wide
glass-formation range (see, for example, Ref. [50]), the
formation of a glassy phase in the Co–Ti binary system
has never, so far as we know, been reported in this system.
This can be understood by looking at the phase diagram of
this system, which does not show any deep eutectic
compositions [46]. The first attempt at preparing an
ordinary amorphous phase of Co 78 Ti 22 alloy was demon-
strated by Inoue et al. [47] when they reported the
possibility of forming an amorphous phase in a very
narrow range (between 21 and 23 at% Ti), using a melt-
spinning method. The present study confirms that a solid-
state amorphization reaction takes place upon high-energy
ball milling elemental powders of Co 1002x Tix under an
argon gas atmosphere at room temperature. Either a
thermally enhanced glass formation reaction (TEGFR) or a
mechanically induced glass formation reaction (MIGFR)
242 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245

Fig. 13. DTA curves of (a) as-mechanically alloyed Co 75 Ti 25 powders for

11 ks and then heated to 710 K, and (b) as-mechanically alloyed Co 75 Ti 25
powders for 86 ks. In the figure, T m is the melting temperature, whereas
T l is the liquidus temperature.

takes place when using the ball milling technique for

synthesizing glassy Co 1002x Ti x (25#x#50) powders.
When the elemental powders are mechanically alloyed for
a short MA time (1.8–3.6 ks), almost all the initial Co and
Ti powders are agglomerated to form large composite
particles, which contain large grains of the reactant materi-
als (Fig. 5a). Further milling time (3.6–11 ks) leads to
disintegration of these agglomerated powders and to
refinement of their ‘lamella’ so that the number of layers
per individual particle and their interfaces are monotonical-
ly increased. The continuous intensive impact and shear
forces that are generated by the milling tools (balls) create
clean well-developed multilayered Co / Ti composite par-
ticles typical of sputtered or evaporated diffusion couples
[51–53]. During the DSC experiments of these
multilayered powders, two clear separate exothermic peaks
appear (Fig. 8). The first exothermic reaction that appears
at 661 K takes place due to a solid-state reaction between
the thin elemental layers of Co and Ti and this leads to the
formation of a homogeneous (Fig. 12) glassy phase (Fig.
10b) with a composition close to the starting nominal
composition (see the EDS analytical results in Fig. 12).
The formation of a glassy phase via post-annealing me-
chanically alloyed powders is not unique for the Co–Ti
binary system. It has been recently shown by El-Eskan-
darany and Inoue [54] that a glassy phase of Cu 33 Zr 67
alloy powders can be also obtained by isothermal-anneal-
ing the multilayered composite powders at the early and
intermediate stage of milling. Such a phenomenon was
Fig. 14. (a) Dependence of the T TEGFR , T g and T x and DT x on the MA
time during ball milling a mixture of Co 75 Ti 25 powders. (b) Correlation
between T g , T x , T m and T l , and Ti content of glassy Co 1002x Ti x alloy
powders that were obtained after 86 ks of the MA time. DT x TEGFR and
DT x MIGFR refer to the supercooled liquid region of the glassy phase that is
formed by way of thermally enhanced glass formation reaction (TEGFR)
and mechanically induced glass formation reaction (MIGFR) processes,
respectively.
also reported for some mechanically alloyed metallic
powders (see, for example, Refs. [27,30,35]). Indeed, post-
annealing the composite powder particles enhances the
solid-state diffusion between the diffusion couples and this
leads to a speeding up of the rate of diffusion at the clean
Co / Ti boundaries. Thus, the free energy changes drastical-
ly from a non stable (the starting reactant materials) to a
more stable phase (glass). For a successful TEGFR, the
applied annealing temperature must be well below the
temperatures that suppress the nucleation and growth of
 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245 243

layers (which became very narrow) increases. Accordingly,

DHTEGFR decreases and approaches minimum values (Fig.
15a). It is worth mentioning that the powders at this early
stage of milling do not contain any mole fractions of the
glassy phase (Figs. 2b and 3a,b), indicating that the glassy
phase of this stage is obtained only by the TEGFR process.
During the next stage of milling (22–32 ks), a considerable
volume fraction of the glassy phase is formed due to
MIGFR (Fig. 1c) so that the glassy phase of this stage is
obtained by both TEGFR and MIGFR.
We denote the heat formation of a glassy phase via
MIGFR by the term DHMIGFR . However, DHMIGFR is not a
measurable value; it can be estimated during the final stage
of milling (where glassy formation peaks are absent, i.e.
DHMIGFR 50), using the following relations:

DHfor 5 DHG 1 DHx (1)

Here, is the reported value of the enthalpy of formation of

an intermetallic compound at specific concentrations of
Co 1002x Ti x , based on Miedema’s model [55], DHG is the
heat formation of a glassy phase and DHx is the enthalpy
of crystallization. During the final stage of milling, where
the glassy phases are formed due to MIGFR, Eq. (1) can
be written as:
DHfor 5 DHMIGFR 1 DHx MIGFR (2)

