Energy Convers. Mgmt Vol. 39, No. 11, pp.

1127±1138, 1998
# 1998 Elsevier Science Ltd. All rights reserved
PII: S0196-8904(98)00025-9 Printed in Great Britain
0196-8904/98 $19.00 + 0.00

REVIEW ON SUSTAINABLE THERMAL ENERGY

STORAGE TECHNOLOGIES, PART I: HEAT STORAGE
MATERIALS AND TECHNIQUES
S. M. HASNAIN
Energy Research Institute, King Abdulaziz City for Science and Technology, P.O. Box 6086,
Riyadh 11442, Saudi Arabia

(Received 9 July 1997)

AbstractÐThis paper reviews the development of available thermal energy storage (TES) technologies
and their individual pros and cons for space and water heating applications. Traditionally, available
heat has been stored in the form of sensible heat (typically by raising the temperature of water, rocks,
etc.) for later use. In most of the low temperature applications, water is being used as a storage med-
ium. Latent heat storage on the other hand, is a young and developing technology which has found
considerable interest in recent times due to its operational advantages of smaller temperature swing,
smaller size and lower weight per unit of storage capacity. It has been demonstrated that, for the devel-
opment of a latent heat thermal energy storage system, the choice of the phase change material (PCM)
plays an important role in addition to heat transfer mechanisms in the PCM. Attempts have also been
made to utilize technical grade phase change materials as storage media and embedded heat exchange
tubes/heat pipes with extended surfaces in order to enhance the heat transfer rate to/from the PCM. #
1998 Elsevier Science Ltd. All rights reserved

Solar energy applications Thermal energy storage Sensible heat storage Phase change
material Extended surfaces Heat pipe

INTRODUCTION
Storage of thermal energy is very important in many engineering applications. For example,
among the practical problems involved in solar energy systems is the need for an e€ective means
by which the excess heat collected during periods of bright sunshine can be stored, preserved
and later released for utilization during the night or other periods. Similar problems arise for
waste heat recovery systems where the waste heat availability and utilization periods are di€er-
ent. Heat storage can also be applied in most types of buildings where heating needs are signi®-
cant and electricity rates allow heat storage to be competitive with other forms of heating.
There are numerous types of commercially available systems, and many new developments in
the technology are taking place. Therefore, the scope of this paper is to review sensible heat sto-
rage and latent heat storage methods for space and water heating applications. In a second
paper (Part II), a state-of-the-art on cool energy storage technologies as a Demand Side
Management (DSM) as well as a Supply Side Management (SSM) tool for electric load manage-
ment is discussed.
The basic types of thermal energy storage techniques can be described as: Sensible heat sto-
rage, in which the temperature of the storage material varies with the amount of energy stored,
and latent heat storage, which makes use of the energy stored when a substance changes from
one phase to another by melting (as from ice to water). Typical data of some relevant properties
of heat storage materials used in thermal stores are given in Table 1 for comparison. The last
row in this table gives the relative volume occupied by each of the storage media for a heat sto-
rage capacity of 106 kJ and a temperature rise of 15 K during heat storage [1].

SENSIBLE HEAT STORAGE

Sensible heat storage is e€ected by raising the temperature of the storage medium. Thus, it is
desirable for the storage medium to have high speci®c heat capacity, long term stability under
thermal cycling, compatibility with its containment and, most importantly, low cost. Sensible
heat storage may be classi®ed on the basis of the heat storage media as Liquid media storage
1127
1128 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY

Table 1. Comparison of various heat storage media (stored energy = 106 kJ = 300 kWh; DT = 15 K)
Heat Storage Material
Sensible heat storage Phase Change Materials
Property Rock Water Organic Inorganic
Latent heat of fusion (kJ/kg) * * 190 230
Speci®c heat (kJ/kg) 1.0 4.2 2.0 2.0
Density (kg/m3) 2240 1000 800 1600
Storage mass for storing 106 kJ (kg) 67000 16000 5300 4350
Relative mass** 15 4 1.25 1.0
Storage volume for storing 106 kJ (m3) 30 16 6.6 2.7
Relative volume** 11 6 2.5 1.0
*Latent heat of fusion is not of interest for sensible heat storage.
**Relative mass and volume are based on latent heat storage in inorganic phase change materials

(like water, oil based ¯uids, molten salts etc.) and Solid media storage (like rocks, metals and
others).

