Materials Transactions, Vol. 47, No. 6 (2006) pp.

1615 to 1618
#2006 The Japan Institute of Metals

RAPID PUBLICATION

Fe-(Cr,Mo)-(C,B)-Tm Bulk Metallic Glasses with High Strength

and High Glass-Forming Ability
Kenji Amiya1 and Akihisa Inoue2
1
2

R&D Institute of Metals and Composites for Future Industries (Tohoku Univ. Lab.), Sendai 980-8577, Japan
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

The glass-forming ability and mechanical properties of (Fe,Co)-(Cr,Mo)-(C,B)-Tm glassy alloys have been investigated. The
(Fe,Co)48 Cr15 Mo14 C15 B6 Tm2 glassy alloys were prepared in a cylindrical form with a diameter of 10 mm. These alloys have high glass forming
ability (GFA) enough to produce a single glassy rods with a diameter above 10 mm. The largest supercooled liquid region before crystallization
in (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 alloys is 90 K for Co48 Cr15 Mo14 C15 B6 Tm2 . These glassy alloys have high fracture strength of over
4100 MPa for the entire composition range and the strength level is almost independent of Co content. The high GFA is attributed to the
retardation of precipitation of the crystallized phases caused by the formation of the stabilized glassy local structure in which short-range ordered
trigonal prisms are connected through glue eect of Tm element. The combination of high strength and high glass-forming ability indicates high
possibility of applying the (Fe,Co)-(Cr,Mo)-(C,B)-Tm glassy alloys to various industrial materials. [doi:10.2320/matertrans.47.1615]
(Received March 20, 2006; Accepted May 9, 2006; Published June 15, 2006)
Keywords: metallic glass, glass-forming ability, iron-base system, high strength

1.

Introduction

Great eort has been devoted to search new non-ferrous

and ferrous glassy alloys with higher glass-forming ability for
the last two decades. As a result, a number of glassy alloys
with high GFA have been synthesized in Ln-Al-TM,1) Mg-YTM,2) Zr-Al-TM,3) Pd-TM-P4) and Ca-Mg-TM5) (Ln =
lanthanide metal, TM = transition metal) base systems.
The largest diameter of bulk metallic glasses (BMG) reaches
about 72 mm for Pd-Cu-Ni-P alloy by the water quenching
method with B2 O3 ux.4) It has been pointed out that the
BMGs with high GFA satisfy the following three empirical
component rules,6,7) i.e., (1) multicomponent systems consisting of more than three elements, (2) signicant dierence
in atomic size above 12% among the main three constituent
elements, and (3) large negative heats of mixing among the
consistent elements. Based on the three component rules, Feand Co-based glassy alloys with high GFA have been
searched for the last one decade. The use of the three
component rules has enabled the fabrication of Fe-B-Si-Nb
BMG with high GFA and high strength above 4000 MPa.8) In
addition, the GFA and soft magnetic properties of Fe-B-SiNb alloys have been improved by the addition of Co. The
resulting cast ((Fe0:5 Co0:5 )72 B0:02 Si0:05 )Nb4 alloy9) exhibits
high fracture strength of 4200 MPa and high GFA with a
critical diameter of 5 mm for formation of a single glassy
phase. Considering the engineering importance of Fe-based
glassy alloys, there has been strong social demand of
developing Fe-based bulk glassy alloys with higher GFA in
conjunction with high strength. Recently, Fe-based BMGs
with critical diameters up to 10 mm were formed in Fe(Cr,Mo)-(C,B)-Y system through the additional eect of
small amounts of Y on the bulk glassy10) Fe-(Cr,Mo)-(C,B)
alloys.11) However, little is reported about the mechanical
properties of Fe-(Cr,Mo)-(C,B)-Y glassy alloys because of
their extremely brittle nature. We have found that Fe(Cr,Mo)-(C,B)-Tm BMG exhibits simultaneously high
strength above 4000 MPa as well as high GFA with a critical

diameter of over 10 mm. We have further examined the eect

of replacement of Fe by Co on the GFA and mechanical
properties in (Fe,Co)-(Cr,Mo)-(C,B)-Tm system. This paper
presents the GFA and mechanical properties of (Fe,Co)(Cr,Mo)-(C,B)-Tm glassy alloys.
2.

