Mechanism of solid-state reaction for fabrication of new

glassy V45Zr22Ni22Cu11 alloy powders and

subsequent consolidation
M. Sherif El-Eskandaranya) and Satoru Ishiharab)
Inoue Superliquid Glass Project, Exploratory Research for Advanced Technology, Japan Science and
Technology Corporation, Yagiyama-Minami 2-1-1, Sendai 982-0807, Japan
A. Inoue
Institute for Materials Research, Tohoku University, Katahira 2-1-1 Sendai, Miyagi 980-8577, Japan

(Received 11 April 2003; accepted 15 July 2003)

A single glassy phase of V45Zr22Ni22Cu11 alloy powders was synthesized by milling

the elemental alloying powders in an argon atmosphere using a low-energy
ball-milling technique. During the early and intermediate stages of milling, the atoms
of Zr, Ni, and Cu migrated and diffused into the V (base material) lattice to form a
body-centered-cubic (bcc) solid-solution, which transformed into a glassy phase with
the same composition upon annealing at 850 K for 300 s in an argon atmosphere
differential scanning calorimeter (thermally-enhanced glass formation reaction). As the
milling time increased, the powders were subjected to continuous defects and lattice
imperfections that led to a gradual change in the free energy so that solid-solution
phase was transformed (mechanically enhanced glass formation reaction) to another
metastable phase (glassy). Toward the end of the milling processing time, the bcc
solid-solution transformed completely into a single glassy phase with the same
composition. The glass-transition temperature, the crystallization temperature, and
the enthalpy change of crystallization of the fabricated glassy powders were 741 K,
884 K, and −2.18 kJ/mol, respectively. This fabricated glassy alloy showed a wide
supercooled liquid region (143 K) of metallic glassy alloy. The glassy powders were
compacted in an argon gas atmosphere at 864 K with a pressure of 780 MPa using a
hot-pressing technique. The consolidated sample was fully dense (above 99.2%) and
maintained its chemically homogeneous glassy structure. The Vickers microhardness of
the consolidated glassy V45Zr22Ni22Cu11 alloy was measured and found to be in the
range between 6.89 GPa to 7.02 GPa.

I. INTRODUCTION make them pioneer materials for several industrial appli-

In the last 30 years, mechanical alloying (MA) using 1,2
the ball-milling and/or rod-milling3 techniques has made
remarkable progress for preparing several advanced en-
gineering materials at room temperature.4 Among these
useful materials, metallic glassy alloys, with their unique
short-range atomic order and desirable properties that
a)
Address all correspondence to this author.
Present address: Mining, Metallurgical and Petroleum Engineer-
ing Department, Faculty of Engineering, Al-Azhar University,
Nasr City 11371, Cairo, Egypt.
e-mail: msherif@mst1.mist.com.eg
b)
Present address: R&D Institute of Metals and Composites for
Future Industries, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-
8577, Japan.
cations,5–8 have been synthesized by the MA method.9–14
The worldwide interest in the metallic glassy materials,
which represent the ultimate state of solid metastability,
has been sustained to a great degree by the clear benefits
seen in the use of them in a number of application
areas.15
Inert gas atomization technique has been considered as
a powerful process for fabrication of large amounts of
spherical glassy powders that can be consolidated into
fully dense compact (above 99%) using hot-pressing, hot
isostatic pressing, hot extrusion, and, recently, plasma-
activated sintering methods.16,17 Another interesting
process for obtaining the source of the glassy powders is
the melt spinning method, which produces homogeneous
ribbons that are pulverized into grit-like powders (e.g.,
Ref. 18). The powders could be then consolidated into
the desired shape, using any of the previously mentioned