Liquid media storage

Heat storage liquids are plentiful and economically competitive. The pros and cons of some
of the selected media are given below.
Storage in water. At low temperature water is one of the best storage media. It has higher
speci®c heat than other materials, and it is cheap and widely available. However, due to its high
vapor pressure, it requires costly insulation and pressure withstanding containment for high tem-
perature applications. Water can be used over a wide range of temperature, say 25±908C. For a
608C temperature change, water will store 250 kJ/kg or 2.5  105 kJ/m3. Hot water is required
for washing, bathing etc., and it is commonly employed in radiators for space heating. Water
can be used as a storage and as a transport medium of energy, for example, in a solar energy
system. Consequently, it is the most widely used storage medium today for solar based warm
water and space heating applications [2, 3]. Because of its simplicity, a large amount of pub-
lished data are available on the design criteria for water storage media [1±4].
Thermal strati®cation or thermocline in a solar water heat storage tank can be established
due to the buoyancy forces, which ensure the highest temperature at the top and the lowest tem-
perature at the bottom of the tank. Strati®cation is achieved through the elimination of mixing
during storage, whereby a two-fold advantage is gained [2, 3]: (i) the eciency with which the
energy can be used will be improved if it is supplied to the load at the temperature it was col-
lected rather than at a lower mixed storage temperature and (ii) the amount of energy collected
may be increased if the collector inlet ¯uid temperature is lower than the mixed storage tempera-
ture.
Water storage tanks are made from a wide variety of materials, like steel, aluminum, re-
inforced concrete and ®ber glass. The tanks are insulated with glass wool, mineral wool or poly-
urethane. The sizes of the tanks used vary from a few hundred liters to a few thousand cubic
meters.
For large scale storage applications, underground natural aquifers have been considered.
Aquifers are geological formations containing ground water, o€ering a potential way of storing
heat for long periods of time. The storage medium in aquifers consists of water saturated gravel
or sand. Large storage volumes are available, as typical aquifer sizes range from hundreds of
thousands to millions of cubic meters. For example, 105 m3 of aquifer material can store about
3 MJ of heat for each 10 K temperature di€erence. This type of storage is well suited for seaso-
nal storage, i.e. transferring heat from the summer season to the heating season. Because of its
bulk nature, aquifer storage is not feasible for small loads, e.g. individual houses. The usefulness
of aquifer thermal energy storage has been widely acknowledged, and several experimental and
theoretical studies on them have been performed [5, 6]. However, because of the multitude of
di€erent systems and physical parameters, a more detailed computer simulation study is needed
to determine the optimum system con®guration. The attractiveness of aquifer storage is due to
its low cost characteristics, its high input/output rates and its large capacity.
 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY 1129

Storage in salty water. Solar ponds o€er a simple and economical method for collecting and
storing large amounts of solar energy in the form of low temperature thermal energy (50±958C).
They have potential in space heating and cooling applications, in supplying industrial process
heat and in electric power generation. Solar ponds can be classi®ed according to four basic fac-
tors: (a) convecting or non-convecting, (b) partitioned (multi-layered) or non-partitioned, (c)
gelled or non-gelled and (d) separate collector and storage or in-pond storage. However, most
of the research e€orts are presently concentrated on the non-convecting salt gradient solar
pond [7±9]. In this type of solar pond, a density gradient is created by using water containing
salt (or sea water), the concentration of which increases with depth from the surface. Sodium
chloride (NaCl) and magnesium chloride (MgCl2) are the salts most commonly used in this type
of pond. The salt gradient pond has a black or dark bottom where the solar radiation is
absorbed, with a consequent increase in water temperature up to 958C. Extraction of the ther-
mal energy stored in the lower layers of the pond can easily be accomplished without disturbing
the upper layers. The largest solar pond in the USA is a 3355 m2 experimental facility in El
Paso, Texas, which has operated reliably since its start-up in 1986. The pond runs a 70 kWe or-
ganic rankine-cycle turbine generator and a 5000 gallons per day desalting unit, while also pro-
viding process heat to an adjacent food processing company. The pond has reached and
sustained temperatures higher than 908C in its heat storage zone, generated more than 100 kWe
during peak power output and produced more than 80,000 gallons of potable water in a 24 h
period [9].
Storage in other ¯uids. The most commonly proposed substitutes for water are petroleum
based oils and molten salts. The heat capacities are 25±40% of that of water on a weight basis.
However, these substitutes have lower vapor pressure than water and are capable of operating
at high temperatures exceeding 3008C. The oils are limited to less than 3508C due to stability
and safety reasons and can be quite expensive. Some of the oil candidates that have been con-
sidered are Therminol and Caloria-HT [2]. A few molten mixtures of inorganic salts have been
considered for high temperatures (3008C and above). One is sodium hydroxide which has a
melting point of 3208C and could be used for temperatures up to 8008C [7]. However, it is
highly corrosive, and there is a diculty in containing it at high temperatures. Liquid metals are
also mentioned as possible sensible heat storage media. While most of their properties are simi-
lar to those of water, they, along with the petroleum based oils, have low speci®c heats and
higher potential for reactivity with the container. They do, however, enjoy higher thermal con-
ductivity. Type 304 stainless steel is the most common material used for containment of oils and
liquid metals, with special attention usually given to the maintenance of an oxygen and oxide
free environment in order to prevent corrosion [10].