Experimental Procedure

Multi-component alloys in (Fe,Co)-Cr-Mo-C-B-Tm system were examined because the signicant additional eect
of Y on Fe50 Cr15 Mo14 C15 B6 alloy. Alloy ingots were prepared by arc melting the mixtures of pure Fe, Cr, Mo, Tm,
pure carbon granular and pure B crystal in an argon atmosphere. The alloy compositions represent nominal atomic
percentages of the mixtures. BMGs in a cylindrical form with
a length of 50 mm and dierent diameters in the range of 2
to 10 mm were produced by a copper mold casting method.
For comparison, glassy alloy ribbons with a thickness of
about 0.03 mm were also prepared by melt spinning. The
glassy structure was examined by X-ray diraction (XRD)
with Mo-K
radiation and optical microscopy with a polarizing lter. The specic heat associated with glass transition,
supercooled liquid region and crystallization was measured
by dierential scanning calorimetry (DSC) at a heating rate
of 0.67 K/s. Mechanical properties of cast rods were
measured with an Instron testing machine at a strain rate of
2  10
4 s
1 under a uniaxial compressive load.
3.

Results

Figure 1 shows the XRD patterns taken from the crosssection of the cast Fe50
x Cr15 Mo14 C15 B6 Tmx (x 0; 1; 2)
alloy rods. Although the Fe50 Cr15 Mo14 C15 B6 rod with a
diameter of 2 mm consists of glassy and crystalline Fe23 B6
phases, the addition of Tm is eective for the suppression of
the precipitation of the crystalline phase, leading to the
formation of a single glassy phase with a diameter of 6 mm at
the Tm concentration of 2 at%. The crystalline phases of the

1616

K. Amiya and A. Inoue

XRD
Mo-K

x=0 d=2 mm

10

20

d=8 mm
d=6 mm

x=2 d=6 mm

Ribbon

40

2 / ( /180)rad

700

Tg

800

Tx

900

1000

Temperature / K

Fig. 1 XRD patterns taken from the cross-section of the cast Fe50
x Cr15 Mo14 C15 B6 Tmx (x 0; 1; 2) rods.

Fig. 3 DSC curves of the cast Fe48 Cr15 Mo14 C15 B6 Tm2 rods with
diameters of 6 to 10 mm. The data of the melt-spun ribbon are also
shown for comparison.

XRD
Mo-K

Fe48Cr15Mo14C15B6Tm2

Intensity (arb. unit)

d=10 mm

x=1 d=6 mm

30

DSC
0.67 K/s

Fe48Cr15Mo14C15B6Tm2

Exothermic

Intensity (arb. unit)

Fe50-xCr15Mo14C15B6Tmx

d=10 mm
d=8 mm
d=6 mm
Fig. 4 Outer surface morphology of the cast Fe48 Cr15 Mo14 C15 B6 Tm2 rod
with a diameter of 10 mm and a length of 50 mm prepared by copper mold
casting.

d=2 mm
10

20

30

40

2/ ( /180)rad
Fig. 2 XRD patterns taken from the cross-section of the cast Fe48 Cr15 Mo14 C15 B6 Tm2 rods with diameters of 2 to 10 mm.

cast Fe50
x Cr15 Mo14 C15 B6 Tmx (x 0; 1) rods are identied

as only a Fe23 B6 phase. The partial crystallization phase is
independent of Tm addition up to 1 at%.
Figure 2 shows the XRD patterns taken from the crosssection of the cast Fe48 Cr15 Mo14 C15 B6 Tm2 rods with
diameters of 2 to 10 mm. These cylindrical samples have
broad diraction peaks and no sharp diraction peak
corresponding to a crystalline phase is seen for all samples,
indicating that a mostly single glassy phase is formed by the
casting method. It is noted that the alloy has high GFA
enough to produce a single glassy phase even in the 10 mm
cylindrical sample.
Figure 3 shows the DSC curves of the cast Fe48 Cr15 Mo14 C15 B6 Tm2 rods with diameters of 6 to 10 mm together
with the data of the melt-spun ribbon. The glass transition

temperature (Tg ), crystallization temperature (Tx ) and the

temperature interval of the supercooled liquid region (
Tx )
of the bulk samples are 862, 914 and 52 K, respectively,
being independent of sample diameter. Furthermore, there is
no appreciable dierence in Tg and Tx between the cast and
melt-spun samples. The heat of crystallization (
Hx ) for the
rst exothermic peak was evaluated to be 0.83 kJ/mol for the
rod of 10 mm in diameter and 0.86 kJ/mol for the ribbon. The

