J. Mater. Sci. Technol., Vol.25 No.

5, 2009 665

Dependence of Amorphous Formation Ability on Intrinsic

Parameters in Dy-Gd-Co-Al Alloys
Lin Luo, Rui Tian and Xueshan Xiao†
Institute of Materials, Shanghai University, Shanghai 200072, China
[Manuscript received May 8, 2008, in revised form October 9, 2008]

A series of Dy(Gd)-based bulk amorphous alloy rods were prepared by water-cooled copper mold method.
Thermal stability and structure of Dy-Gd-Co-Al alloys were investigated by differential scanning calorimetry
and X-ray diffraction, respectively. The results show that the Dy-Gd-Co-Al alloys have good glass-formation
ability, and the Dy31 Gd25 Co20 Al24 alloy can be readily cast into full glassy rods up to 5 mm in diameter. The
glass-forming ability of multicomponent alloys was greatly dependent on their chemical interaction and the
equivalent bond parameters among atoms such as equivalent electronegativity difference, equivalent atomic
size parameter. The Dy (Gd)-based bulk amorphous alloys could be expected as potential functional materials.
KEY WORDS: Dy(Gd)-based; Glass forming ability; Intrinsic parameters

1. Introduction in Perkin-Elmer differential scanning calorimeter

Compared with crystalline counterparts, bulk
metallic glasses have excellent mechanical properties,
good magnetic properties, corrosion resistance and
oxidation resistance. So they have gained consid-
erable interests for the new industrial applications.
In recent years, many new multicomponent metal-
lic glasses such as Pd-Cu-Ni-P[1] , Zr-Ti-Cu-Ni-Be[2] ,
Mg-Cu-Y[3] , Zr-Al-Ni-Cu-Be[4] , Cu-Zr-Ti-Be[5] , Nd-
Al-Fe[6] , Ce-Al-Ni-Cu[7] , RE55 Al25 Co20 [8] were devel-
oped. Rare-earth-based alloys are known as the ma-
terials with particular magnetic properties, for exam-
ple, the compounds Gd(Zn1−x Cdx ) with good magne-
tocaloric effect[9] . Liang et al. found that GdDyAlCo
bulk metallic glasses had the larger refrigerating ca-
pacities (RC) than those of conventional crystalline
materials[10] . However, the effect of intrinsic parame-
ters on formation ability of Dy(Gd)-based bulk amor-
phous alloys is unknown. In this work, a series of
Dy(Gd)-based bulk metallic glasses (BMG) formed in
Dy-Gd-Co-Al alloys were revealed, and the reason for
high glass-forming ability (GFA) was also discussed.
These studies may be significant for designing other
new bulk amorphous alloys.
2. Experimental
Ingots with nominal compositions of
Dy56−x Gdx Co20 Al24 (x=0, 10, 15, 22, 25, 28, 31,
41 and 56 at. pct), Dy51−y Gd25 Coy Al24 (y=15, 18,
20 and 23 at. pct) and Dy55−z Gd25 Co20 Alz (z=20,
22, 24, 26 and 28 at. pct) were prepared by arc
melting the mixture of pure metals (Dy, Gd, Co
and Al) with a purity of more than 99.5 wt pct
under a Ti-gettered argon atmosphere (99.999%).
The ingots were remelted at least four times to en-
sure the homogeneity of the multicomponent alloys.
The pre-alloyed ingots were arc-melted once again
and then were suck-cast into a water-cooled copper
mold to obtain cylindrical rods. The structure of
the as-cast alloys was identified by X-ray diffraction
(XRD) using a D/max-rc diffractometer with Cu-
Kα radiation.Thermal properties were investigated
† Corresponding author. Prof., Ph.D.; Tel.: +86 21 56331484;
E-mail address: xsxiao@mail.shu.edu.cn (X.S. Xiao).
(DSC) at a heating rate of 0.33 K/s under pure argon
atmosphere.
3. Results and Discussion
The XRD patterns and DSC curves of as-cast
Dy56−x Gdx Co20 Al24 (x=0, 10, 15, 22, 25, 28, 31, 41,
56 at. pct) with a diameter of 1 mm are shown in
Fig. 1. The XRD patterns in Fig. 1(a) for the al-
loys of Dy56−x Gdx Co20 Al24 (x=22, 25, 28, 31, 41 at.
pct) consists only of a broad diffused scattering peak,
with no evidence of any crystalline Bragg peaks within
the detectable limitation of the XRD, which indicates
that they are completely amorphous structure. While
a few sharp diffraction peaks corresponding to crys-
talline phase superimposed on the broad amorphous
peaks are observed for the others, indicating that they
are partially amorphous with a significant fraction of
crystalline phases. In Fig. 1(b), all curves exhibit an
obvious endothermic heat event characteristic of the
glass transition, followed by a broad supercooled liq-
uid region and then exothermic reactions due to crys-
tallization. Tg (glass transition temperature, defined
as the onset temperature of the endothermic event),
and Tx (the onset crystallization temperature) appear
in succession on the DSC curves. ∆Tx (=Tx −Tg ,) is
referred to as the width of supercooled liquid region.
With the increase in Gd content from 0 at. pct to
56 at. pct, both Tg and Tx gradually decreases grad-
ually from 627.6 K to 588.7 K for Tg and from 682 K
to 643.5 K for Tx , respectively. While the ∆Tx first
increases from 54.4 K to 62.4 K, and then decreases
to 54.8 K.
Figure 2(a) shows the XRD patterns of the as-cast
Dy51−y Gd25 Coy Al24 (y=15, 18, 20, 23 at. pct) sam-
ples with a diameter of 1 mm. Only a broad peak
for y=20 alloy exists while there are appreciable dif-
fraction peaks that may correspond to some small
crystalline phases for y=15, 18, 23 alloys. The DSC
curves of the as-cast Dy51−y Gd25 Coy Al24 (y=15, 18,
20, 23 at. pct) are shown in Fig. 2(b). The alloys
have two crystallization peaks for y=15, 18, 20 alloys
while there is only one crystallization peak for y=23
alloy. With the increase of Co content, Tx gradu-
ally increases while the ∆Tx first increases from 20 K
(y=15) to 62 K (y=20) and then decreases to 55 K
666 J. Mater. Sci. Technol., Vol.25 No.5, 2009