DHMIGFR is the total heat formation of Co 1002x Ti x glassy

phase via the MIGFR process (ball milling) and DHx MIGFR
is the enthalpy of crystallization for the glassy phases that
are formed by the MIGFR. In fact, this value is very
difficult to be estimated at the intermediate stage of milling
in which the glassy phase results from TEGFR and
MIGFR together.
Then, DHMIGFR can be given as follows:

DHMIGFR 5 DHfor 2 DHx MIGFR (3)

The measured values of DHTEGFR (heat of formation of

Fig. 15. (a) Dependence of DHTEGFR and (b) DHx on the MA time during
ball milling a mixture of Co 1002x Ti x powders.
glassy alloys), the estimated values of DHMIGFR of glassy
Co 1002x Ti x (x525, 33 and 50) and the relative heat of
glassy formation ratio (DHMEGFR /DHTEGFR ) are listed in
Table 2. At all compositions, DHMEGFR /DHTEGFR , ratio has

the equilibrium phase, i.e. the crystallization temperature. Table 2

The remarkable decrease in the magnetic polarization of Heat formation of glassy Co 1002x Ti x alloy powders via thermally en-
hanced glass formation reaction, TEGFR (DHTEGFR ) and mechanically
as-annealed powders (Fig. 11b) suggests the completion of induced glass formation reaction, MIGFR (DHMIGFR ), and the relative
the solid-state reaction and the decreasing of Co-free atoms heat of glassy formation ratio
in the composite powders upon annealing at 710 K. DH MIGFR
Ti concentration DHTEGFR DHMIGFR ]]
In the present study, the term DHTEGFR refers to the heat (at%) (kJ mol 21 ) (kJ mol 21 )
DH TEGFR

formation of the glassy phase (enthalpy of glassy forma-

25 20.56 227.65 49.4
tion) via annealing the multilayered milled powders. This 31 20.44 232.77 74.5
value is measured directly from the area under the amor- 33 20.43 235.82 83.3
phization peak during the DSC scans of the ball-milled 50 20.39 240.53 103.9
alloy powders at the early and intermediate stages of MA. The values of DHTEGFR were directly measured from the DSC scans of
Once the thickness of Co and Ti layers decreases with the mechanically alloyed powders, whereas DHMIGFR were estimated from
increasing the MA time (Fig. 5), the number of these fresh Eq. (2) (see the main text).
244 M. Sherif El-Eskandarany et al. / Journal of Alloys and Compounds 350 (2003) 232–245
large values, suggesting that the glassy phases are mainly
formed by MIGFR.
In the MIGFR process, the solid-state reaction takes
place in the same manner as occurs in the TEGFR process,
except with a lower diffusion rate and a longer MA time
(Fig. 2). This is attributed to the milling temperature that is
assumed to be far below than in TEGFR (710 K). At the
initial milling stage, crystalline elemental powders are
mechanically crushed and fresh surfaces are rapidly
created. Kneading of such ground powders enhances the
atomic diffusion of elemental atoms and step-by-step local
alloying [42]. Thus, the interdiffusion between Co and Ti
layers occurs slowly. Since MA introduces many vac-
ancies, lattice defects, grain boundaries and surfaces, the
ball-milled powders store a large amount of mechanical-
strain energy [36,56,57]. Increasing the MA time during
the intermediate stage of milling leads to a continuous
movement of the milling media which leads to an excess
of the lattice imperfections that assist the diffusion be-
tween the Co–Ti diffusion couple which have already
negative heats of mixing [55]. In the milling process,
friction between balls, balls and the lining surface of a vial
generate frictional heat. As a result of the ball motion and
their collisions, the interdiffusion in the multilayered
powders is enhanced. In fact, such heat not only acceler-
ates diffusion of the constitutional atoms of the powder
mixture, but also contributes to thermal annealing of the
unprocessed multilayered composite powders, which may
remain in the mixture.
In contrast to the crystallization process of melt-spun
Co 78 Ti 22 which takes place through two steps [46], the as
MA–Co 1002x Ti x glassy alloys transform into the equilib-
rium phases through single sharp exothermic reactions.
This is attributed to the high capability of the mechanically
induced solid state reaction to homogenize the powders at
an atomic scale during the different stages and to over-
come the precipitation of any short or medium range order
in the glassy matrix. The formed glassy phase at the last
stage of milling is homogeneous, indicated by the near
values of Js , T g , T x and DHx of the powders. In addition,
the EDX analyses for the final product of the glassy
powders have not shown any significant concentration
gradients or compositional fluctuation, indicating that the
obtained glassy phases are uniform and homogeneous at
the atomic scale.
5. Conclusions
Glassy Co 1002x Ti x alloy powders have been synthesized
by high-energy ball milling the elemental powders at room
temperature, using the mechanical alloying method. During
the early and intermediate stages of milling, post-annealing
of the mechanically deformed Co / Ti multilayered compo-
site powders at 710 K leads to the formation of a glassy
phase (thermally enhanced glass formation reaction). When
the elemental mixed powders are milled for longer MA
time (86 ks), the glass formation reaction is taking place
due to mechanically induced solid state reaction. The final
products of the Co-rich glassy alloys, that were obtained
after ball milling for 86 ks, exhibit good soft magnetic
properties. The fabricated glassy alloys have large values
for the supercooled liquid region before crystallization,
DT x (larger than 50 K).
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