J. Mater. Res., Vol. 18, No. 10, Oct 2003 © 2003 Materials Research Society 2435
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
compaction techniques. Unfortunately, both fabrication
powder methods depend on the traditional melting and
casting techniques, which restrict the fabrication of
glassy powders that may have high melting points or for
those systems that have poor glass forming abilities. In
the current study we have used the MA processing route,
which is now recognized and respected as a competitive
technology and an alternative to casting or conventional
glass forming, for fabrication of new multicomponent
V45Zr22Ni22Cu11 glassy alloy powders. It has been real-
ized that metallic glassy alloys show superplasticity in
the supercooled liquid state due to the Newtonian viscous
flow.19,20 Such unique characteristics add an important
dimension that makes the consolidation step powerful in
respect to the expected full dense behavior of the com-
pacted glassy materials. One aim of the current work is to
describe a process for forming fully dense glassy
V45Zr22Ni22Cu11 alloy using the MA method as a source
of glassy powders. In addition, the mode of the solid-
state glassy formation that took place upon low-energy
ball-milling of elemental V45Zr22Ni22Cu11 powders are
proposed and described in terms of structure, morphol-
ogy, and calorimetric points of view.
II. EXPERIMENTAL
Pure elemental powders (99.9% or better) of V
(70 ␮m), Zr (50 ␮m), Ni (25 ␮m), and Cu (10 ␮m) were
balanced to give the desired nominal composition (at.%)
of V45Zr22Ni22Cu11 and were mixed in a glove box under
an argon (99.999%) atmosphere. The mixed powders of
the starting reactant materials were then sealed into a
tempered chromium steel vial (1000 ml in volume) to-
gether with 50 tempered chromium steel balls (14 mm in
diameter) in the glove box. A ball-to-powder weight ratio
of 25:1 was chosen. The MA process was performed at
room temperature using a tumbling mill at a rotation
speed of 1.1 s−1. To avoid an increase in the vial tem-
perature, the milling was operated under a continuous
flow of air. The milling process was interrupted after
selected MA times, and the powders were completely
discharged from the vial in the glove box. Hence, new
reactant elemental powders were charged again into the
vial for further milling runs. The structural changes with
the milling time were monitored by x-ray diffraction
(XRD) with Cu K␣ radiation and high-resolution trans-
mission electron microscopy (HRTEM) using a 300-kV
field-emission microscope. The morphology and metal-
lography of the mechanically alloyed powders were char-
acterized by scanning electron microscopy (SEM) using
a 15-kV field-emission electron microscope. The
samples were thermally analyzed via differential scan-
ning calorimetry (DSC) and differential thermal analysis
(DTA) under a flow of purified argon gas using a heating
rate of 0.67 K/s. The glass-transition temperature (Tg)
2436 J. Mater. Res., Vol. 18, No. 10, Oct 2003
was confirmed by heating the sample above its onset Tg
and cooled back to about 310 K. Then, a second (and
sometimes third) heating run was achieved to ensure the
same thermal history. Energy dispersive spectroscopy
(EDS) measurements using an electron beam of 5 nm
have been used to analyze the concentration of the con-
stituent elements and to detect the degree of iron
contamination in the milled powder. The oxygen con-
tamination content was determined by the helium carrier
fusion-thermal conductivity method. The powders at the
end product (806–900 ks) were slightly contaminated
with iron (0.18 at.%) and oxygen (0.23 at.%). The final
glassy powders obtained after 806 ks of MA were used
for subsequent consolidation. The consolidation proce-
dure was performed using uniaxial hot-press equip-
ment under an argon atmosphere. The powders were
pressed under a pressure of 780 MPa in a metallic die
with an inner diameter of 20 mm. The die set under
application of the pressure was heated at heating rate
of 0.33 K/s up to 863 K and then cooled by flowing
argon gas. The consolidated button was characterized
by means of XRD, HRTEM/EDS, SEM, and DSC. The
density of the consolidated sample was measured by
the Archimedean method using toluene. The microhard-
ness of the compacted sample was determined using
Vickers indenter with a load of 1 kg. The hardness values
reported subsequently are averaged from at least ten
indentations.
III. RESULTS
A. Formation of body-centered-cubic
solid-solution V45Zr22Ni22Cu11 powders and the
effect of annealing
Figure 1 displays the XRD patterns of mechanically
alloyed V45Zr22Ni22Cu11 powders during the early (43–
130 ks) and intermediate (130–173 ks) stages of ball
milling. After 43 ks of MA time, the powders were a
polycrystalline mixture of body-centered-cubic (bcc)-V
(base material), hcp-Zr, face-centered-cubic (fcc)-Ni, and
fcc-Cu with no indications of the existence of any reacted
phase [Fig. 1(a)]. After 86 ks of MA time, the Bragg-
peaks that come from fcc-Cu were hardly seen, and
the peak intensities of the metallic alloying elements of
Ni and Zr are decreased [Fig.1 (b)], indicating the
progress of the solid-state reaction. At the beginning of
the intermediate stage of MA (130 ks), almost all of the
minor peaks for the alloying elements are disappeared
[Fig. 1(c)]. Considerable broadening in the major Bragg-
peaks of bcc-V and the alloying elements can be seen at
the XRD pattern of the sample that was obtained after
173 ks of MA time [Fig. 1(d)]. This is indicative of
the subsequent dissolution of the alloying elements in
the V matrix.
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
After 259 ks of milling, all the Bragg-peaks that cor-
respond to the crystalline alloying elements have disap-
peared [Fig. 2(a)] and the XRD pattern of the milled
powders reveal a single bcc-structure with a lattice param-
eter a0 of 0.3034 nm. This value is considerably larger than
that one for pure V (0.3027 nm), indicating the formation of
metastable phase of bcc-VZrNiCu solid solution.
The image of the HRTEM and the corresponding
nanobeam diffraction pattern (NBDP) of the mechani-
cally alloyed powders after 259 ks are shown in Fig. 3.
Obviously displayed, the micrograph reveals lattice
fringe images of a metastable bcc-VZrNiCu solid-
solution phase [Fig. 3(a)]. The measured fringe spacing
is 0.21422 nm and matches well with the interplanar
spacing of bcc-VZrNiCu (110), as displayed in Fig. 3(b).
Likewise, the corresponding indexed NBDP implies the
presence of a single phase of bcc-VZrNiCu solid-
solution with no indication of any residual phases of
unprocessed elemental crystal and/or amorphous phase
[Fig. 3(c)]. This fact was confirmed throughout TEM/
NBDP observations of several particles of the powders at
this stage of milling.
FIG. 1. XRD patterns of mechanically alloyed V45Zr22Ni22Cu11 powders
after (a) 43 ks, (b) 86 ks, (c) 130 ks, and (d) 173 ks of ball-milling time.
J. Mater. Res., Vol. 18, No. 10, Oct 2003
We have used a DSC technique to examine the thermal
stability of the obtained solid-solution phase. The DSC
curve of the mechanically alloyed powders that were
obtained after 259 ks of milling is displayed in Fig. 4(a).
The scan reveals two exothermic reactions. The first exo-
thermic peak is broad with an onset temperature of 567 K
and extends up to 850 K. The second, however, is sharp
with an onset temperature of 921 K. Both reactions were
absent in the second heating run (dotted line), suggesting
that the detected peaks come from irreversible reactions.
Obviously, there is an endothermic event in the region
between the two exothermic reactions (850 K to 921 K).
To explore the origin of the fully separated exothermic
reactions, a sample was heated in the differential scan-
ning calorimeter up to 850 K and then annealed at this
temperature for 300 s [Fig. 4(b)]. A small amount of the
annealed powders [I in Fig. 4(a)] was used for XRD and
HRTEM/EDS investigations. All the Bragg-peaks that
correspond to the crystalline bcc-VZrNiCu solid solution
are replaced with primary and secondary haloes
[Fig. 2(b)], indicating the solid solution–amorphous
phase transformation.
FIG. 2. XRD patterns of mechanically alloyed V45Zr22Ni22Cu11 pow-
ders after (a) ball milling for 259 ks and (b) ball milling for 259 ks and
then annealed at 850 K for 300 s.
2437
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders

