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24
Soft magnetic properties of bulk nanocrystalline
Fe–Co–B–Si–Nb–Cu alloy with high saturated magnetization
of 1.35 T
Baolong Shen
a)
and Akihisa Inoue
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan; and
Research and Development Project, Core Research for Evolution Science and Technology, Japan
Science and Technology Agency, Sendai 980-8577, Japan
(Received 3 February 2004; accepted 1 July 2004)
Bulk nanocrystalline body-centered cubic- (bcc) (Fe,Co) alloy with high saturated
magnetization and good soft magnetic properties was synthesized by the simple
process of casting and annealing for the glass-type Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
alloy.
It crystallizes through two exothermic reactions. The cylindrical glassy rod with the
diameter of 1.5 mm was produced by copper mold casting. The subsequent annealing
at the temperature higher than that of the first exothermic peak causes the formation of
bcc-(Fe,Co) nanocrystalline with particle sizes between 10 and 15 nm. The bcc-(Fe,Co)
alloy rods exhibit good soft magnetic properties of 1.35 T for saturation magnetization
and 5 A/m for coercive force.
Since the first successful synthesis of Fe-based bulk
glassy alloys in an Fe–Al–Ga–P–C–B system by copper
mold casting in 1995,
1
various kinds of Fe-based bulk
glassy alloys have been produced by the copper mold
casting method.
2
The main Fe-based bulk glassy alloy
systems can be listed in the order of evolution as follows:
Fe–(Nb,Cr,Mo)–(Al,Ga)–(P,C,B),
3
Fe–(Nb,Cr,Mo)–Ga–
(P,C,B),
4
Fe–(Zr,Hf,Nb)–B,
5
Fe–Ga–(P,C,B),
6
Fe–Co-Ga–
(P,C,B),
7
Fe–(Nb,Cr,Mo)–(P,C,B),
8
Fe–(Cr,Mo)–C–B,
9
and Fe–B–Si–Nb.
10
These Fe-based bulk glassy alloys
have been synthesized on the basis of the following three
component rules for stabilization of supercooled liq-
uid:
2,11,12
(i) multi-component consisting of more than
three components, (ii) significant atomic size mismatches
above 12 at.% among the three elements, and (iii) nega-
tive heats of mixing among their elements. All these bulk
glassy alloys exhibit a glass transition, followed by su-
percooled liquid and then crystallization. We have also
shown that the addition of a small amount of Cu as well
as the decrease of B content from the optimum content of
(Fe
0.75
B
0.15
Si
0.1
)
96
Nb
4
bulk glassy alloy causes the
change in the crystallization mode from the single stage
to two stages, but the alloy still exhibited higher glass-
forming ability (GFA), thus enabling us to synthesize a
bulk glassy rod in the diameter of 0.5 mm.
13
In addition,
the precipitation of the ␣–Fe primary crystalline phase
resulted from the addition of Cu leads to the formation of
nanocrystalline body-centered cubic (bcc) phase embed-
ded in the remaining amorphous phase by annealing the
sample at the temperature higher than that of the first
peak.
13
This crystallization behavior is similar to that of
Fe–Si–B–Nb–Cu (FINEMET) even though FINEMET
has a higher Si and lower B content.
14
Very recently, the
possibility of enhancing the GFA and soft magnetic
properties of bcc phase bulk alloys was investigated. We
found that the replacement of Fe by an optimum Co
content is effective for increase in the GFA that the Fe–
Co–B–Si–Nb–Cu bulk glassy alloy with the diameter of
1.5 mm can be produced by the copper mold casting
method, and the nanocrystalline Fe–Co–B–Si–Nb–Cu
bcc bulk alloys exhibiting saturation magnetization (I
s
)
of 1.26 T are obtained by subsequent annealing.
15
On the
other hand, Y. Yoshizawa et al. have recently reported
that the I
s
of FINEMET can be increased to 1.5 T by
optimizing the Cu content.
16,17
Therefore, it is also im-
portant to examine the possibility of increasing the I
s
with almost no effect on the glass-forming ability for
Fe–Co–B–Si–Nb–Cu bulk nanocrystalline alloys by op-
timizing the composition of Fe–Co–B–Si–Nb–Cu glassy
alloy. This communication intends to report the results of
optimizing the Cu content to increase the I
s
of bulk
nanocrystalline bcc alloys without decreasing the GFA.
