CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 33 (2009) 478–486
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CALPHAD: Computer Coupling of Phase Diagrams and
Thermochemistry
journal homepage: www.elsevier.com/locate/calphad
A critical thermodynamic assessment of the Mg–Ni, Ni–Y binary and Mg–Ni–Y
ternary systems
Mohammad Mezbahul-Islam, Mamoun Medraj
*
Department of Mechanical Engineering, Concordia University, 1455 de Maisonneuve Blvd. West, H3G 1M8, Montreal, Canada
article info
Article history:
Received 19 August 2008
Received in revised form
5 January 2009
Accepted 5 January 2009
Available online 17 January 2009
Keywords:
Thermodynamic modeling
Modified quasichemical model
Mg-alloys
Hydrogen storage
Metallic glass
abstract
A thorough review and critical evaluation of phase equilibria and thermodynamic data for the phases
in the Mg–Ni–Y ternary system have been carried out over the entire composition range from room
temperature to above the liquidus. This system is being modeled for the first time using the modified
quasichemical model which considers the presence of short range ordering in the liquid. The Gibbs
energies of the different phases have been modeled, and optimized model parameters that reproduce all
the experimental data simultaneously within experimental error limits have been obtained. For the liquid
phases, the modified quasichemical model is applied. A sublattice model within the compound-energy
formalism is used to take proper account of the structures of the binary intermediate solid solutions. The
Mg–Ni and Ni–Y binary systems have been re-optimized based on the experimental phase equilibrium
and thermodynamic data available in the literature. The optimized thermodynamic parameters for the
Mg–Y system are taken from the previous thermodynamic assessment of the Mg–Cu–Y system by the
same authors. The constructed database has been used to calculate liquidus projection, isothermal and
vertical sections which are compared with the available experimental information on this system. The
current calculations are in a good agreement with the experimental data reported in the literature.
© 2009 Elsevier Ltd. All rights reserved.
1. Introduction
Batteries can be a useful source of energy for spacecraft,
military and defense, communication, power tools and consumer
appliances because of their ability to store energy in a clean,
convenient and efficient manner and hence there is a growing
need for high-specific power, high-specific energy and low-cost
batteries [1]. Currently nickel/cadmium rechargeable batteries are
commonly used for these purposes. But due to the relatively
low capacity and environmental concerns more efficient and safe
substitutes for cadmium are urgently needed. The nickel-metal
hydride battery (MH) with a hydrogen storage alloy as a negative
electrode has shown a high potential in that aspect [1,2]. That
is why extensive attention has been paid to the utilization of
magnesium-based alloys as hydrogen storage materials owing
to their high storage capacity and low specific weight [3]. The
Mg–Ni–Y system is considered to be one of the promising
candidates [1]. Besides, this ternary is one of the promising Mg-
based metallic glass systems [4]. Hence it is becoming clear that a
detailed investigation on this system is needed.
The aim of the present work is to provide a comprehensive crit-
ical thermodynamic evaluation and optimization of the Mg–Ni–Y
system over the entire composition range from room tempera-
*
Corresponding author.
E-mail address: mmedraj@encs.concordia.ca (M. Medraj).
ture to liquidus temperature. Two of the three constituent binaries,
Mg–Ni and Ni–Y, have been optimized using the modified quasi-
chemical model [5–7] for the liquid phase. The Mg–Y system was
optimized earlier by the same authors [8] and the model parame-
ters have been used directly in this work. The Toop [9] geometric
model with Mg as the asymmetric component has been used for
the extrapolation of the binaries to the ternary system.
2. Literature review
2.1. Ni–Y system
The phase diagram of the Ni–Y system was first investigated
by Beaudry and Daane [10] and later by Domagala et al. [11].
Beaudry and Daane [10] used metallographic, thermal analysis
and X-ray diffraction (XRD) methods in their investigation and
reported the existence of nine intermetallic compounds; NiY
3
,
Ni
2
Y
3
, Ni
2
Y, Ni
3
Y, Ni
7
Y
2
, Ni
4
Y, Ni
17
Y
2
, NiY and Ni
5
Y. Except for the
last two, all other compounds undergo peritectic decomposition.
Domagala et al. [11], however, reported eight compounds and
missed the existence of Ni
7
Y
2
. However, another investigation
by Buschow [12] on several phases of the Ni–RE (RE =
rare earth) showed that an Ni
7
RE
2
phase occurs in all the heavier
Ni–RE systems. So the existence of the Ni
7
Y
2
compound in
the Ni–Y system is consistent with the general trend and has
been included in this work. Domagala et al. [11], also, disagreed
0364-5916/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.calphad.2009.01.001