FIG. 3. (a) HRTEM image and (c) the corresponding indexed SADP of mechanically alloyed V45Zr22Ni22Cu11 powders after ball milling for
259 ks. A part of the indexed region in image (a) is displayed in (b) in another scale.

The HRTEM image of the annealed sample is shown
together with the corresponding selected area diffraction
pattern (SADP) in Figs. 5(a) and 5(b), respectively. The
overall sample is homogeneous with a “maze contrast” of
an amorphous phase [Fig. 5(a)]. Some fringe contrast
comes from the nanocrystalline phase of untransformed
bcc solid solution that is embedded into the amorphous
matrix. The SADP [Fig. 5(b)] taken from the middle of
the micrograph reveals a clear halo pattern of an amor-
phous phase coexisted somewhat with some spots that
come from the crystals of untransformed solid-solution
phase. To assess the distribution of the alloying elements
in the annealed powders, the local composition and the
degree of homogeneity of the annealed sample have been
examined by the HRTEM/EDS technique. Some selected
examined regions for this sample are indexed in Fig. 5(a).
The corresponding EDS analyses for the selected regions
are listed in Table I. Obviously, the compositions are
essentially very close to the nominal starting composition
of V45Zr22Ni22Cu11; however, it varies markedly from
region to region, as shown in Table I.
To examine the thermal stability of the obtained amor-
phous phase, an individual DSC run for the as-annealed
solid-solution powders was performed. The DSC curve
of as-milled powders for 259 ks and then annealed at
850 K for 300 s is presented in Fig. 4(c). One can see that
the first broad exothermic reaction has completely dis-
appeared, and a clear visible endothermic event, which
lies at an onset temperature of 745 K, appears. This en-
dothermic event was confirmed by heating the samples to
a temperature just above its onset temperature (755 K)
and then cooled down to about 350 K. The existence of
the endothermic event in three consecutive runs indicates
that it is reproducible and can be related to the glass
transition of the formed glassy phase. The XRD of the
sample that was taken after the completion of the exo-
thermic reaction (not shown here) shows the formation of
a polycrystalline mixture of V3Ni, Zr2Ni, and Zr2Cu,
indicating that the exothermic peak with onset at 911 K
(Tx) is taking place due to the crystallization of the ob-
tained glassy phase.
Thus, we can conclude that a bcc-VZrNiCu solid-
solution phase can be transformed into a glassy phase
(Tss→G) with the same composition (polymorphous reac-
tion) upon annealing the powders at 850 K.
B. Solid solution–glassy phase transformation
and the effect of milling time
To realize any possible phase transformations that
probably occurred during further milling of the obtained
bcc-VZrNiCu solid solution, the ball-milling procedure
was performed for longer MA times. The XRD patterns
of the powders that were milled for long-term runs (360–
806 ks) are displayed in Fig. 6. Considerable broadening
in the diffracted lines can be seen in the sample that
milled for 360 ks [Fig. 6(a)]. As the MA time increases
(540 ks), the intensities of the Bragg-peaks that corre-
spond to the metastable solid-solution decrease and the
diffracted peaks show further boarding, indicating the ex-
istence of an amorphous phase [Fig. 6(b)]. Toward the
end of the MA time (720 ks), all of the Bragg-peaks that
belong to the bcc-VZrNiCu solid-solution phase have
completely disappeared and broad diffuse haloes appear,

