Materials Science and Engineering A 375–377 (2004) 399–402

Preparation of bulk amorphous Fe–Cr–Mo–Ga–P–C–B alloys

by copper mold casting
M. Stoica∗ , J. Eckert, S. Roth, L. Schultz
IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, D-01171 Dresden, Germany

Abstract

The Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5 bulk glassy alloy was prepared in the shape of rods and ribbons using copper mold casting and
melt spinning, respectively. The structure was investigated by X-ray diffraction (XRD) and the thermal stability was checked by differential
scanning calorimetry (DSC). It was found that the samples consist of an a single amorphous phase and exhibit a rather wide supercooled liquid
region before crystallization. Some characteristic thermal properties of the amorphous samples as a function of the geometrical dimensions
are discussed, as well as the dependence of the glass-forming ability on composition. Additionally, some magnetic data like coercivity Hc ,
saturation polarization Js and Curie temperature Tc are presented.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Bulk metallic glass; Iron-based alloys; Thermal stability; Supercooled liquid region; Glass-forming ability

1. Introduction quenching allows to produce rods with 4 mm diameter.

The iron-based amorphous alloys found a few years ago
by Inoue and Gook [1,2] and Inoue et al. [3] exhibit a large
supercooled liquid region between the glass transition tem-
perature Tg and the crystallization temperature Tx visible
upon heating at a constant rate to elevated temperatures.
They have good soft magnetic properties characterized by
a low coercive force and a high permeability [4–6]. Using
copper mold casting or water quenching techniques, such al-
loys can be cast in form of bulk specimens directly suitable
for use as magnetic cores [7]. However, the critical cool-
ing rate of about 102 K s−1 required for glass formation is
higher than the value of about 1–10 K s−1 characteristic for
alloys with very good glass-forming ability [8]. Thus, the
maximum achievable diameter of these Fe-based alloys is
limited to only a few millimeters [8]. The other hindrance
that can influence bulk glass formation is the presence of
impurities in the melt [9] that can be removed using fluxing
techniques, or of crystalline inclusions that can form upon
solidification of the melt.
In the case of Fe–Cr–Mo–Ga–P–C–B alloys, Shen and
Schwarz [7] used the flux-melting technique to remove
the oxide inclusions from the melt, and subsequent water
∗ Corresponding author.
E-mail address: stoica@dvz.ifw-dresden.de (M. Stoica).
The nominal composition Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 was
found to have the best thermal stability. Concerning the
magnetic properties, the coercive force is below 5 A m−1 ,
and the saturation polarization is around 0.8 T. The mag-
netic characteristics might be improved by increasing the
iron content, but this may deteriorate the glass-forming
ability. The present work focuses on the possibility to cast
Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5 alloy directly in bulk
form using the copper mold casting technique and to in-
vestigate the effect of the composition on the glass-forming
ability.
2. Experimental
In a first step, Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5 with
2 ≤ x ≤ 4, 2 ≤ y ≤ 4, 0 ≤ z ≤ 4, master alloy ingots
for different x, y and z content were obtained by induction
melting starting from Fe–B, Fe–C, Fe–Ga, Fe–P pre-alloys
and Mo (99.4% purity), Cr (99.95% purity), Fe (99.9% pu-
rity), or crystalline B (99.99% purity) pure elements. Induc-
tion melting of Fe with B, Fe with C (99.9% purity) and
Fe with Ga (99.7% purity) allowed to produce the respec-
tive pre-alloys. Mechanical alloying of Fe powder (99.9%
purity, less than 10 ␮m particle size) with amorphous red
P (99% purity, less than 100 ␮m particle size) for 5 h in a