Hx is also being nearly the same between the rods and
ribbon. It is thus concluded that the sequent transition
behavior of glass transition, supercooled liquid and crystallization is independent of cooling rate in the preparation
process.
Figure 4 shows the outer surface morphology of the cast
Fe48 Cr15 Mo14 C15 B6 Tm2 rod with a diameter of 10 mm and a
length of 50 mm prepared by copper mold casting. Neither
holes nor cavities are seen on the outer surface of the cast
sample and its surface has good luster. Considering that the
shape and dimension of the cast sample are just the same as
the inner shape of the copper mold, the metallic mold

Fe-(Cr,Mo)-(C,B)-Tm Bulk Metallic Glasses with High Strength and High Glass-Forming Ability

10

d=10 mm

8
6
4
2
0

(853)

(943)

d=8 mm
(943)

(850)

d=6 mm
0

0.2

0.4

0.6

0.8

1.0

(857)

Co content, x

Tg(857)

700

Discussion

We discuss the reason for the signicant increase in the

dmax for glass formation above 10 mm by the addition of
2 at%Tm to the previously reported glass-type Fe-(Cr,Mo)-

800

Tx(943)

900

1000

Temperature (K)
Fig. 6 DSC curves of the cast Co48 Cr15 Mo14 C15 B6 Tm2 rods with
diameters of 6 to 10 mm.

5000

(Fe1-xCox)48Cr15Mo14C15B6Tm2

Co=0 0.2 0.4 0.6 0.8 1.0

4000
Stress / MPa

pressure casting method seems to be useful for the production

of the bulk samples with various shapes and dimensions.
The compositional dependence of the critical diameter for
formation of the single glassy phase (dmax ) was examined for
(Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 alloys. Figure 5 shows the
plots of the diameter for glass formation as a function of Co
content for the (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 alloys. The
bulk glassy alloys of 10 mm in diameter are formed over the
whole composition range. It is noted that the large dmax
exceeding 10 mm is independent of Co content. The DSC
curves of the cast Co-based Co48 Cr15 Mo14 C15 B6 Tm2 rods
with diameters of 6 to 10 mm are shown in Fig. 6, together
with the data of the melt-spun Co48 Cr15 Mo14 C15 B6 Tm2
glassy ribbon. It is seen that the cast alloys exhibited the
distinct glass transition at 853 K, followed by a large
supercooled liquid region of 90 K. The Tg and Tx of the bulk
samples are about 855 and 943 K, respectively. Furthermore,
there is no appreciable dierence Tg and Tx between the cast
and melt-spun samples. The previous data indicate that the
largest
Tx for Co-based glassy alloys is 98 K for Co40 Fe22 Nb6 Zr2 B30 alloy, while the dmax of the alloy is 1.5 mm.12)
The present results of the Co48 Cr15 Mo14 C15 B6 Tm2 glassy
alloy are believed to be the rst evidence for the good
combination of the large
Tx of over 90 K and high GFA
leading to the formation of a single glassy phase even in the
10 mm cylindrical sample for Co-based BMGs.
Mechanical properties of the cast (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 (x 0{1) rods with a diameter of 2 mm
were measured by the compression test. Figure 7 shows
stress-strain curves of the cast (Fe1
x Cox )42 Cr15 Mo14 C15 B6 Tm2 (x 0{1) rods. It is seen that the (Fe,Co)48 Cr15 Mo14 C15 B6 Tm2 alloys exhibit the compressive strength of
over 4100 MPa and elastic elongation of 1.7% to 1.9%, being
independent of Co content. It is again noticed that the high
strength of 4340 MPa in conjunction with large dmax above
10 mm is achieved for the (Fe0:2 Co0:8 )48 Cr15 Mo14 C15 B6 Tm2
BMGs.

(943)

Ribbon

Fig. 5 Change in the structure of the cast (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2
rods with sample diameter and Co content.

4.

DSC
0.67 K/s

Co48Cr15Mo14C15B6Tm2

Glass

Exothermic

Diameter / mm

(Fe1-xCox)48Cr15Mo14C15B6Tm2

1617

3000

2000

1000

1%

0
Strain

Fig. 7 Stress-strain curves of the cast (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2
(x 0{1) cylindrical rods.