2438 J. Mater. Res., Vol. 18, No. 10, Oct 2003

 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders

implying a single amorphous phase with no indication
for any residual crystalline phase [Fig. 6(c)] Increasing
the MA time (806 ks) does not lead to any further phase
transformations, and the sample of this stage of milling is
still a single amorphous phase [Fig. 6(d)], suggested by
the absence of any sharp Bragg-peaks and the similarity
in the positions of the primary amorphous maxima with
the last sample (no. 720 ks). We should emphasize that
this amorphous phase maintains it random structure even
after loner ball-milling times, as long as 900 ks to 1000 ks.
The bright-field image (BFI), HRTEM and the SADP
of the mechanically alloyed powders of the end-product
(806 ks) are shown in Fig. 7. The low-magnification
BFI of an individual equiaxed amorphous particle [Fig.
7(a)] shows that the powders at this stage of milling
possess excellent morphological characteristics for hav-
ing spherical-like morphology with a fine particle size of
2525 nm (∼2.5 ␮m) in diameter. The HRTEM of an
indexed area in Fig. 7(a) (the circular area at the bottom
pole of the particle) is shown in Fig. 7(b). Overall, the
sample, which appears featureless and homogeneous in
its internal structure, shows a maze contrast with no
indication of precipitates of any crystalline phases
[Fig. 7(b)], implying the homogeneity in structure within
the nanoscale. Moreover, the SADP displays a typi-
cal halo-diffraction of an amorphous phase with the ab-
sence of sharp rings and/or spots of any unprocessed
crystalline [Fig. 7(c)]. It is worth noting that the EDS
analyses (Table II) of some selected regions of this
sample [see the indexed regions in Fig. 7(b)] does not

FIG. 5. (a) HRTEM image and (b) the corresponding SADP of me-
chanically alloyed V45Zr22Ni22Cu11 powders after milling for 259 ks
and then annealed at 850 K for 300 s. The indexed circles in image (a)
refer to the EDS-examined regions, and the analytical results are listed
in Table I.

TABLE I. The local compositional analyses of mechanically alloyed

V45Zr22Ni22Cu11 powders ball-milled for 259 ks and then annealed at
850 K for 300 s [Fig. 5(a)].

V Zr Ni Cu
FIG. 4. DSC thermograms of mechanically alloyed V45Zr22Ni22Cu11
powders after ball milling for 259 ks. Whereas the curve in (a) shows I 44.9 22.1 22.2 10.8
the full scan of the milled powders, the curve in (b) displays the II 45.4 21.8 22.1 10.7
scan of a DSC run that was achieved just above the first exothermic III 44.8 22.2 21.9 11.1
reaction (up to 850 K). Point I in (b) denotes to the annealing tem- IV 45.1 21.7 22.3 10.9
perature of the sample. The DSC curve of the annealed powders [at I V 44.9 22.1 21.8 11.2
in (b)] is presented in (c). The disappearance of the first exothermic VI 45.2 21.8 21.9 11.1
reaction and the appearance of a clear visible endothermic event,
which corresponds to the glass transition, are the general features of The analyses have been achieved using HRTEM/EDS technique with an
this DSC run. electron beam of 5-nm diameter. The results are given in at.%.