0921-5093/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2003.10.190
400 M. Stoica et al. / Materials Science and Engineering A 375–377 (2004) 399–402
SPEX 8000 ball mill using hardened steel balls and vial and
a ball-to-powder weight ratio of 3:1 and consolidation of the
resulting powders by cold pressing and subsequent induc-
tion melting was employed to obtain the Fe–P pre-alloy. All
materials were handled in a glove box under purified argon
atmosphere (less than 1 ppm O2 and H2 O).
Amorphous rods with various diameters between 1.5 and
3 mm and a length of 70 mm, as well as ribbons (10 mm ×
0.03 mm) were prepared from the master alloy. The rods
were obtained by induction melting under argon atmosphere
at a pressure of 80 × 103 Pa and injection of the melt into
a copper mold under an applied pressure of 3 × 105 Pa.
The ribbons were prepared by single-roller melt spinning
under argon flow on a copper wheel at 24 m s−1 tangential
velocity of the wheel. The oxygen content of the master
alloys and pre-alloys was checked by hot extraction using a
C436 LECO analyzer. We found values of around 50 ppm
for master alloys, 180 ppm for Fe–P and 130 ppm for the
other pre-alloys, respectively.
The amorphous structure of the samples was checked by
X-ray diffraction (XRD) using a Phillips PW 3020 diffrac-
tometer with Co K␣ radiation (λ = 0.17889 nm). For the
XRD measurements, the cast rods were crushed to small
pieces and bonded into amorphous resin in order to have
good resolution. The thermal stability was examined by dif-
ferential scanning calorimetry (DSC), using a Netzsch DSC
404 under a flow of purified argon. The glass transition tem-
perature Tg and the crystallization temperature Tx were de-
termined as the onset temperatures of the glass transition
and the crystallization events, respectively, during heating
with a constant rate of 40 K min−1 . In addition, the melting
temperature Tm defined by the liquidus temperature Tliq at
the onset of solidification upon cooling with a constant rate
of 10 K min−1 was measured using the same Netsch DSC
404 calorimeter.
The magnetic properties of the samples were also in-
vestigated. The coercive force, Hc , was measured using
a Foerster Koerzimat with premagnetizing field pulses of
2000 A cm−1 , the saturation polarization, Js , was measured
by a vibrating sample magnetometer (VSM) under a max-
imum dc magnetic field of 15 000 A cm−1 and the variation
of the saturation polarization versus temperature by a Fara-
day magnetometer at a heating rate of 10 K min−1 .
3. Results and discussion
Fig. 1 shows the XRD scans for Fe77.5−x−y−z Crx Moy Gaz
P12 C5 B5.5 glassy alloys as a function of composition and
shape. The patterns display mainly just a broad maximum
around 2θ = 51◦ which is characteristic for an amorphous
phase. For the ribbons, there is no doubt concerning com-
plete amorphicity. At least for the rods with 3 mm diameter
in the case of Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 , 1.5 mm diame-
ter in the case of Fe67.5 Cr4 Mo4 Ga2 P12 C5 B5.5 , and certainly,
1.5 mm diameter in the case of Fe69.5 Cr4 Mo4 P12 C5 B5.5 ,
x = y =z = 2
ribbon
x =y =4, z =0 φ1. 5 mm
x =y =4, z =0 ribbon
x =y =4, z =2 φ 2 mm
Intensity [a.u.]
x =y =4, z =2 φ1. 5 mm
x =y =4, z =2 ribbon
x = y =z = 4
φ 3 mm
x =y =z =4
φ 2. 5 mm
x = y =z = 4
φ 2 mm
x =y =z =4
φ 1.5 mm
x = y =z = 4 ribbon
2 0˚ 3 0˚ 4 0˚ 5 0˚ 6 0˚ 7 0˚ 80˚ 90˚
Diffraction Angle, 2
Fig. 1. The XRD patterns for as-cast Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5
glassy alloy samples at room temperature.
there are additional weak diffraction peaks superimposed
on the broad diffraction maximum of the amorphous phase.
This points to the formation of crystalline inclusions coex-
isting with the glass. Their influence on the magnetic prop-
erties will be discussed later. However, this type of investi-
gation cannot rule out the possible existence of a small vol-
ume fraction of nanoscale crystalline inclusions. The pres-
ence of such crystalline phase(s) as well as their formation
can be clearly revealed by in situ X-ray diffraction measure-
ments in transmission configuration using a high intensity
high-energy monochromatic synchrotron beam. In previous
work [10], we presented in detail the XRD patterns taken at
ESRF Grenoble for the Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 glassy
alloy.
The influence of the composition on the glass-forming
ability and thermal stability can be evaluated from thermal
measurements. For all the samples, the DSC scans show a
glass transition followed by a supercooled liquid region and
crystallization. The values for Tg , Tx and the liquidus tem-
peratures Tliq as a function of the composition and the geo-
metrical dimensions for as-cast samples are given in Table 1.
Using these values the extension of the supercooled liquid
region Tx and the reduced glass transition temperatures
Tg /Tliq were calculated. Their variation with the composi-
tion for melt-spun ribbons is plotted in Fig. 2.
The glass transition temperatures and the crystallization
temperatures slowly increase with increasing rod diam-
eter in the case of Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 and re-
main almost constant for Fe67.5 Cr4 Mo4 Ga2 P12 C5 B5.5 and
 M. Stoica et al. / Materials Science and Engineering A 375–377 (2004) 399–402 401

Table 1
Glass transition temperatures Tg , crystallization temperatures Tx and 520 x=y=z=2
Curie temperature, Tc [K]

liquidus temperatures Tliq for as-cast Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5
glassy alloy 500

x, y, z Sample Tg (K) Tx (K) Tliq (K) 480

4, 4, 4 Ribbon 743 809 1256 460 x=y=z=4
Rod ␾1.5 750 811 1251
Rod ␾2 753 814 1248 440
Rod ␾2.5 755 815 1250 ribbons
x = y = 4, z = 2
Rod ␾3 757 817 1255 420
4, 4, 2 Ribbon 752 811 1299
400 x = y = 4, z = 0
Rod ␾1.5 755 811 1299
Rod ␾2 753 811 1299
0,0 0,5 1,0 1,5 2,0 66 68 70 72 74
4, 4, 0 Ribbon 747 794 1314 Diameter, [mm] Fe content [at.%]
Rod ␾1.5 747 794 1311
2, 2, 2 Ribbon 736 781 1301 Fig. 3. Curie temperature for as-cast Fe77.5−x−y−z Crx Moy Gaz P12 C5 B5.5
glassy alloys as a function of sample diameter at different Cr, Mo and
Ga content and in the case of ribbons as a function of iron content.