(a) Dy Gd Co Al (a)
56-x x 20 4 Dy Gd Co Al
51- y 25 y 24

x=56

x=41 y=23

Intensity / a.u.
Intensity / a.u.

x=31
y=20
x=28

x=25 y=18
x=22

x=15 y=15

x=10
20 30 40 50 60 70 80
x= 0
2 / deg.

20 30 40 50 60 70 80

2 / deg.

(b) 0.33 K/s Dy Gd Co Al

y
51- 25 y 24

0.33 K/s
(b)
T T Dy
56- x
Gd Co Al
x 20 24
y=23
x=56

Exothermic / a.u.
x
g

x=41
x=31
Exothermic / a.u.

x=28 y=20
x=25 Tg T
y=18
x

x=22
x=15
x=10 y=15
x=0

450 500 550 600 650 700 750 800 850

T/K
450 500 550 600 650 700 750 800 850

T/K
Fig. 1 X-ray diffraction patterns and DSC curves of the Fig. 2 X-ray diffraction patterns and DSC curves of as-
as-cast Dy56−x Gdx Co20 Al24 (x=0, 10, 15, 22, 25, cast Dy51−y Gd25 Coy Al24 (y=15, 18, 20, 23 at.
28, 31, 41, 56 at. pct) alloys with a diameter of pct) with a diameter of 1 mm: (a) X-ray diffrac-
1 mm: (a) X-ray diffraction patterns, (b) DSC tion patterns, (b) DSC curves
curves
n−1
X n
X
(y=23). chem chem
The XRD patterns of the as-cast ∆Hamor = ci · cj · ∆Hij (2)
i=1 j=i+1
Dy55−z Gd25 Co20 Alz (z=20, 22, 24, 26, 28 at.
pct) samples with a diameter of 1 mm are shown n
X
in Fig. 3(a). The XRD curve shows a typical ∆H topo = (3.5 i
Ci Tm )/1000 (3)
broad halo pattern of an amorphous structure for i=1
Dy55−z Gd25 Co20 Alz (z=20, 22, 24, 26, 28 at. pct) n−1 n
alloys. From the DSC curves shown in Fig. 3(b), the X X
form chem
∆Hamor = Ci Cj ∆Hij +
crystallization peaks reduce with the increase of Al
i=1 j=i+1
content, which suggests that Al content would change
n
X
the crystallization behavior. Tg increases slightly i
while Tx increases significantly, the ∆Tx increases (3.5 Ci Tm )/1000 (4)
from 28 K for z=20 to 74 K for z=26, and then i=1