J. Mater. Res., Vol. 18, No. 10, Oct 2003 2439

 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders

show compositional gradient, and the calculated average [Fig. 8(c)], indicating the formation of a single homoge-
composition is very close to the starting nominal com- neous glassy phase. Whereas Tg slightly shifts to the
position of V45Zr22Ni22Cu11. low-temperature side (740 K), Tx maintains its tendency
The thermal stability of the obtained amorphous for shifting to a higher temperature side (883 K), indi-
V45Zr22Ni22Cu11 alloy powders was examined by DSC cating a slight compositional change. It is worth men-
and DTA techniques. The typical DSC thermograms of tioning that the supercooled liquid region before
the mechanically alloyed powders during the final stage crystallization, ⌬Tx (⌬Tx ⳱ Tx − Tg) of the end product
of ball-milling (540–900 ks) are shown in Fig. 8. In (806 ks) exhibits a large value (143 K) for a metallic
contrast to the powders of the intermediate stage of mill- glassy alloy. This implies the excellent stability of the
ing [Fig. 4(a)], the low-temperature exothermic peak is obtained glassy phase. The DSC curve of the sample that
absent from the DSC traces for all the traces of the was further milled for 900 ks is displayed in Fig. 8(d).
samples at the intermediate (540–806 ks) and the final
(806–900 ks) stages of milling. The scan of the powders
milled for 540 ks [Fig. 8(a)] reveals two opposite events:
the first is an endothermic with onset at 762 K and refers
to the glass transition (Tg); the second is exothermic with
an onset temperature (Tx) of 871 K and is due to the
crystallization of the glassy V45Zr22Ni22Cu11 phase.
This crystallization reaction becomes more visible and
sharp for the sample that was milled for 720 ks [Fig. 8(b)],
indicating the progress of the solid-state reaction and a
continuous increasing in the volume fraction of the ob-
tained glassy phase. The crystallization peak becomes
very sharp for the sample that was milled for 806 ks

FIG. 7. (a) Low-magnification TEM, (b) HRTEM for the indexed

region in (a), and (c) SADP of mechanically alloyed V45Zr22Ni22Cu11
powders after 806 ks of ball-milling time. The indexed circles in image
(b) refer to the EDS-examined regions and the analytical results are
listed in Table II.

TABLE II. The local compositional analyses of glassy V45Zr22Ni22Cu11

alloy powders obtained after 806 ks of ball-milled time [Fig. 7(b)].

V Zr Ni Cu
I 44.8 21.9 22.1 11.2
II 45.1 22.2 21.9 10.8
III 45.2 21.8 22.2 10.8
IV 44.9 21.9 22.1 11.1
V 45.1 22.2 21.9 10.8
VI 44.8 22.1 22.2 10.9
FIG. 6. XRD patterns of mechanically alloyed V45Zr22Ni22Cu11 pow-
ders after (a) 360 ks, (b) 540 ks, (c) 720 ks, and (d) 806 ks of ball- The analyses have been achieved using HRTEM/EDS technique with an
milling time. electron beam of 5-nm diameter. The results are given in at.%.

2440 J. Mater. Res., Vol. 18, No. 10, Oct 2003

 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
Further information on the crystallization reaction is
given by the enthalpy change of crystallization (⌬Hx),
presented in Fig. 9 as a function of MA time. The ⌬Hx is
dependent on MA time and tends to increase monotonically
from a value of 1.21 kJ/mol after 540 ks of MA to approach
FIG. 8. DSC thermograms of mechanically alloyed V45Zr22Ni22Cu11
powders after (a) 540 ks, (b) 720 ks, (c) 806 ks, and (d) 900 ks of
ball-milling time.
FIG. 9. Correlation between the MA time and the enthalpy change
of crystallization, ⌬Hx, of mechanically alloyed V45Zr22Ni22Cu11
powders.
J. Mater. Res., Vol. 18, No. 10, Oct 2003
saturation value of 2.18 kJ/mol during the final stage of
MA (806−900 ks). This monotonic increase indicates an
increase in the volume fraction of the obtained glassy
phase and the progress in the solid-state reaction.
In addition to the above analysis, the melting (Tm) and
liquidus (Tl) temperatures of the sample that was ob-
tained after 900 ks of MA time were characterized using
DTA technique (not presented here) and found to be
1485 K and 1533 K (Tl), respectively. The low value
(0.48) of the reduced glass-transition temperature here,
Trg (Tg/Tl), may indicate the difficulties of obtaining such
a glassy phase by the traditional melting and casting
techniques.
C. Consolidation of the glassy powders into fully
dense bulk metallic glass
To determine some physical and mechanical proper-
ties of the obtained glassy alloy, the powders of the
end product were consolidated into compact, using a hot-
pressing method technique. Figure 10(a), which displays
the XRD pattern of the as-consolidated sample, gives
broad primary and secondary diffraction maxima of typi-
cal glassy phase. Comparing this pattern with that shown
in Fig. 6(d), one can conclude that this consolidation step
does not lead to the crystallization of the glassy phase,
and the compact sample still maintains its unique random
structure.
We have also examined the thermal stability of the
obtained metallic bulk glass, using the DSC method.
The DSC trace of the consolidated sample [Fig. 10(b)]
displays a typical trace of a glassy phase, characterized
by a clear Tg and ⌬Tx that are followed by a single sharp
exothermic crystallization reaction (Tx). The absence of
any other reactions, plus the fact that the thermal char-
acteristics, indexed by Tg, Tx, and ⌬Tx of the consoli-
dated glassy sample, are the same with those of the
glassy powders [before consolidation; Fig. 8(c)], indi-
cates a complete consolidation procedure for fabrication
of metallic bulk glass.
The SEM micrograph of the cross-sectional view
for the consolidated sample is presented together with
the HRTEM image and SADP in Fig. 11. The com-
pact sample that has a uniform and fine microstruc-
ture does not have porous structure and is void-free
[Fig. 11(a)], indicating the formation of fully dense
glassy compact.
The HRTEM image of this sample shows a maze pat-
tern contrast [Fig. 11(b)] with a clear halo diffraction of
an amorphous phase [Fig. 11(c)]. The similarity in the
microscopic characterizations between the as-milled
powder and compact samples suggests a high capability
of the hot-pressing method to maintain the crystal
structure of the consolidated powders without any phase
transformations (e.g., crystallization) during the pressing
and sintering procedures.
2441
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders

