APPLIED PHYSICS LETTERS VOLUME 79, NUMBER 8 20 AUGUST 2001

Pressure-induced amorphization of ZrTiCuNiBe bulk glass-forming alloy

Wei Hua Wang,a) R. J. Wang, D. Y. Dai, D. Q. Zhao, M. X. Pan, and Y. S. Yao
Institute of Physics and Center for Condensed Matter Physics, Chinese Academy of Sciences, P. O. Box
603, Beijing 100080, People’s Republic of China
共Received 27 December 2000; accepted for publication 29 June 2001兲
Zr41Ti14Cu12.5Ni10Be22.5 alloy can be cooled under high pressure 共HP兲 to a bulky glassy state at very
low cooling rates. The structure and properties of the bulk metallic glass 共BMG兲 are investigated by
differential scanning calorimetry, x-ray diffraction, ultrasonic study, and density measurements. The
effects of pressure on the glass formation are discussed from the points of view of nucleation
kinetics and thermodynamics. The BMG obtained under HP is in a high-density amorphous state
that is different in structure and property from low-density amorphous phase quenched in water.
Solidification under HP is a promising way not only for synthesizing BMGs with more densely
packed structures and different properties, but also for understanding the glass formation
mechanism. © 2001 American Institute of Physics. 关DOI: 10.1063/1.1396321兴

The recent discovery of complex multicomponent bulk
metallic glasses 共BMGs兲 with excellent glass forming ability
共GFA兲 and physical properties is exciting for both fundamen-
tal and practical reasons.1– 4 A Zr41Ti14Cu12.5Ni10Be22.5 glass-
forming system represents one such group of the BMGs.2
The BMG containing five constituents with significantly dif-
ferent atomic sizes is of high viscosity in melt, and a long-
range diffusion is very difficult. However, since the BMG
crystallizes to crystalline phases with composition and local
microstructure different from that of the glassy state, redis-
tribution by long-range diffusion is required for the
crystallization.4 These characteristics make the crystalliza-
tion in the supercooled liquid region very difficult, and the
alloy is of excellent GFA.4,5 High pressure 共HP兲 can be ap-
plied to control the nucleation and growth in the BMGs.6 It is
found that HP annealing facilitate the synthesis of very fine-
grained nanostructural bulk nanocrystalline alloys by con-
trolling the nucleation and growth.7 On the other hand, the
application of pressure causes the melting point of most al-
loys to increase and leads to a larger undercooling of the
liquid alloy. The applied pressure can also suppress the
nucleation and growth of the undercooling melts. Therefore,
applied pressure during the solidification process of a glass-
forming alloy may improve the GFA, and provide a useful
way to study the formation mechanism of the BMG. In
this work, the effects of HP on the GFA of the
Zr41Ti14Cu12.5Ni10Be22.5 glass-forming alloy are studied. The
ultrasonic study, density measurement, differential scanning
calorimetry 共DSC兲, and x-ray diffraction 共XRD兲 are used to
monitor the microstructural and property differences.
Ingot with a nominal composition of
Zr41Ti14Cu12.5Ni10Be22.5 was prepared by melting a mixture
of elements in a Ti-gettered arc furnace, and remelted in a
vacuum-sealed quartz tube, and then quenched in water to
get a rod with a diameter of 12 mm. The amorphous nature
as well as the homogeneity of the rod was ascertained by
a兲
Author to whom correspondence should be addressed; also at National
Microgravity Laboratory of Chinese Academy of Sciences, 100080
Beijing, People’s Republic of China; electronic mail:
whw@aphy.iphy.ac.cn
XRD, transmission electron microscope, reduced density
function analyses.5,8 The rod was machined down to 10 mm
in diameter for removing any possible oxide materials from
the quartz tube container. The rod was cut to a cylinder with
a length of 8 mm for HP melting and cooling. HP was per-
formed in an apparatus with six anvils. Hexagonal boron
nitride (h-BN) powder was used as pressure transmitting
medium. NiCr–NiAl thermocouple was brought into the
pressurized zone and near the sample. The pressure was cali-
brated by the phase transition of known materials of Pb and
Bi, the accuracy was better than ⫾0.1 GPa. The accuracy of
measuring the temperature of the sample itself under applied
pressure was about ⫾3 K. The sample was first pressurized
to high pressure, and then heated to 1373 K and kept in these
conditions for 10 min, and then the heating electrical current
was switched off and the sample was naturally cooled under
HP. Because the sample was covered with thick pyrophyllite
and h-BN with low thermal conductivity, the solidifying heat
release condition for the molten sample was very poor. The
cooling rate was estimated to be about 1 K/s. The details of
the HP experiment were described in Ref. 7. The structure of
the samples were checked by XRD, density, ultrasonic, and
DSC. XRD was performed using a MAC M03 XHF diffrac-
tometer with Cu K ␣ radiation. DSC measurements were car-
ried out under a purified argon atmosphere in a Perkin–
Elmer DSC-7 at a heating rate of 0.33 K/s. Density ␳ was
measured by the Archimedian principle and the accuracy was
evaluated to be 0.005 g/cm3 . The Vicker’s hardness, H ␯ ,
was measured with a Newphoto-21 microhardness tester at a
load of 200 g. For ultrasonic measurements, the ends of the
cylinder were carefully polished flat and parallel. The acous-
tic velocities were measured by using a pulse echo overlap
method.9 The travel time of ultrasonic waves propagating
through the sample with a 10 MHz frequency was measured
using a MATEC 6600 ultrasonic system with a measuring
sensitive of 0.5 ns.
Figure 1 shows XRD patterns of the
Zr41Ti14Cu12.5Ni10Be22.5 alloy with diameter of 10 mm
cooled under various pressures. For comparison, the XRD
trace for the alloy cooled at roughly the same cooling rate at

