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Energy Procedia 105 (2017) 4328 – 4333

The 8th International Conference on Applied Energy – ICAE2016

Al/Al2O3 Form-Stable Phase Change Material for High

Temperature Thermal Energy Storage
Yang Xua, Ya-Ling Hea,* Gui-Hua Zhub, Shuo Lvb, Bo Shana
a
Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, School of Energy and Power Engineering,
Xi’an Jiaotong University, Xi’an 710049, China
b
Department of Chemical Engineering, Northern University for Ethnics, Yin chuan 750021, China

Abstract

In this paper, a novel form-stable phase change material (PCM) for high-temperature thermal energy storage was
prepared and characterized to overcome the leakage and incompatibility issue of PCM. Al was used as PCM and
Al2O3 as skeleton material. An improved mixed sintering method was employed for preparation, and thermophysical
properties such as melting point, latent heat and thermal conductivity were measured to evaluate the performance of
the form-stable PCM. The results showed that the optimum molding condition was 400 MPa for 5min to obtain a
have good compactness and stability. The maximum mass fraction of Al without leakage was 60%, and the peak
values of latent heat and thermal conductivity of the composite was 194.2 J/g and 2.15 W/m·K, respectively.

©
© 2017
2016Published by Elsevier
The Authors. Ltd. This
Published by isElsevier
an open Ltd.
access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or peer-review under responsibility of ICAE
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
Keywords: High-temperature latent thermal energy storage; Concentrating solar power; Form-stable phase change material; Metallic
material; Aluminum

1. Introduction

Aggravation of global energy crisis and environmental problem urge the rapid development of
renewable energy especially solar energy. Thermal energy storage (TES) can ease the discontinuity and
instability of solar energy and reduce the mismatch between the supply and the demand, hence plays a big
part in promoting the utilization efficiency of solar energy. Among the TES methods, latent heat thermal
energy storage (LHTES) has a highly promising prospect since PCM can provide relatively large energy
storage density and almost constant working temperature. Cost-effective and high-performance PCM is
vitally important as the basis of LHTES. However, most PCMs are disadvantaged by their natural defects
of low thermal conductivity, poor shape stability and incompatibility with container material, which limit

* Corresponding author. Tel.: +86-29-8266-5930; fax: +86-29-8266-5445.

E-mail address: yalinghe@ xjtu.edu.cn.

1876-6102 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
doi:10.1016/j.egypro.2017.03.907
 Yang Xu et al. / Energy Procedia 105 (2017) 4328 – 4333 4329

the heat transfer efficiency of the TES system and may bring about leakage and safety problem. As one of
the solutions to these limitations, form-stable composite PCM can keep the melting PCM from leakage
and contact with container. Impregnation of PCM into skeleton material, which is a typical example of
form-stable PCM, has been research focuses in the recent years [1-3]. Nevertheless, most of current
studies concentrate on PCM e.g. paraffin waxes [4-5], fatty acids [6-7] and alcohols [8] for low
temperature utilization. As for medium to high temperature form-stable PCM, studies are more urgent due
to speedy progress of concentrating solar power (CSP) technologies. Increasing operation temperature
will be needed in the near future.
Molten salts and metallic materials are two main kinds of PCM for high temperature thermal energy
storage. Kenisarin [9] reviewed the properties of high temperature PCMs and concluded that phase
change metal alloys deserve more attention. Compared with molten salts, most metallic materials have
higher thermal conductivity and larger latent heat during liquid-solid phase change. Being the most
abundant metallic element in the Earth's crust, aluminum together with aluminum alloy has recently
raised a great deal of attentions because of their appropriate melting temperature for TES system in CSP,
high thermal conductivity, large phase change heat and relatively low cost [10-11]. But the highly
corrosive nature impedes their direct use in the LHTES equipment. Leiby [12] tested Al (99.999% purity)
in Inconel X-750 container for 130 thermal cycles. It was found that Al alloyed with the container
material; therefore some measures must be taken to prevent Al from direct contacting with the container
material. Form-stable PCMs can provide a solution to this corrosion issue. Skeleton material can be added
to hold Al within the support structure, so the leakage problem and the direct interaction between
container material and Al can both be prevented.
In this study, we introduced a novel form-stable PCM for high temperature LHTES (>650ƕC). Al acted
as PCM and Al2O3 was chosen as skeleton material because of no chemical reaction between them.
Thermal properties of the form-stable PCM such as melting point, melting heat and thermal conductivity
were investigated. The optimum synthesis condition was discussed and the maximum content of Al was
determined to optimize the performance of the form-stable PCM.

