Materials Research Bulletin 95 (2017) 300–306

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Thermal reliability of Al-Si eutectic alloy for thermal energy storage

Zhengyun Wanga,b , Hui Wangc, Mei Yangb , Wenwen Sunb , Guangfu Yina,* ,
Qinyong Zhangb,* , Zhifeng Renc,*
a
College of Materials Science and Engineering, Sichuan University, Chengdu, Sichuan 610065, China
b
Key Laboratory of Fluid and Power Machinery of Ministry of Education & Center for Advanced Materials and Energy, Xihua University, Chengdu, Sichuan
610039, China
c
Department of Physics and TcSUH, University of Houston, Houston, TX 77204, USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 17 May 2017 The thermal reliability of Al-Si eutectic alloy as phase change materials (PCMs) was investigated through
Received in revised form 6 July 2017 vacuum thermal cycling 250, 500, 750, and 1000 times going through the solid-liquid phase change. The
Accepted 26 July 2017 changes in thermal properties of Al-Si eutectic alloy, including melting point, latent heat, specific heat,
Available online 3 August 2017 thermal diffusivity and thermal conductivity, were investigated using differential scanning calorimetric
(DSC) and laser flash apparatus. The results revealed that, with increasing the number of cycles, the
Keywords: melting point and latent heat of fusion of the Al-Si eutectic alloy showed almost no changes. Moreover,
Al-Si eutectic alloy the thermal conductivity showed an outstanding stability after 1000 thermal cycles. Therefore, it is
Phase change material
concluded that the thermal reliability of Al-Si eutectic alloy is more than adequate for long-term
Thermal energy storage
performance as a phase change material for thermal energy storage (TES) applications.
Thermal cycles
Thermal reliability © 2017 Elsevier Ltd. All rights reserved.

1. Introduction
In order to slow down the increasing of the global warming gas
emissions, various sources of renewable energy have been studied
[1–9], for which the so-called low-grade waste heat or solar
generated heat, is being considered as promising [2,8–12].
Among the various ways of solar energy utilization, concen-
trating solar power (CSP) technology, which uses phase change
materials for thermal energy storage, is one of the most important
options to produce electricity [2,8,11,13–15]. It is well known that
because of the large amount of thermal energy stored by the phase
transition materials with a constant temperature, the using of
PCMs in CSP plants is capable to provide the electricity generation
at the time when the peak demand of electricity comes in [16]. In
terms of the economic benefits, successful implementation of the
CSP plants also depends very much on the availability of low cost
heat storage solutions, which allowing smoothing the operation of
the solar generated plant over a long time period [17]. Therefore,
the attractive technology of TES, especially the high temperature
* Corresponding authors.
E-mail addresses: nic0700@scu.edu.cn (G. Yin), bohr123@163.com (Q. Zhang),
zren@uh.edu (Z. Ren).
TES, would play a more and more important role in CSP plants even
though it is one of the systems less developed.
Utilization of heat storage with high-temperature PCMs for the
CSP applications, as many researchers believe, will considerably
increase the efficiency of solar energy utilization [18]. The thermal-
physical properties of several perspective metals and alloys have
been reported when they were used as high-temperature PCMs
[19–24]. In the past a few decades, because of the suitable phase
change temperature, high solid-liquid latent heat density, Al-Si
eutectic alloy was intensely investigated as PCM in high-
temperature TES systems [25–27]. However, as the high-tempera-
ture PCMs used in CSP, the influence of thermal cycling on the
thermal-physical properties of Al-Si eutectic alloy were indispens-
able but have been rarely reported. Therefore, it is necessary to
study the performance reliability of Al-Si eutectic alloy upon
thermal cycling for the long life span of CSP plants.
Five Al-Si eutectic samples as high-temperature PCMs were
prepared by arc-melting for thermal cycling test. The main
objective of this paper is to investigate the change of important
physical properties of the material in detail, including the melting
temperature, the latent heat of the solid-liquid phase transition,
and the temperature-dependent thermal conductivity. Combined
with microstructure and SEM morphology analysis, the long-term
thermal cycling performance of Al-Si eutectic alloy under the
simulated conditions of CSP plants was studied.

http://dx.doi.org/10.1016/j.materresbull.2017.07.040
0025-5408/© 2017 Elsevier Ltd. All rights reserved.
 Z. Wang et al. / Materials Research Bulletin 95 (2017) 300–306 301

Fig. 1. The microstructure of Al-Si eutectic alloy after different number of thermal cycles: (a) 0 time, (b) 250 times, (c) 500 times, (d) 1000 times.