FIG. 10. (a) XRD pattern and (b) DSC scan for glassy
V45Zr22Ni22Cu11 alloy powders after consolidation under pressure of
780 MPa at 864 K, using a uniaxial hot-press.

To get more information about the consolidated glassy

sample, we have measured the density of the obtained
compact and found it to be 7.06 mg/m3. Comparing this
value with the calculated theoretical density of the
V45Zr22Ni22Cu11 alloy (7.12 mg/m3), one can conclude
that the obtained glassy compact is fully dense with a
relative density of about 99.2%.
The Vickers microhardness (HV) of the compact
glassy sample was investigated. The HV values do not
severely fluctuate and slightly vary from 6.89 GPa to
7.02 GPa. Comparing this value with those for many me-
tallic glassy alloys, one can say that glassy V45Zr22Ni22Cu11
alloy exhibits high hardness value.
IV. DISCUSSION
Among the several techniques for preparing multicom-
ponent glassy alloys, the MA method has been used for
fabrications of wide varieties of metallic glasses (e.g.,
FIG. 11. (a) SEM micrograph of the cross-sectional view, (b) HRTEM
image, and (c) the corresponding SADP for glassy V45Zr22Ni22Cu11
alloy powders after consolidation under pressure of 780 MPa at 864 K,
using a uniaxial hot-press.
Refs. 21–23). The current study shows the possibility of
preparing multicomponent V45Zr22Ni22Cu11 glassy alloy
by ball-milling the elemental alloying powders at room
temperature. Furthermore, we have consolidated the final
product of the milled powders into a bulk metallic glass,
using the hot-pressing technique. The nonstrict limita-
tions in the thickness of the formed bulk metallic glass
via the MA/hot-pressing route may worth this process.