We selected the Fe
61.5
Co
10
B
13.5
Si
10
Nb
4
Cu
1
alloy for in-
vestigation because it exhibits larger GFA according to
the former results.
15
To increase the Fe content, the Nb
content was decreased from 4 to 3 at.%, and Cu content
was decreased from 1 to 0.7 at.%, respectively.
a)
Address all correspondence to this author.
e-mail: shen@imr.tohoku.ac.jp
DOI: 10.1557/JMR.2004.0360
J. Mater. Res., Vol. 19, No. 9, Sep 2004 © 2004 Materials Research Society 2549
http://journals.cambridge.org Downloaded: 21 May 2014 IP address: 111.68.102.24
An Fe–Co-based alloy ingot with composition of
Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
was prepared by arc melt-
ing the mixtures of pure Fe, Co, Nb, and Cu metals and
pure B and Si crystals in an argon atmosphere. A rapidly
solidified alloy ribbon with a cross section of 0.02 ×
1 mm
2
was produced from the pre-alloyed ingot by the
melt-spinning method in an argon atmosphere. Cylindri-
cal alloy rods with a length of 50 mm and diameters of
1–3 mm were produced by the copper mold casting
method. Glassy and crystallized structures were analyzed
by x-ray diffraction (XRD) with Cu K

radiation and
investigated by transmission electron microscopy
(TEM). Cylindrical alloy rods in as-cast and annealed
states were sectioned by fine cutter for XRD measure-
ment. Thermal stability associated with glass transi-
tion, supercooled liquid and crystallization was examined
by differential scanning calorimetry (DSC) at a constant
heating rate of 0.67 K/s. Magnetic properties of I
s
and
coercive force (H
c
) were measured with a vibrating
sample magnetometer (VSM) under an applied field
of 400 kA/m and a B-H loop tracer under a field of
800 A/m. The Curie temperature was determined from
the DSC curve.
Figure 1 shows the outer shape and surface morphol-
ogy of the as-cast Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
alloy rod
with a diameter of 1.5 mm. The rod sample shows a
smooth outer surface and metallic luster. Neither rugged-
ness nor concavity due to the precipitation of a crystalline
phase is observed across the whole outer surface. Cu K

XRD patterns taken on disks cut from the as-quenched
rods have broad diffraction peaks with rounded tops, cen-
tered at 44° and 78° shown in Fig. 2, which means that
the as-cast sample maintains an amorphous structure.
Fi g u r e 3 s h o ws t h e DSC c u r v e o f t h e
Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
bulk glassy alloy. The Cu-
rie temperature (T
c
),
18
the temperature corresponding to
the formation of Cu-rich clusters (T
p
),
15,19
the glass tran-
sition temperature (T
g
), the crystallization temperature
(T
x
), and supercooled liquid temperature (⌬T
x
) were
found to be 647, 770, 815, 845, and 30 K, respectively.
These temperature values are in agreement with those
found for the melt-spun amorphous ribbons of the same
composition,
20
indicating the amorphous nature of the
as-cast bulk metallic sample. Moreover, the DSC curve
FIG. 3. DSC curve of the Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
bulk glassy
alloy with a diameter of 1.5 mm.
FIG. 1. Outer shape of cast Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
glassy alloy
rod with a diameter of 1.5 mm.
FIG. 2. XRD patterns of the alloy rod with a diameter of 1.5 mm
subjected to annealing for 300 s at 873 K (that is higher than the
temperature of the first peak), and 600 s at 983 K (that is higher than
the temperature of the second peak), respectively, together with the
data of the as-cast alloy rod.
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of the alloy consists of two exothermic peaks, indicating
that the crystallization proceeds through two stages. The
crystallization behaviors were investigated by XRD. The
XRD patterns of the alloy rod with a diameter of 1.5 mm
subjected to annealing for 300 s at 873 K (that is higher
than the temperature of the first peak), and 600 s at
983 K (that is higher than the temperature of the second
peak), respectively, are also shown in Fig. 2. After an-
nealing for 300 s at 873 K, the diffraction pattern consists
of three peaks, which can be indexed as a bcc-(Fe,Co)
phase. A bright-field TEM image of the material is
shown in Fig. 4. It can be seen that the bcc-(Fe,Co) grains
with particle sizes between 10 and 15 nm disperse ho-
mogeneously in the glassy matrix phase. Therefore, the
first-stage exothermic reaction is due to the precipitation
of the nanocrystalline bcc-(Fe,Co) phase. After annealing
for 600 s at 983 K, the diffraction peaks can be identified
as bcc-(Fe,Co), (Fe,Co)
23
B
6
, (Fe,Co)
3
Si, (Fe,Co)
2
Nb,
(Co,Fe)NbB and face-centered-cubic-Cu phases, indicat-
ing that the second exothermic peak is due to the decom-
position of the remaining amorphous phase into these six
phases.