Solid media storage

For a low as well as high temperature thermal energy storage, solid materials such as rocks,
metals, concrete, sand, bricks etc., can be used. In this case, the energy can be stored at low or
high temperatures, since these materials will not freeze or boil. The diculties of the high vapor
pressure of water and the limitations of other liquids can be avoided by storing thermal energy
as sensible heat in solids. Moreover, solids do not leak from their container. The highest pro-
duct in the list of solid materials for sensible heat storage is cast iron, which exceeds the energy
density level of water storage [11]. However, cast iron is more expensive than stone or brick
and, hence, the payback period is much longer. Pebble beds or rock piles are generally preferred
as the storage material due to their low cost.
Storage in rocks. The pebble bed or rock pile consists of a bed of loosely packed rock material
through which the heat transport ¯uid can ¯ow. The thermal energy is stored in the packed bed
by forcing heated air into the bed and utilized again by recirculating ambient air into the heated
bed. The energy stored in a packed bed storage system depends, apart from the thermophysical
properties of the material, on several parameters, including rock size and shape, packing density,
heat transfer ¯uid etc.
Solar energy can also be stored in rocks or pebbles (packed in insulated vessels), and it is con-
venient for use in buildings. This type of storage is used very often for temperatures up to
1008C in conjunction with solar air heaters [12]. Typically, the characteristic size of the pieces of
1130 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY

rock used varies from 1 to 5 cm. An approximate thumb rule followed for sizing is to use 300±
500 kg of rock per square meter of solar collector area for space heating applications. For a
temperature change of 508C, rocks and concrete will store around 36 kJ/kg or about 105 kJ/m3.
Rock or pebble bed storage can also be used for much higher temperatures, up to 10008C. King
and Burns [12] use a number of characteristics, typically particle size, void fraction, bed cross-
sectional area and bed length, super®cial air velocity and Reynolds number, in order to describe
the thermal and geometric properties of packed beds. Like rock beds, ¯uidized beds can be uti-
lized for low, intermediate and high temperature solar applications [13]. In addition, the rate of
heat exchange between the heat carrying ¯uid and the storage medium is much faster in ¯ui-
dized beds than in rock beds, which can be an advantage in several applications. The ¯uidized
bed thermal storage can also be used for waste heat recovery purposes.
Storage in building fabric. Heat storage is applicable to both new and existing buildings and
can be integrated with both air and water distribution systems. The most prevalent storage ma-
terial is ceramic brick, consisting of olivine, magnesite, microtherm or feolite. Building mass and
structural cement can also be used with active or passive storage designs. Improvements in insu-
lation and storage materials continue to be made by manufacturers. The most common con-
®guration using building mass for thermal storage is ¯oor warming. The ¯oor becomes a large
low temperature radiating surface with the concrete acting as the heat storage medium. The
¯oor can be warmed with a heat transfer ¯uid, such as water, with direct electric resistance wir-
ing or with air ducts. Water is the most common heat transfer medium. Many buildings with
¯oor warming do not utilize o€ peak electricity to charge the storage, although they could be
retro®tted with a control system to utilize o€ peak heating. An advanced phase change material
for ¯oor storage heating has been developed by a Swiss manufacturer, with applications in the
UK, Spain, Korea and Japan [14].
Two other categories of building mass storage are building inertia and hollow core construc-
tion. Controls to minimize electricity costs for heating by using the overall mass of the building
to decrease heating during on peak periods are being developed [15, 16]. Use of inertia in build-
ing mass is a technique where no additional HVAC equipment is installed but special controls
are required. Hollow core ventilation systems were developed in Sweden, in which the supply air
is distributed through the ¯oor slabs, coupling it to the building mass [17].
Storage in metals. Most of the materials proposed for high temperature (120±14008C) energy
storage are either inorganic salts or metals [11, 18, 19]. Among the metals, aluminium, mag-
nesium and zinc have been mentioned as suitable examples. The use of metal media may be ad-
vantageous where high thermal conductivity is required and where cost is of secondary
importance. Solid industrial wastes like copper slag, iron slag, cast iron slag, aluminium slag
and copper chips could be used as storage material for energy storage.