2. Experimental

2.1 Material

The PCM (Al powder, Shanghai Shanpu Chemical Co., Ltd, China) and ceramic skeleton (Al2O3
powder, Sinopharm Chemical Reagent Co., Ltd, China) used in this study were initially dried at 150°C
under vacuum condition for 2 hours and then sifted through a 160 mesh sieve. Polyvinyl alcohol (PVA)
provided by Sinopharm Chemical Reagent Co., Ltd. was used as binder agent. All reagents used in this
study were of analytical-grade and used without further purification.

2.2 Preparation of composites

Al/Al2O3 form-stable PCM was prepared by mixed sintering method. Firstly, Al powder, Al2O3
powder and sintering aids were premixed by weight percentage. Al powder accounted for 40% of the total
weight and sintering aids accounted for 5%. The mixture was put into four Teflon jars (100mL) and
grinded in a planetary ball mill for 1 h with a rotation speed of 200 r/min. A ball-to-powder weight ratio
of 4:1 was employed with zirconium balls of 8mm and 5mm diameter. After ball milling, polyvinyl
alcohol solution of 5wt. % concentration was added to the powder mixture and then well mixed. The
weight ratio of polyvinyl alcohol solution to the powder mixture was about 8%. Secondly, 0.5g mixture
was put into a mold and shaped into disk-like green samples by uniaxial compression. To determine the
4330 Yang Xu et al. / Energy Procedia 105 (2017) 4328 – 4333

optimum preparation condition, a series of Al/Al2O3 PCM samples were prepared with different molding
pressure (200MPa, 300MPa, 400MPa, 500MPa and 600MPa) and different molding time (2.5min, 5min,
7.5min and 10min). The green samples were dried in vacuum oven at temperature of 120ƕC for 2 hours to
remove moisture in case of crack during sintering. Finally, the samples were sintered in a resistance
furnace following this heating procedure: heating from 25 to 660ƕC at 5ƕC /min, holding at 660ƕC for 10
min, heating from 660 to 950ƕC at 15ƕC /min and holding at 950ƕC for 120min, then naturally cooled to
room temperature.

2.3 Characterization

In order to evaluate the performance of the Al/Al2O3 form-stable PCM, thermophysical properties
(such as latent heat and melting point) were measured by a thermal analyzer (STA 449F3 Jupite®,
Netzsch, Germany) following the ASTM E967 standard. The analysis was performed at 10ƕC/min heating
rate under a 50 ml/min nitrogen flow at atmospheric pressure. The thermal conductivity was calculated by
the equation

O D u U ucp (1)
where the thermal diffusivity Į and specific heat cp were measured by a laser flash apparatus (LFA 457
MicroFlash®, Netzsch, Germany) in accordance with ASTM E1461 specification and density ȡ was
obtained by Archimedes method. The results of conductivity were average of three measurements to
reduce errors.