(C,B) alloy.11) The Fe-(Cr,Mo)-(C,B) system as the base

alloy system is not perfect in the satisfaction of the three
empirical rules. The atomic size ratio is 1.00 to 1.10 for
(Cr,Mo)/Fe and 1.39 to 1.45 for Fe/(C,B). The addition of
Tm element is eective for the increase in the degree of the
satisfaction of the three component rules. That is, the addition
of Tm element causes the more sequential change in the
atomic size in the order Tm > Mo > Cr > Fe > B > C as
well as the generation of new atomic pairs with various
negative heats of mixing. This leads to the diculty in the
rearrangement of the constituent elements on a long-range
scale. Furthermore, it is known that the glassy alloys of Fe-BNb and Fe-B-Ln systems with high GFA have local atomic
congurations of the triangular prism structure.13) The Ln
element plays an important role as the glue atom which joins

1618

K. Amiya and A. Inoue

the triangular prism to each other. The Fe23 B6 phase which

contains the triangular prism structure precipitates as the
partial crystallization phase in the Fe-B-Nb and Fe-B-Ln
glassy alloys. The partial crystallization phase is identied as
Fe23 B6 phase in the Fe50 Cr15 Mo14 C15 B6 and Fe49 Cr15 Mo14 C15 B6 Tm1 alloys. The triangular prisms structure may
exist in the glassy phase of Fe-Cr-Mo-C-B and Fe-(Cr,Mo)(C,B)-Tm systems. The main dierences between Fe-Cr-MoC-B and Fe-(Cr,Mo)-(C,B)-Tm system may be attributed to
the result that the former alloy consists only of the isolated
prism structure, while the latter system alloy is composed of
the network-like prism structure which bonded to each other.
The addition of Tm element is indispensable to gluing on the
triangular prism to improve GFA in Fe-(Cr,Mo)-(C,B)
system. The fracture strength of the Fe-Cr-Mo-C-B-Tm
BMG with a diameter of 2 mm is 4200 MPa which is higher
by 300 MPa than that of the Fe-Cr-Mo-C-B amorphous
ribbon.14) The improved strength seems to result from the
development of the bonded prism structures. Thus, the
addition of Tm is eective for the simultaneous improvements of GFA and mechanical strength.
5.

Summary

The maximum diameter for formation of a glassy phase

exceeds 10 mm for all alloys in (Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 system. The maximum diameter of the rod above
10 mm is independent of Co content. The highest
Tx in the
(Fe1
x Cox )48 Cr15 Mo14 C15 B6 Tm2 alloys is 90 K for Co48 Cr15 Mo14 C15 B6 Tm2 . These glassy alloys have high fracture
strength above 4100 MPa which is independent of Co
content. The high GFA is attributed to the retardation of
precipitation of the crystalline phases caused by the formation of the stabilized glassy local structure in which

trigonal prisms may be connected with each other through the

glue atom of Tm. The simultaneous achievement of high
strength and high GFA indicates the possibility of applying
the (Fe,Co)-(Cr,Mo)-(C,B)-Tm glassy alloys to various
engineering materials.
Acknowledgment
This study is funded by the New Energy and Industrial
Technology Development Organization (NEDO) under
Processing Technology for Metallic Glasses project.
REFERENCES
1) A. Inoue, H. Yamaguchi, T. Zhang and T. Masumoto: Mater. Trans.,
JIM 31 (1990) 104109.
2) A. Inoue, K. Ohtera, K. Kita and T. Masumoto: Jpn. J. Appl. Phys. 27
(1988) L2248L2251.
3) A. Inoue, T. Zhang and T. Masumoto: Mater. Trans., JIM 31 (1990)
177183.
4) A. Inoue, N. Nishiyama and T. Matsuda: Mater. Trans., JIM 37 (1996)
181184.
5) K. Amiya and A. Inoue: Mater. Trans. 43 (2002) 25782581.
6) A. Inoue: Mater. Trans., JIM 36 (1995) 866875.
7) A. Inoue: Bulk Amorphous Alloys, (Trans Tech Publication, Zurich,
1998) pp. 136.
8) K. Amiya, A. Urata, N. Nishiyama and A. Inoue: Mater. Trans., JIM 45
(2004) 12141218.
9) B. Shen, A. Inoue and C. Chang: Appl. Phys. Let. 85 (2004) 4911
4913.
10) Z. P. Lu, C. T. Liu, J. R. Thompson and W. D. Porter: Phys. Rev. Lett.
92 (2004) 245503.
11) S. J. Pang, T. Zhang, K. Asami and A. Inoue: Corrosion Sci. 44 (2002)
18471856.
12) T. Itoi and A. Inoue: Mater. Trans., JIM 41 (2000) 12561262.
13) A. Inoue and A. Takeuchi: Mater. Trans. 43 (2002) 18921906.
14) A. Inoue, T. Masumoto, S. Arakawa and T. Iwadachi: Proc. RQ3
(1978) 265272.