0003-6951/2001/79(8)/1106/3/$18.00 1106 © 2001 American Institute of Physics

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Appl. Phys. Lett., Vol. 79, No. 8, 20 August 2001
FIG. 1. XRD patterns of the Zr41Ti14Cu12.5Ni10Be22.5 alloy with diameter of
10 mm cooled under various pressures and the alloy with diameter of 10 mm
cooled at roughly the same cooling rate at ambient pressure for comparison
are shown.
ambient pressure in HP apparatus is also presented. The
samples with applied pressure show a broad scattering peak
indicating the formation of amorphous phase, there are few
weak sharp crystalline peaks superimposing on the broad
peak with a fraction about 10%. However, the sample cooled
in the same cooling rate without applied pressure shows only
sharp crystalline peaks demonstrating that the alloy mostly
consists of crystalline phases, because the cooling rate for
this method is about 1 K/s, and much less than the critical
cooling rate for the fully glassy formation of 10 K/s2 . XRD
results indicate that the GFA of the Zr41Ti14Cu12.5Ni10Be22.5
alloy is enhanced under HP.
Figure 2 exhibits DSC traces of the
Zr41Ti14Cu12.5Ni10Be22.5 alloy quenched in water, and cooled
with and without applied pressure in HP apparatus. The alloy
cooled without pressure in HP apparatus shows no heat re-
lease during the continuous heating process confirming no
amorphous phase in the alloy. Both the DSC traces of alloys
quenched in water and under 6 GPa exhibit endothermic
characteristic of a glass transition followed by exothermic
crystallization reactions at higher temperature. However, the
glass transition temperature T g , crystallization temperature
T x , and supercooled liquid region, ⌬T⫽T x ⫺T g , are notice-
able different for the alloys. The T g , T x , and ⌬T for the
alloy quenched in water 共alloy A兲 are 623 K, 697 K, and 74
K respectively. For the alloy cooled under 6 GPa 共alloy B兲,
the T g , T x , and ⌬T are 633 K, 707 K, and 74 K, respec-
TABLE I. A comparison of properties (Y a ) of the Zr41Ti14Cu12.5Ni10Be22.5 BMG obtained by water quenched
共alloy A兲, and properties (Y HP) of the BMG obtained under HP 共cooled from 1373 K under 6 GPa兲 共alloy B兲 is
presented.
␳ ␯l
Sample (g/cm3 ) 共km/s兲
Alloy A 6.108 5.13
Alloy B 6.181 5.30
(Y HP⫺Y a )/Y a (%) 1.2 3.3
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Wang et al. 1107
FIG. 2. DSC traces of the Zr41Ti14Cu12.5Ni10Be22.5 alloy quenched in water,
and quenched in HP apparatus with and without applied high pressure are
shown.
tively. The T g and T x of alloy B are increased, indicating that
the amorphous phase is more stable.
To compare the structural and property differences be-
tween the two BMGs, the density ␳, microhardness, and the
acoustic velocities, which are particularly sensitive to the
microstructural change and properties, were measured for al-
loys A and B. Table I gives a comparison of the properties
(Y a ) of alloy A, and properties (Y HP) of alloy B. It contrasts
the large increases in ␳ 共1.2%兲, ␯ s 共11.5%兲, ␪ D 共11.5%兲, G
共about 26.0%兲 and H ␯ 共22%兲, and small changes in ␯ l
共3.3%兲 and K 共0.4%兲 for alloy B relative to alloy A. The
results indicate the marked differences in structure and prop-
erties between the two BMGs. 11.5% increase in ␯ s and ␪ D ,
and 25.8% increase in G of alloy B indicate stiffness of shear
elastic modulus 共i.e., the stiffness of the transverse phonons兲
relative to alloy A. The relative density increase of alloy B is
1.2%. Previous work10 shows that the fully crystallized
Zr41Ti14Cu12.5Ni10Be22.5 BMG has only 1.1% density in-
crease relative to the as-prepared BMG. The result indicates
that the BMG obtained under HP has high density or highly
denser randomly packed microstructure, the observed density
increase under HP could also be simply due to reduce the
formation of voids and free volume during solidification. A
number of experiments show a wide range of low density
amorphous to high density amorphous transition induced by
HP, in other words, coordination change could happen in