3. Results and discussions

3.1 Determination of the optimum molding pressure and molding time

Figure 1 shows the photographs of Al/Al2O3 PCM samples prepared under a series of molding
pressures with a molding time of 5min. It is clear that samples are intact when the molding pressure is no
more than 400 MPa. When the pressure is larger, obvious leakage of Al can be found and larger pressure
causes more serious leak. Fig. 2 shows the variation curves of density and thermal conductivity of these
samples with molding pressure. It can be observed from Fig. 2 that the density increases with the
increasing pressure and reaches the maximum when the molding pressure is 400MPa, then decreases with
the increasing pressure. The thermal conductivity increases with increase of molding pressure and stays
almost constant when the molding pressure is over 400MPa.
Based on Fig. 1 and Fig. 2, it can be found that the variation trends of density and thermal conductivity
with molding pressure show a certain degree of similarity, and the integrity of samples influences the
density and thermal conductivity. The reasons is explained as follows. With the molding pressure
increasing, the amount of void space within the samples is reduced and the compactness of the sample is
improved; therefore the density is increased. At the same time, the enhanced contact between each
particle leads to a higher efficiency of heat transfer, so the thermal conductivity is also improved.
Nevertheless, it is noted that a volume change happens during the melting process of aluminum, about
10% calculated from the density of its solid and liquid phase, while the volume expansibility of ceramic
skeleton formed by Al2O3 with temperature can be ignored. When the molding pressure is more than
400MPa, the space of each aluminum particle becomes very limited. During the sintering process, the
solid aluminum melts and expands, but there is no enough space for melting aluminum, so leakage occurs.
The loss of Al decreases the weight ratio of Al in the samples, so the density is decreased. In terms of
 Yang Xu et al. / Energy Procedia 105 (2017) 4328 – 4333 4331

thermal conductivity, it can be positively affected by the improved compactness of the sample but
negatively affected by the loss of aluminum. These two opposite effects nearly compensate each other, so
the thermal conductivity stays almost constant when the molding pressure is more than 400MPa.
Therefore, 400MPa was chosen as the optimum molding pressure in this study.

Fig. 1 Al/Al2O3 PCM samples prepared under different molding Fig. 3 Al/Al2O3 PCM prepared under a molding
pressures (a) 200MPa, (b) 300MPa, (c) 400MPa, (d) 500MPa and (e) pressure of 400MPa with different molding time (a)
600Mpa 2.5min, (b) 5min, (c)7.5min and (d)10min

1.40 1.8 1.38 1.70

Density

-1
-1

Thermal conductivity / W·m ·K

Thermal conductivity  W˜m ˜K
1.35 1.6 Thermal conductivity 1.65
1.36

-1
-1
1.30 1.4 1.60
-3

-3
Density / kg·m

Density / kg·m
1.34
1.25 1.2 1.55
1.32
1.20 1.0 1.50
1.30 1.45
1.15 Density 0.8
Thermal conductivity
1.10 0.6 1.28 1.40
100 200 300 400 500 600 700 2 3 4 5 6 7 8 9 10 11
Molding pressure / MPa Molding time / min

Fig. 2 Density and thermal conductivity of Al/Al2O3 PCM Fig. 4 Density and thermal conductivity of Al/Al2O3 PCM
samples prepared under different molding pressure samples prepared with different molding time

Figure 3 displays images of Al/Al2O3 PCM prepared under a molding pressure of 400MPa with
different molding time. It can be noticed that when the molding time is 2.5min or 5min, the PCM samples
are clean without escape of Al. However, longer molding time yields some leakage. Fig. 4 shows the
variation of density and thermal conductivity of the samples over the molding time. Density and thermal
conductivity both reach the maximum when the molding time is 5 min. This result can be explained by
that long molding time has similar effects on the properties of the form-stable PCM with large molding
pressure. During the molding time, the stress is gradually passed from the surface to the interior of the
sample. Short molding time results in insufficient compress, but if the molding time is too long, the
samples can be over compressed and leakage will happen.
In a conclusion, improper molding pressure and molding time are harmful to the integrity and the
thermal conductivity of the samples. After experimental comparison, the optimum molding pressure for
Al/Al2O3 PCM is 400 MPa, and the corresponding optimum molding time is 5 min to obtain relatively
high thermal conductivity and density, and avoid leakage of phase change material.