2442 J. Mater. Res., Vol. 18, No. 10, Oct 2003

 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
A. Crystalline–glassy phase transformations in
mechanically alloyed V45Zr22Ni22Cu11 powders
Based on the results of the current study, a single
glassy phase with a wide supercooled liquid region could
be obtained either by the heat treatment of the powders at
the intermediate stage of milling thermally enhanced
glass formation reaction (TEGFR) or by long-term ball
milling mechanically enhanced glass formation reaction
(MEGFR). For the two cases, broad diffraction maxima
and the absence of any residual crystalline phases (un-
processed starting materials) are indicative of glass for-
mation [Fig. 2(b) and Figs. 6(c) and 6(d)]. In addition, the
average local compositions of the two glasses are very
close, indicating the similarity of the formed glassy alloy
(Tables I and II). However, though such agreement be-
tween these two glassy alloys may indicate a very similar
actual composition and short-range order topology of the
obtained glassy phase, the mode of amorphization of
the two kinds of the glassy alloys differ widely. The
mechanism and the mode of glass formation of each
process will be discussed in this section using Fig. 12,
which presents the correlation between the Tg, Tss→G and
Tx, and the MA time.
During the early stage of milling (43–130 ks), almost
all of the starting soft metallic powders tend to agglom-
erate to form larger particles that have layered-structure
metallography (e.g., Ref. 24). Further milling (130 ks)
leads to an increase of the shear forces, and this enhances
the interdiffusion reaction similar to that occurring dur-
ing the synthesis of amorphous alloys in thin film mul-
tilayers.25 Such intensive stresses are able to create many
vacancies in the lattices for the milled powders.24,26,27 As
the MA time increases (173 ks), the vacancies in the V
FIG. 12. Influence of the MA time on Tss→G, Tg and Tx. Whereas
Tss→G refers to the onset temperature of the first exothermic event in
Figs. 4(a) and 4(b), Tg and Tx are the onset temperatures of endother-
mic (glass transition) and exothermic (crystallization) events, respec-
tively (Fig. 8).
J. Mater. Res., Vol. 18, No. 10, Oct 2003
lattice (based material) increase so that the atoms of the
alloying elements for Zr, Ni, and Cu tend to migrate to
the open defected lattice of metallic bcc-V. The increase
of the lattice a0 during this stage of ball milling is in-
dicative for the mixing reaction and the subsequent
dissolution of the alloying elements into the bcc-V.
The concept of this process is quite similar to that oc-
curring during the synthesis of binary Cu–Er and Ni–Er
amorphous28 or multicomponent Zr–Al–Ni–Cu glassy
alloys29 via cold rolling of elemental foils. This continu-
ous dissolution is concomitant with further milling time
(259 ks) and leads to an expansion of the bcc-lattice. The
reported rapid solution of the solute alloying elements
into the V matrix was early reported by Sagel et al.22
when they mechanically alloyed multicomponent
Zr60Al10Ni9Cu18Co3 powders.
The DSC curves for the powders at the intermediate
stage of milling (Fig. 4) reveal two independent exother-
mic reactions. The first one, which is observed at rela-
tively low temperature, takes place due to the TEGFR.
During this stage of MA, the onset temperature of Tss→G
does not change with change of the MA time and has the
same values (Fig. 12). The second exothermic peak,
however, occurs due to the crystallization of the obtained
glassy phase via TEGFR. During this stage of milling
(86–540 ks), Tx tends to decrease monotonically, indi-
cating continuous compositional changes. Here, there is
no evidence for the formation of any glassy phase in the
as-milled powders (Figs. 2(a) and 3), and the amorphiza-
tion occurs upon annealing the powders of the supersatu-
rated solid solution at 850 K for 7.2 ks [Figs. 2(b) and 5].
The formation of a glassy phase upon annealing the
mechanically alloyed powders is not unique for this re-
ported alloy. It has also been established that an amor-
phous phase can be obtained upon isothermal-annealing
the multilayered composite powders at the early and
intermediate stage of milling (e.g., Refs. 26, 30–33). In-
deed, 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 metal–metal boundaries. It has been reported
that a supersaturated bcc solid-solution of binary34,35 or
multicomponent36 systems can be transformed into an
amorphous phase with the same composition upon
annealing the ball-milled powders. Such observed un-
usual solid solution–amorphous phase transformation
seems to be not unique for a particular binary system, and
it can even take place in multicomponent metallic system
to form a glassy phase, as investigated here. This kind of
transformation, which involves the amorphization of a
metastable phase (solid-solution) upon annealing, is
termed “inverse melting.”37 For a complete crystalline–
amorphous transformation, the glassy phase must have a
lower entropy38 compared with the crystalline phase. We
here assume that the TEGFR takes place due to the
2443
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
large amount of lattice strain energy, which are ab-
sorbed by the milled powders. These strains are able
to provide a driving force for such unusual phase
transformation.24,39–42
The obtained powders of the solid solution are then
subjected to heavy mechanical deformations upon further
milling times (360–806 ks). The MEGFR requires the
existence of chemical disordering, point defects (intersti-
tials and vacancy), and lattice defects (dislocations and
disclinations). As a result of these defects, the free energy
of the formed solid-solution phase has been changed to
form another metastable phase (glassy). In addition, the
atomic arrangement of the bcc solid solution tends to be
randomly distributed, indicating the progress of the plas-
tic deformation during the milling procedure that leads
disordering.24,39,43 It was suggested by Palvov44 that
crystal-to-amorphous phase transformation in heavily de-