2. Experimental description Aesar) were weighed accordingly. In order to ensure the

2.1. Preparation of samples
Al-12.2Si eutectic alloy (atomic ratio) was prepared by arc-
melting, and then the samples were used for thermal cycling test.
Pure Al (shot, 99.999%, Alfa Aesar) and pure Si (bulk, 99.9999%, Alfa
composition homogeneous, each sample was melted for five
times by arc-melting. The whole arc-melting process was
conducted under the protection of argon gas. Before the thermal
cycling test, the as-melted samples were vacuum-sealed in quartz
tubes and annealed for 100 h in a muffle furnace at 550  C. Then the
five annealed samples were heated from 500  C to 650  C with

Fig. 2. The crystalline phase of Al-Si eutectic alloy analyzed by XRD after cycling of 250, 500, 750, and 1000 times.
302 Z. Wang et al. / Materials Research Bulletin 95 (2017) 300–306

Fig. 3. The melting temperature and latent heat of Al-Si eutectic alloy measured by DSC after thermal cycles of 250, 500, 750, and 1000 times.

10  C min 1 and then cooled to the temperature of 500  C with 250) respectively, and the crystalline phases were analyzed by X-
6  C min 1 for the 250, 500, 750, and 1000 times thermal cycles. ray diffraction (XRD, Bruker D2).

2.2. Microstructure, morphology and crystalline phase observation 2.3. Phase change characterization

The Al-Si eutectic samples after different number of thermal
cycles were polished and lightly etched, their microstructure and
surface morphology were observed by optical microscope (Olym-
pus-Tokyo) and scanning electron microscopy (SEM, Quanta FEG
The thermal properties including the melting temperature and
solid-liquid phase change latent heat of the Al-Si eutectic alloy
after different number of thermal cycles were investigated by a
differential scanning calorimetry thermal analyzer (Netzsch DSC
404C). Around 15 mg of each sample was used for DSC

Fig. 4. The structure morphology of Al-Si eutectic alloy after different number of thermal cycles: (a) 0 time, (b) 250 times, (c) 500 times, (d) 1000 times.
 Z. Wang et al. / Materials Research Bulletin 95 (2017) 300–306 303

Fig. 5. The specific heat dependence of temperature of Al-Si eutectic alloy measured by DSC.

measurement, which was performed with a heating rate of 3. Results

10  C min 1 under the protection of a constant stream of argon
with a flow rate of 50 ml min 1. 3.1. Microstructure of Al-Si eutectic alloy

2.4. Thermal conductivity measurement
The thermal diffusivity D, density r, and specific heat Cp were
measured by laser flash apparatus (Netzsch LFA 457), Archimedes
method, and differential scanning calorimetry thermal analyzer,
respectively. The thermal conductivity k of the samples was
calculated using equation k = DrCp.
As shown in Fig. 1, the Al-Si eutectic alloy composed of white
alpha solid solution (which is Al with a very small amount of Si
inside), gray beta eutectic silicon (which is Si with a very small
amount of Al inside) and some small black pores. Clearly, the
morphology of eutectic silicon changed gradually from granular to
acicular after long time thermal cycling. At the early stage of
thermal cycling, the acicular silicon phase is relatively small, but it

Fig. 6. The thermal diffusivity of Al-Si eutectic alloy measured by DSC.