3.2 Effect of mass fraction of aluminum on thermal properties

Mass fraction of Al in the form-stable PCM directly influences the latent heat and thermal conductivity
of the samples. Increasing the mass fraction of Al means enhancing the latent heat and thermal
conductivity simultaneously, but excessive Al may lead to leakage. Based on the optimum synthesis
4332 Yang Xu et al. / Energy Procedia 105 (2017) 4328 – 4333

condition discussed above, a series of Al/Al2O3 form-stable PCM samples with different mass fraction of
Al (40%, 45%, 50%, 55%, 60% and 65%) were prepared. The thermal properties such as phase change
temperature, latent heat and the thermal conductivity of the samples were studied and the best mass
fraction of Al was determined.
The DSC-TG curves of the form-stable PCM with different mass ration of Al are shown in Fig. 5,
where corresponding data of phase change temperature are also noted. The DSC analysis of Al powder
was set as a reference to study the thermal property changes after the synthesis of the form-stable PCM.
The TG curves show that samples with different mass ratio of Al have good thermal stability. The masses
of the samples stay nearly constant during the temperature range of 300-750 ć. It is also clear that the
DSC curves of these samples all have similar shapes to that of the Al powder, signifying that it is the
aluminum that serves as the latent thermal energy storage material during the melting process. Data in
Fig.5 show that the melting temperatures of form-stable PCM with different mass fraction of Al are
approximately the same with that of the Al powder. Therefore, the preparation process of the form-stable
PCM does not affect the stability and melting point of aluminum. The melting point which is around
655oC indicates their application for high temperature thermal energy storage
Figure 6 shows the latent heat and thermal conductivity of the form-stable PCM with different mass
ratio of Al. It can be seen from Fig. 6 that the latent heat and thermal conductivity both increase with the
increase of mass ratio of aluminum at first, get the maximum value 194.2 J/g and 2.15 W/m·K
respectively when the mass ratio reaches 60%, and then slightly decrease with the mass fraction more
increase. Therefore, there exists an optimum mass ratio of aluminum to maximize the latent heat and
thermal conductivity of the form-stable PCM. Excessive aluminum can cause serious leakage issue, so
fails to enhance the latent heat and thermal conductivity.

200 2.4
100

-1
Endo.

Thermal conductivity / W·m ·K

180 2.1

-1
Melting point 90
-1

o
655.9 C
Heat flow / mW˜mg

-1

100% Al 160 1.8

Latent heat / J˜ g

o
65% Al 654.7 C 80
m/%

o 140 1.5
60% Al 655.1 C
o
55% Al 655.6 C 70
120 1.2
o
50% Al 654.8 C
o
655.1 C 60 100 Latent heat 0.9
45% Al
o thermal conductivity
654.5 C
40% Al 80 0.6
50 35 40 45 50 55 60 65 70
300 350 400 450 500 550 600 650 700 750
o
Temparature / C Mass fraction of Al / %
Fig. 5 DSC-TG curves of the form-stable PCM with different Fig. 6 Thermal conductivity of the form-stable PCM with
mass ration of Al different mass ratio of Al

4. Conclusions

To overcome the poor shape stability and corrosion issue of metallic material, a novel Al/Al2O3 form-
stable PCM was fabricated for high-temperature thermal energy storage. Phase change material Al and
skeleton material Al2O3 were two main components. The optimum molding pressure and molding time
were determined to be 400 MPa and 5 min respectively to obtain high thermal conductivity and density,
and avoid leakage of phase change material. Effects of mass fraction of Al to the thermal properties such
 Yang Xu et al. / Energy Procedia 105 (2017) 4328 – 4333 4333

as melting point, latent heat and thermal conductivity of the form-stable PCM were discussed. The form-
stable PCMs with different mass ratio of Al have good thermal stability and approximately constant phase
change point. The latent heat and thermal conductivity reach their peak values 194.2 J/g and 2.15 W/m·K
respectively when the mass fraction of Al is 60%. Larger mass fraction is not suggested because leakage
problem can be caused.

Acknowledgements

This work was supported by the National Key Basic Research Program of China (973 Program)
(2013CB228304, 2013CB228303) and the Key Project of National Natural Science Foundation of China
(No.51436007).

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Biography
Ya-Ling He is currently a professor of Xi’an Jiaotong University, China and director of the Key
Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education. She is an
Associate Editor of Applied Thermal Engineering and Heat Transfer Research. She is also
International Institute of Refrigeration-Vice President of Commission B1, and Members of the
Scientific Council of ICHMT.