Figure 5 shows the hysteresis I-H loop of the as-cast
Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
alloy rod subjected to an-
nealing for 300 s at 873 K, together with the data of the
melt-spun alloy ribbon annealed under the same condi-
tion. Although one can see the difference in the I-H loops
due to the demagnetizing field resulting from the signifi-
cant difference in the morphology between the ribbon
and bulk samples, there is just a little deference in the I
s
and H
c
values between the two samples. I
s
and H
c
are
found to be 1.35 T and 3 A/m, respectively, for the melt-
spun ribbon and 1.35 T and 5 A/m, respectively, for the
glassy alloy rod.
It is known that bulk glassy alloys are formed in the
alloy systems in which the components satisfy the three
empirical rules as mentioned in the introduction. The
third rule is the “negative heats of mixing among their
elements.”
2,11,12
The extent of the satisfaction for this
rule decreases for the Fe
61.5
Co
10
B
13.5
Si
10
Nb
4
Cu
1
glassy
alloy with decreasing Nb content from 4 to 3 at.% be-
cause the negative mixing heats among Nb and Fe, Co,
B, Si elements are very large, which is −16 kJ/mol for
Nb–Fe pair, −25 kJ/mol for Nb–Co pair, −39 kJ/mol for
Nb–B pair and −39 kJ/mol for Nb–Si pair, respectively.
21
However, the ⌬T
x
is maintained to 30 K for the
Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
glassy alloy. It is proposed
that the maintenance of ⌬T
x
is attributed to the decrease
of Cu content from 1 to 0.7 at.% because the mixing
heats are positive among the Cu and Fe, B, Nb, which is
13 kJ/mol for the Cu–Fe pair, 6 kJ/mol for the Cu–Co
pair, 15 kJ/mol for the Cu–B pair, and 3 kJ/mol for the
Cu–Nb pair. The mixing enthalpy between the Cu and Si
is negative, but the value is very small, −2 kJ/mol for
Cu-Si atomic pair.
21
Therefore, the extent of the satis-
faction for the third rule increases with decreasing the Cu
content, the effect of decreasing Nb content on the GFA
FIG. 4. Bright-field TEM image of the Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
bulk glassy alloy with a diameter of 1.5 mm subjected to annealing for
300 s at 873 K.
FIG. 5. Hysteresis I-H loop of the cast Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
alloy rod with a diameter of 1.5 mm subjected to annealing for 300 s
at 873 K. The data of the melt-spun glassy alloy ribbon annealed under
the same condition are also shown for comparison.
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is reduced. As a result, the ⌬T
x
is maintained at 30 K,
which enables us to produce the bulk glassy sample with
a diameter in 1.5 mm by copper mold casting method.
Otherwise, it is also confirmed that the small decrease of
Cu addition from 1 to 0.7 at.% does not change the
crystallization behavior, which enabled us to obtain the
high I
s
of 1.35 T by annealing the bulk sample at 873 K,
which is higher than the temperature of the first crystal-
lization peak.
In conclusion, the glass-type alloy Fe
62.8
Co
10
B
13.5
Si
10
Nb
3
Cu
0.7
with glass transition and supercooled liquid
region before crystallization was formed. The appearance
of the supercooled liquid region before crystallization
enabled us to form cylindrical glassy alloy rod with a
diameter of 1.5 mm by the copper mold casting process.
The subsequent annealing for 300 s at 873 K caused the
formation of nanocrystalline bcc-(Fe,Co) phase with par-
ticle sizes between 10 and 15 nm. The nanocrystalline
bcc-(Fe,Co) alloy rod exhibited good soft magnetic prop-
erties of 1.35 T for I
s
and 5 A/m for H
c
, which could be
compared with the FINEMET with I
s
of 1.5 T and H
c
of
3 A/m in ribbon form.
17
The success of forming the
nanocrystalline soft magnetic bcc-(Fe,Co) alloys in a
bulk form exhibiting high saturated magnetization and
good soft magnetic properties is promising for future use
as a new type of magnetic materials with three dimen-
sional shapes.