Fe69.5 Cr4 Mo4 P12 C5 B5.5 . The differences in thermal stabil-

ity between rods with different diameters and melt-spun
ribbons prepared of same composition are caused by a
different degree of relaxation stemming from the different
cooling rates achieved during solidification. Another reason
can be a slightly different composition of the glasses ob-
tained by the different synthesis routes and the decreasing
cooling rate of the melt with increasing rod diameter. Such
compositional variations may arise if at least the rods with
larger diameters are not fully amorphous but contain some
crystalline phase(s) which may form due to an insufficient
cooling rate for complete glass formation upon casting.
This agrees well with the conclusions drawn from the XRD
patterns. Some crystalline inclusions can form even from
the molten state. In a previous paper [11] the formation of
such crystalline phase(s) was presented in detail, as well as
the entire mechanism of crystallization and phase transfor-
mation for the Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 glassy alloy.
The extension of the supercooled liquid region de-
creases with the increasing iron content (Fig. 2). For
70
60
∆ Tx [K]
the 65.6 at.% iron content Tx is around 66 K. For the
Fe67.5 Cr4 Mo4 Ga2 P12 C5 B5.5 amorphous alloy it decrease
to 59 K, for Fe69.5 Cr4 Mo4 P12 C5 B5.5 to 47 K and for
Fe71.5.5 Cr2 Mo2 Ga2 P12 C5 B5.5 Tx reaches 45 K. The re-
duced glass transition temperature Tg /Tliq shows a similar
decreasing trend with increasing Fe content, i.e. Tg /Tliq
drops from 0.59 for x = y = z = 4 to 0.56 for x = y = z =
2. This indicates that the glass-forming ability decreases
with increasing iron content, and this is reflected in the
possibility to cast such alloys directly in bulk shape.
All the completely amorphous samples exhibit a very low
coercive force Hc , below 10 A m−1 . The lowest coercivity
value of about 1 A m−1 is found for the ribbons and the co-
ercivity increases to 5–9 A m−1 for the cast rods. However,
the coercivity does not increase monotonically with increas-
ing diameter of the rods, i.e. does not depend on the geome-
try of the sample, but is probably most sensitive to residual
stresses induced during the casting and to crystalline inclu-
sions. For the as-cast rod with 3 mm diameter in the case of
Fe65.5 Cr4 Mo4 Ga4 P12 C5 B5.5 , with 1.5 mm diameter in the
case of Fe67.5 Cr4 Mo4 Ga2 P12 C5 B5.5 and with 1.5 mm diam-
Tx
eter in the case of Fe69.5 Cr4 Mo4 P12 C5 B5.5 the samples are
Tg/Tliq not fully amorphous. The coercivity increases by one order
of magnitude, reaching values between 17 and 75 A m−1 ,

50 ribbons and it is expected to depend on the volume fraction of crys-

talline inclusions.
40 The values of the Curie temperature, Tc , as a function of
composition and sample diameter are plotted in Fig. 3. As
0.60
a general trend it is observed that the Curie temperature is
ribbons larger for rod samples in comparison to the ribbon samples,
Tg/Tliq

0.55 as well as it increases with increasing rod diameter. Such a

variation of the Curie temperature is due to a more relaxed
65 66 67 68 69 70 71 72
amorphous structure of the rods with increasing diameter
Fe content [at.%]
and in comparison with the ribbon. Concerning the com-
Fig. 2. Extension of the supercooled liquid region Tx = Tx − Tg position, the Curie temperature decrease with the increas-
and the reduced glass transition temperature Tg /Tliq of Fe77.5−x−y−z ing Fe content when the Ga content decreases, from 435 K
Crx Moy Gaz P12 C5 B5.5 amorphous ribbons as a function of iron content. for 65.5 at.% Fe to 402 K for 69.5 at.% Fe, but increases
402 M. Stoica et al. / Materials Science and Engineering A 375–377 (2004) 399–402

to 515 K for 71.5 at.% Fe when the content of Cr, Mo and
Ga are all 2 at.%. The values of the saturation polarization
are in the range of 0.77–0.82 T for the as-cast samples with
65.5 at.% Fe content and increase to 1.16 T for the samples
with 71.5 at.% Fe. The main errors that can appear during
the magnetic characterization are due to the difficulties to
estimate precisely the rather small cross-section of the rib-
bons.
Acknowledgements
The authors thank K. Biswas for his help with some mea-
surements and H. Schulze and M. Peschel for technical as-
sistance. This work was supported by the EU within the
framework of the RTN-Network on bulk metallic glasses
(contract HPRN-CT-2000-00033).

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