decreases to 55 K for z=28. form

where ∆Hamor is the amorphous formation enthalpy;
As mentioned above, a new series of Dy-Gd-Co-Al chem
∆Hamor is chemical part of amorphous formation en-
metallic glasses with a diameter of 1 mm have been thalpy; ∆H topo is topological part of amorphous for-
fabricated, and the results show that alloy compo- chem
mation enthalpy; ∆Hij is the chemical enthalpy
nents played an important role in the glass-forming between element i and j; Ci is the atomic percentage
ability. Meanwhile, intrinsic parameters are deter- i
of the element i. and Tm is the melting point of the
mined by alloy components. Many scientists have element i.
tried to find out the interrelation between glass form- While
ing ability and intrinsic parameters of alloys such as R
chem
electronegativity, atomic size or atomic arrangement ∆Hij = fjs ∆Hiint s
ln j + fi ∆Hj ln i (5)
on the view of chemistry and topology. According to
Miedema0 s theory, the formation enthalpy of amor- fjs = xsi [1 + σ(xsi xsj )2 ] (6)
phous alloys in multicomponent alloys could be esti- 2/3
mated as follows[11–13] : ci Vi
xsj = 2/3 2/3
(7)
ci Vi + cj Vj
form chem
∆Hamor = ∆Hamor + ∆H topo (1)
 J. Mater. Sci. Technol., Vol.25 No.5, 2009 667

(a) Dy Gd Co Al
55-z z -24 Dy
xGdxCo20Al24
25 20
56-

Dy
yGd25CoyAl24
51-

z=28 -26 Dy
zGd25Co20Alz
55-

/ (kJ/mol)
Intensity / a.u.

-28
z=26

form
-30
z=24

H amor
z=22 -32

x=20 -34

0 10 20 30 40 50 60

20 30 40 50 60 70 80 Atomic percent / %
2 / deg.

Fig. 4 Relationship between the amorphous formation

enthalpy and components of Dy-Gd-Co-Al alloys
(b) 0.33 K/s Dy
z
55-
Gd C
25
o20
Al
z
z=28 decrease gradually with increasing Co or Al content
for Dy51−y Gd25 Coy Al24 (y=15, 18, 20, 23 at. pct)
xothermic / a.u.

z=26 and Dy55−z Gd25 Co20 Alz (z=20, 22, 24, 26, 28 at.
pct) alloys. The phenomenon above suggests that the
amorphous alloys can form only when the amorphous
z=24 formation enthalpies of alloys are moderate, or else
Tg Tx compounds or solid solutions may be formed.
z=22 In order to further clarify the relationship between
E