amorphous materials.11–13 The change of short-range order
and existence of different polymorphs were well documented
for pressure induced nonergodic manifestation of a transfor-
␯s G K ␪D H␯
共km/s兲 GPa GPa K GPa
2.43 36.1 112.6 321.2 5.9
2.71 45.4 113.1 358.1 7.2
11.5 25.8 0.4 11.5 22.0
1108 Appl. Phys. Lett., Vol. 79, No. 8, 20 August 2001
mation. The most intriguing question is that if there exist
so-called low density amorphous phase and high density
amorphous phase in the BMG and if the BMG undergoes a
phase transition from low density amorphous phase to high
density amorphous phase upon pressure. The distinct proper-
ties change appears to provide evidence for supporting the
existence of two possibly amorphous states in the BMG. The
changes of alloy B in ␯ s , ␪ D , and G relative to alloy A are
comparable to those induced by fully crystallization 共The
changes of the fully crystallized state in ␯ s , ␪ D , and G
relative to the as-prepared BMG are 11.4%, 11.4%, and 26%,
respectively兲.10 Such similarities in the marked properties
and density changes between crystallization and the BMG
obtained under HP also suggest that there may exist amor-
phous to amorphous transformation upon HP in the BMG.
Our previous work14 shows that a transition between short-
range order to medium-range order occurs when annealed the
BMG under HP. However, more work should be done to
elucidate the question.
In HP solidification, pressure can cause the annihilation
of the free volume, reduce voids through compressing the
melt structure, and increase the viscosity of the melt.15,16 The
nucleation, especially the growth in the melt, is more diffi-
cult because the redistribution of atoms and the subsequent
growth of the nucleation sites in the melt is inhabited by the
extremely slow atomic mobility. This leads to the increased
GFA of the alloy. The highly packed microstructure of the
BMG obtained under HP is of extremely slow atomic mobil-
ity and makes high resistance against crystallization, and re-
sults in high thermal stability. The pressure enhanced GFA of
the alloy can also be understood in thermodynamics. Accord-
ing to the Clausius–Clapeyron equation, the application of
pressure causes the melting temperature of most alloys to
increase:17
⌬T T m 共 V l ⫺V s 兲
⫽ , 共1兲
⌬P ⌬H m
where, ⌬T and ⌬ P are increases of temperature and pres-
sure, respectively, T m , the equilibrium melting temperature,
V l and V s are the specific volumes of the liquid and solid,
respectively, and ⌬H m , the heat of fusion. For the
Zr41Ti14Cu12.5Ni10Be22.5 alloy, T m ⫽937 K, ⌬H m ⫽6.6
kJ/mol3 , the volume difference between liquid and solid is
about 1%.18 So, at 6 GPa, ⌬T is estimated to be about 100 K.
The increase of melting temperature under HP has been con-
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Wang et al.
firmed in our experiments. The equilibrium T m increases
with the increasing pressure and leads to larger undercooling
of the liquid alloy. According to the classic nucleation theory,
the nucleation activation energy ⌬G * and growth rate of the
nuclei are closely related to the undercooling.19,20 The high
undercooling induced by HP may lead to higher activation
energy and slow growth rate for nucleation during the solidi-
fication. This suppresses the nucleation of crystalline phases
and results in high GFA.
In conclusion, the Zr41Ti14Cu12.5Ni10Be22.5 alloy has im-
proved GFA when quenched under HP. The BMG obtained
under HP exhibits denser microstructure, higher density, and
enhanced thermal stability. The BMG also shows marked
differences in acoustic, elastic, and mechanical properties.
Our results indicate that there exists the so-called low density
amorphous phase and high density amorphous phase in the
BMG upon pressure. Solidification under HP is a promising
way for synthesizing BMGs.
The authors are grateful for the financial support of the
National Natural Science Foundation of China 共Grant Nos.
59925101, 50031010, 59871059, and 19874075兲.
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