304 Z. Wang et al. / Materials Research Bulletin 95 (2017) 300–306
Table 1
Densities of Al-12.2Si alloy.
Cycles/times 0 250 500 750 1000
Density/(g cm 3
) 2.62 2.62 2.62 2.63 2.63
grows and becomes thicker after repeated thermal cycling.
Through observation, it is found that there is no large amount
of coarse crystalline silicon before and after the thermal cycling,
and there is no obvious phase segregation either. Fig. 2 shows the
crystalline phase of Al-Si eutectic alloy after cycling. Consistent
with microstructure analysis results, it is proved that the alloy after
different times thermal cycling was composed of Al and Si phases,
and there is no other phases. The phase composition of Al-Si
eutectic alloy didn't change with the increase of thermal cycling
times.
3.2. Thermal properties of Al-Si eutectic alloy
Fig. 3 shows the thermal behavior with melting temperature
and latent heat of the Al-Si eutectic alloy after different number of
thermal cycles. From the curves, the melting point and latent heat
can be obtained. Obviously, the Al-Si eutectic alloy absorb thermal
energy during the melting process, all the samples display sharp
peaks and high solid-liquid latent heats, which are all higher than
490 J g 1. The latent heat measured by the DSC is decrease from
499.2 J g 1 to 493.4 J g 1 with increasing the number of thermal
cycles to 1000 times, but the start melting point of Al-Si eutectic
alloy stay almost the same of 580  C after 1000 times thermal
cycling. The changes of melting point and latent heat of the Al-Si
eutectic alloy after 1000 times thermal cycling are very small,
which satisfy the thermal property requirements for the long-term
span uses of CSP plants.
Fig. 7. Thermal conductivity of Al-Si eutectic alloy.
Because of the minor structure change of Al-Si eutectic alloy
shown in Fig. 4, the latent heat of the alloy decreases very little
with the increase of the number of thermal cycles. That is, the high
temperature and non-equilibrium cooling in the arc-melting
process make the alpha solid solution containing supersaturated
silicon, but the instability of structure makes supersaturated
silicon dissolve out gradually from the relatively homogeneous
alpha solid solution after the repeated thermal cycling, which does
not really change the thermal properties at all.
3.3. Thermal conductivity of Al-Si eutectic alloy
Fig. 5 shows the temperature-dependence specific heat (Cp) of
Al-Si eutectic alloy studied by DSC. The specific heat capacity of the
Al-Si eutectic alloy increases gradually with increasing of
temperature, and all the samples have almost the same specific
heat. Because the specific heat is closely related to the type and
state of the materials, specific heat curves can tell the nature of the
materials. For the Al-Si eutectic samples, even after they have gone
through a different number of thermal cycling, the curves are very
similar, which proved that the material did not change after so
many times of thermal cycling. It is clear that there is a slope
change at about the temperature of 380  C, that is because the
value of electron specific heat at normal temperature is insignifi-
cant compared with that of the lattice specific heat, but it has a
great contribution at high temperature range, that leads to the
rapid increase of the specific heat.
The temperature-dependent thermal diffusivity (D) is mea-
sured by laser flash apparatus and is presented in Fig. 6. Obviously,
all the samples exhibit high thermal diffusivity, which is above
75 mm2 s 1 at 50  C and 55 mm2 s 1 at 500  C. We also noted that
the thermal diffusivity of Al-Si eutectic alloy decreased with
increasing of temperature, and there is an obvious trend that the
thermal diffusivity of Al-Si eutectic alloy increased first and then
decreased with the increasing of the number of thermal cycles
 Z. Wang et al. / Materials Research Bulletin 95 (2017) 300–306
Fig. 8. The SEM morphology of Al-Si eutectic alloy after different number of thermal cycles: (a) 0 time, (b) 250 times, (c) 500 times, (d) 1000 times.
time over the whole temperature range, the highest thermal
diffusivity is observed in the Al-Si eutectic sample after 500
thermal cycles.
The density (r) of the five samples determined by Archimedes
method is listed in Table 1. The thermal conductivity of all the Al-Si
eutectic samples is calculated by k = DrCp and presented in Fig. 7.
As shown in Fig. 7, the thermal conductivity values of all the
samples are pretty high, which indicate the heat charging and
discharging rate of this material can be very fast. Generally, the
thermal conductivity of all the samples decreases first and then
increases with the increasing of temperature, meanwhile the
thermal conductivity increases first and then decreases with the
increasing of the alloy's thermal cycling time. The highest thermal
conductivity over the whole temperature range is the Al-Si eutectic
sample after 500 thermal cycles.
For the changes of thermal conductivity of Al-Si alloy, the
density shown in Table 1 increased because of the gradual
elimination of pores in the alloy after many times of vacuum
thermal cycling. But on the other hand, the thermal cycling can also
cause the disordered growth of the beta eutectic silicon and lead to
inhomogeneous structure of Al-Si eutectic alloy, as shown in Fig. 8,
which could result in anharmonicity degree of lattice vibration and
lattice wave scattering increases, mean free path of phonons
decreases. Because of that, it cause the continuous reduction of the
alloy's thermal conductivity with increasing thermal cycling.
Considering both the effect of the pore elimination and structure
inhomogeneity on the thermal conductivity of the Al-Si eutectic
alloy, the thermal conductivity of the alloy show the trend of
increases first and then decreases over the whole temperature
range as shown in Fig. 7.
4. Conclusions
In this study, the thermal properties of five Al-Si eutectic
samples were studied through a different number of thermal
cycles for potential CSP plants' TES applications. The results
indicated that the Al-Si eutectic alloy is a potentially good
candidate for TES applications. The melting point and latent heat
305
of the studied Al-Si eutectic alloy show almost no change after
more than 1000 thermal cycles. The thermal conductivity of the Al-
Si eutectic alloy is still as high as 182 W m 1 K 1 at 500  C after
1000 times thermal cycles, which is more than adequate for fast
heat charging and discharging. The high thermal energy storage
capacity and fast charging and discharging rate are crucial for such
applications.
Acknowledgements
This work is supported by Opening Foundation of Sichuan
Province Engineering Center for Powder Metallurgy (Award
Number: SC-FMYJ2017-004), Chun Hui Project of the PRC Ministry
of Education (Award Number: Z2016126), Sichuan Province
Foundation for Returnees and Foundation of Sichuan Educational
Committee (Award Number: 16ZB0156). The work performed at
University of Houston is funded by the US Department of Energy
under Contract DE-SC0010831.
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