the intrinsic parameters and glass forming ability in

z=20 multi-component alloys, the equivalent bond parame-
ters among atoms such as the equivalent electronega-
tivity difference and the equivalent atomic size differ-
450 500 550 600 650 700 750 800 850
ence ∆X are defined as follows[14] :
v
T/K u n
uX
Fig. 3 X-ray diffraction patterns and DSC curves of as- ∆X = t Ci (Xi − X̄)2 (9)
cast Dy55−z Gd25 Co20 Alz (z=20, 22, 24, 26, 28 at. i=1
pct) with a diameter of 1 mm: (a) X-ray diffrac-
tion patterns, (b) DSC curves v
u n
uX ri
δ=t Ci (1 − )2 (10)
i=1
r̄
(Vi )2/3
∆Hiint
ln j = ³ ´ {−P (∆ϕ)2
where n is the number of components of the alloy; Xi
1 1
2
n
1
1/3
+
n
1
1/3 and ri are, respectively, the Pauling electronegativity
wsi wsi
and atomic radius of element i, which is obtained from
+ Q(∆n1/3 2 ∗
ws ) − R ∗ P } (8) literature [15–18], Ci is the atomic percentage of the
element i in the alloy, Xi is the electronegativity of
where ∆Hiint
is the interfacial enthalpy for element
ln j the element i, X̄ and and r̄ are the arithmetic mean
i, solved in infinite dilution in element j; fis is order
value of electronegativity and atom radius of the alloy.
parameter; Vi is the atomic volume of element i; xsi
is surface coefficient; σ is the short-range order con- n
X
1/3
stantfor amorphous alloys σ=5; ∆nws is the electron X̄ = Ci · Xi (11)
1/3 i=1
concentration difference; nwsi is the electron concen-
tration of element i; P , Q are experimental constants; n
X
∆ϕ is work function difference; ∆ϕ and R∗ is the in- r̄ = Ci · ri (12)
teraction parameter of d-p electrons. i=1
Relationship between the amorphous for- Because coordination number (Zi ) can effect the
form
mation enthalpy ∆Hamor and components of equivalent electronegativity difference of multi-
Dy56−x Gdx Co20 Al24 (x=0, 10, 15, 22, 25, 28, 31, component alloys and it was not considered in Eq. (9),
41, and 56 at. pct), Dy51−y Gd25 Coy Al24 (y=15, 18,
so it was amended by Fang et al.[19] later as follows:
20 and 23 at. pct), Dy55−z Gd25 Co20 Alz (z=20, 22,
v
24, 26 and 28 at. pct) alloys is shown in Fig. 4. It u n
can be seen that the formation enthalpies of amor- uX
∆X = t Zi · Ci (1 − Ci ) · (Xi − X̄)2 (13)
phous alloys decrease firstly and then increase for i=1
Dy56−x Gdx Co20 Al24 (x=0, 10, 15, 22, 25, 28, 31,
41, and 56 at. pct), and reaches a minimum value h √ i ³ ´
form
∆Hamor of −33.8 KJ/mol at x=28 at. pct, which 4π 1 − 23 1.68 × rr̄i + 1
Zi = √ = r ³ ´ (14)
may mean that their glass-forming ability increases ri (ri +2r̄)
firstly, and then declines with the increase of Gd con- 1− ri +r̄
ri
+ 1 − rr̄i rr̄i + 2
r̄
tent. The formation enthalpies of amorphous alloys
668 J. Mater. Sci. Technol., Vol.25 No.5, 2009

best glass-former in multi-component alloys results

0.86
1 Dy
56

2 Dy
Co

Gd
20
Al

Co
24

Al
from the mutual interaction of the intrinsic parame-
12
Bulk metallic glasses
ters. So the Dy31 Gd25 Co20 Al24 alloy can be cast into
46 10 20 24

3 Dy Gd Co Al
41 15 20 24

0.84
4
6
7 15
16
4 Dy
34

5 Dy
Gd

Gd
22
Co

Co
20
Al

Al
24
full glassy rods up to 5 mm in diameter. Figure 6
13

shows the photograph and X-ray diffraction pattern

31 25 20 2

5
14 8 6 Dy Gd Co Al
28 28 20 2
0.82

of Dy31 Gd25 Co20 Al24 alloy with a diameter of 5 mm.

3 11 7 Dy Gd Co Al
25 31 20 24

2 8 Dy Gd Co Al
15 41 20 24

Nocrystalline peaks occur in the cure, which indicates

X

0.80 9 Gd Co Al
56 20 24

10 Dy Gd Co Al

that a full amorphous structure is formed.

10 36 25 15 24

11 Dy Gd Co Al
0.78 9 33 25 18 24

12 Dy Gd Co Al
28 25 23 24

0.76
1
13 Dy

14 Dy
35
Gd

Gd
25
Co

Co
20
Al

Al
24
4. Conclusions
33 25 20 22

15Dy Gd Co Al

0.74
0.128 0.130 0.132 0.134 0.136 0.138
16 Dy
29

27
Gd
25

25
Co
20

20
26

Al
28
A series of bulk metallic glasses of Dy-Gd-Co-Al
alloys with diameters of at least 1 mm were suc-
Fig. 5 Relationship among amorphous formation-ability, cessfully fabricated by conventional Cu-mold casting
equivalent atomic size parameter and equivalent method. The glass-forming ability of the Dy-Gd-Co-
electronegativity difference in Dy-Gd-Co-Al alloys Al alloys was controlled by intrinsic parameters of al-
loys such as the equivalent electronegativity difference
∆X, the equivalent atomic size parameter δ and the
form
amorphous formation enthalpy ∆Hamor . The ∆X, δ
form
and ∆Hamor in a certain range will be helpful for the
amorphous forming ability. The intrinsic parameters
are effective on studying the glass-forming ability of
multicomponent alloys.

Acknowledgements
The authors are grateful for the financial support of
the National Natural Science Foundation of China (No.
50571054).
(b)

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Fig. 6 The photograph (a) and XRD pattern (b) of
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