formed intermetallics can be achieved as a result of the
accumulation of lattice defects.
At this final stage, all the exothermic reactions of the
DSC curves that come from the solid solution–glassy
phase transformation have disappeared, indicating that
the glass formation in this stage is achieved via MEGFR
only. Because the glass formation here is taking place
due to the mechanical imperfections in the lattice of the
bcc solid solution without remarkable compositional
changes (polymorphous reaction), the onset temperature
of Tx does not remarkably change upon increasing the
MA time (Fig. 8) and saturated at a certain value
(Fig. 12). Contrary to the Tx, Tg tends to change slightly
with increasing of the MA time (Figs. 8 and 12). Because
Tg reflects the materials intrinsic time scale for structural
rearrangement, the decreased Tg for a given MA time,
therefore, corresponds to sluggish structural rearrange-
ment. This change in the value of Tg is unique for the
mechanically alloyed powders.22
B. Consolidation of glassy powders into bulk
metallic glassy compact
Consolidation of the mechanically alloyed powder into
fully dense compacts is a big challenge and is a necessary
step for most of the industrial applications.45 It is also a
must for investigations of many physical and mechanical
properties.46 One problem, which is usually associated
with the consolidation procedure of the amorphous and
glassy powders, is the crystallization or partial crystalli-
zation that may occur during the consolidation proce-
dure. The unique existence of the supercooled liquid
region in the glassy metallic powders offers a good op-
portunity for obtaining fully dense compacts.
In contrast to the pulverization of the glassy ribbons,
the MA process offers a single process for obtaining
spherical glassy powders that are suitable for many con-
solidation techniques. Needless to say, the mechanically
2444 J. Mater. Res., Vol. 18, No. 10, Oct 2003
alloyed powders can be consolidated into fully dense
compacts due to the extremely fine particle size of the
end product [Fig. 7(a)]. The ultrafine powder particles
with their large surface area have a greater interparticle
contact (number of necks) and, hence, more paths for
volume diffusion can be achieved. The small particle size
plus the nature in topology and morphology of the me-
chanically alloyed powders can also be considered as
important reasons for enhancing the driving force. It is
well known that the ball-milling procedure introduces
huge amounts of lattice imperfections to the milled pow-
ders. The presence of greater than normal amounts of
lattice imperfections such as dislocations in the end prod-
uct of the ball-milled powders, usually resulting from
plastic deformation, can promote consolidation because
such defects enhance diffusional processes during sinter-
ing. Accordingly, internal particle porosity can promote
sintering by increasing the driving force; this can be a
consequence of simply greater surface area or, because
such porosity is often extremely fine, greater stresses in
the solid promoting neck growth, pore rounding, and
pore shrinkage.
One drawback of the mechanically alloyed powders
that are used here, as the source materials for consolida-
tion, is the presence of impurities, especially oxygen that
contaminates the surface of the particles. Such surface
oxidation normally reduces the surface energy of the
powders, leading to the formation of a porous consoli-
dated glassy button. This effect is not a serious concern
here because our glassy V45Zr22Ni22Cu11 powders have
a low level of oxygen contamination (0.23 at.%). In ad-
dition, the glassy powders were simply crushed in an
argon atmosphere glove box using agate mortar and
pestle. This step is important to remove the oxide film
that may coat the outermost surfaces of the powders and
to create fresh oxide-free powder surfaces. The severely
controlled atmosphere with negligible oxygen content
(less than 10 ppm) during the consolidation procedure
leads to a clean and complete sintering step.
The current work presents a typical complete consoli-
dation procedure to obtain a fully dense (99.2%) glassy
compact, which maintains its glassy structure after the
consolidation step [Figs. 10(a) and 11(b)]. The existence
of the T g during the DSC examination of the
as-consolidated button [Fig. 10(b)] can be considered as
important evidence for maintaining the glassy behavior
of the bulk sample after this compaction step.
V. CONCLUSIONS
A low-energy ball-milling technique has been used
for room-temperature synthesis of new glassy
V45Zr22Ni22Cu11 multicomponent alloy powders using
the mechanical alloying method. A single phase of bcc
solid solution is obtained after 259 ks of milling time.
 M. Sherif El-Eskandarany et al.: Mechanism of solid-state reaction for fabrication of new glassy V45Zr22Ni22Cu11 alloy powders
This metastable phase of bcc-VZrNiCu solid solution
tends to transform into a glassy phase with the same
composition upon annealing at 850 K for 300 s
(TEGFR). Further ball-milling times lead to a MEGFR in
which the bcc solid solution is gradually transformed into
the glassy V45Zr22Ni22Cu11 phase. Toward the end of the
milling processing time, the bcc solid solution trans-
formed completely into a single glassy phase with the
same composition. The glass transition and crystalliza-
tion temperatures and the supercooled liquid region of
the fabricated glassy powders are 741 K, 884 K, and
143 K, respectively. The enthalpy change of crystalliza-
tion is –2.18 kJ/mol. We have used uniaxial hot-pressing
to consolidate the glassy powders of the end product
at 864 K with a pressure of 780 MPa. The as-
consolidated sample is fully dense and maintains its
glassy structure without any phase or compositional
changes. The Vickers microhardness of the consolidated
glassy V45Zr22Ni22Cu11 alloy is measured and found to
be in the range between 6.89 GPa to 7.02 GPa.
ACKNOWLEDGMENT
The authors would like to thank the referees of the
paper for their crucial criticisms and for kind suggestions.
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