REFERENCES
1. A. Inoue, Y. Shinohara, and J.S. Gook: Thermal and magnetic
properties of bulk Fe-based glassy alloys prepared by copper mold
casting. Mater. Trans. JIM 36, 1427 (1995).
2. A. Inoue: Stabilization of metallic supercooled liquid and bulk
amorphous alloys. Acta Mater. 48, 279 (2000).
3. A. Inoue and J.S. Gook: Effect of additional elements (M) on the
thermal stability of supercooled liquid in Fe
72-x
Al
5
Ga
2
P
11
C
6
B
4
M
x
glassy alloys. Mater. Trans. JIM 37, 32 (1996).
4. T.D. Shen and R.B. Schwarz: Bulk ferromagnetic glasses prepared
by flux melting and water quenching. Appl. Phys. Lett. 75, 49
(1999).
5. H. Koshiba, A. Inoue, and A. Makino: Fe-based soft magnetic
amorphous alloys with a wide supercooled liquid region. J. Appl.
Phys. 85, 5136 (1999).
6. B.L. Shen, H. Koshiba, T. Mizushima, and A. Inoue: Bulk amor-
phous Fe–Ga–P–B–C alloys with a large supercooled liquid re-
gion. Mater. Trans. JIM 41, 873 (2000).
7. B.L. Shen, H.M. Kimura, A. Inoue, and T. Mizushima: Bulk
glassy Fe–Co–Ga–P–C–B alloys with high glass-forming ability,
high saturation magnetization and good soft magnetic properties.
Mater. Trans. JIM 41, 1675 (2000).
8. S.J. Pang, T. Zhang, K. Asami, and A. Inoue: Synthesis of
Fe–Cr–Mo–C–B–P bulk metallic glasses with high corrosion re-
sistance. Acta Mater. 50, 489 (2002).
9. S.J. Pang, T. Zhang, K. Asami, and A. Inoue: Formation of bulk
glassy Fe
75-x-y
Cr
x
Mo
y
C
15
B
10
alloys and their corrosion behavior.
J. Mater. Res. 17, 701 (2002).
10. A. Inoue and B.L. Shen: Soft magnetic bulk glassy Fe–B–Si–Nb
alloys with high saturation magnetization above 1.5 T. Mater.
Trans. 43, 766 (2002).
11. A. Inoue: High strength bulk amorphous alloys with low critical
cooling rates. Mater. Trans. JIM 36, 866 (1995).
12. A. Inoue: Bulk Amorphous Alloys (Trans Tech Publications,
Zurich, Switzerland, 1998), pp.1–33.
13. A. Inoue, B.L. Shen, and T. Ohsuna: Soft magnetic properties of
nanocystalline Fe–Si-B-Nb-Cu rod alloys obtained by crystalliza-
tion of cast amorphous phase. Mater. Trans. 43, 2337 (2002).
14. Y. Yoshizawa and K. Yamauchi: Fe-based soft magnetic alloys
composed of ultrafine grain structure. Mater. Trans. JIM 31, 307
(1990).
15. A. Inoue and B.L. Shen: Soft magnetic properties of nanocrystal-
line Fe–Co–B–Si–Nb–Cu alloys in ribbon and bulk forms.
J. Mater. Res. 18, 2799 (2003).
16. Y. Yoshizawa: Magnetic properties and applications of nanostruc-
tured soft magnetic materials. Scripta Mater. 44, 1321 (2001).
17. Y. Yoshiazawa, S. Fujii, D.H. Ping, M. Ohnuma, and K. Hono:
Magnetic properties of nanocrystalline FeMCuNbSiB alloys
(M: Co, Ni). Scripta Mater. 48, 863 (2003).
18. H.S. Chen: Effects of composition and structure on magnetic
properties of amorphous Fe–P–C alloys. Phys. Status Solidi A 17,
561 (1973).
19. M. Ohnuma, K. Hono, H. Onodera, J.S. Pedersen, and S. Linderoth:
Cu clustering stage before the crystallization in Fe–Si–B–Nb–Cu
amorphous alloys. Nanostruct. Mater. 12, 693 (1999).
20. B.L. Shen: unpublished data. (2003).
21. F.R. Boer, R. Boom, W.C.M. Mattens, A.R. Miedema, and
A.K. Niessen: Cohesion in Metals (North-Holland, Amsterdam,
The Netherlands, 1988), pp. 217–258.
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