LATENT HEAT STORAGE

Latent heat storage is a particularly attractive technique, since it provides a high energy sto-
rage density and has the capacity to store heat as latent heat of fusion at a constant temperature
corresponding to the phase transition temperature of the phase change materials (PCMs). For
example, in the case of water, 80 times as much energy is required to melt 1 kg of ice as to raise
the temperature of 1 kg of water by 18C. This means that a much smaller weight and volume of
material is needed to store a certain amount of energy.
PCMs undergo solid±solid, liquid±gas, and solid±liquid phase transformations. Relatively few
solid±solid PCMs have been identi®ed that have heats of fusion and transition temperatures
suitable for thermal storage applications. Liquid±gas PCMs usually have high heats of trans-
formations, however, due to the large volume change during transformation, they are not
usually considered for practical applications. Solid±liquid PCMs are useful because they store a
relatively large quantity of heat over a narrow temperature range, without a corresponding large
volume change [20]. Typically, the PCM is placed in long thin tubes stacked in a container.
During a heat storage cycle, the collected solar heat from the collector is circulated through
narrow spaces between the tubes and melts the PCM by storing the heat as sensible heat as well
as latent heat of fusion. During the heat recovery cycle, the circulation of low temperature air
 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY 1131

would pick up the stored energy from the PCM and transport it to the heat load. Therefore, the
latent heat storage units utilize the sensible heat in the solid and liquid phases and additionally
the latent heat due to a phase change during melting or freezing of the storage medium.
Any latent heat thermal energy storage system must possess at least the three following basic
components [11, 20]: (a) a heat storage substance that undergoes a solid-to-liquid phase tran-
sition in the required operating temperature range and where the bulk of the heat added is
stored as the latent heat of fusion, (b) a container for holding the storage substance and (c) a
heat exchanging surface for transferring heat from the heat source to the PCM and from the lat-
ter to the heat sink. The development of a latent heat thermal energy storage (LHTES) system,
therefore, involves an understanding of two essentially diverse subjects: heat storage materials
(or PCMs) and heat exchangers. These two main subjects will be discussed in the following two
sections.

Phase change materials (PCMs)

A large number of latent heat storage materials have been reported in the literature for ther-
mal storage applications in temperature ranges suitable for heating and cooling [20±38]. Some
of them according to their temperature range are listed in Table 2. PCMs can be classi®ed into
the following major categories: inorganic compounds, organic compounds and eutectics of inor-
ganic and/or organic compounds. Inorganic compounds include salt hydrates, salts, metals and
alloys, whereas organic compounds are comprised of parans, non-parans and polyalcohols.
Salt hydrates. A number of salt hydrates, such as sodium sulfate decahydrate (Glauber's salt),
calcium chloride hexahydrate, sodium thiosulphate pentahydrate, sodium acetate trihydrate and
barium hydroxide octahydrate, were investigated largely because of their low
cost [23, 24, 27, 30, 31, 35±39]. Some of the literature and measured thermophysical properties of
important PCMs are listed in Tables 3 and 4. The contents of these tables show a di€erence in
literature and measured thermophysical properties of salt hydrates. It is worth noting that most
manufacturers do not perform any tests on thermophysical properties of technical grade ma-
terials, but instead, they rely on the available data for analytical grade materials.
Major problems with most of the salt hydrates are supercooling and phase segregation.
Supercooling has been prevented in several salt hydrates by adding nucleating agents or by pro-
moting nucleation by rough container walls or using the cold ®nger technique [24, 28, 30, 34]. To
prevent phase segregation, several techniques, such as use of thickening agents, rotating storage
devices and direct contact heat transfer, have been used [34, 38]. The encapsulation of PCMs in
metal and plastic matrices has been tried extensively. The macro-encapsulation of PCMs can (i)
avoid large phase separations, (ii) increase the rate of heat transfer and (iii) provide a self sup-
porting structure for the PCM. The most cost e€ective containers are plastic bottles and tin pla-
ted food cans/mild steel cans [31]. However, corrosion could lead to disastrous consequences if
internal and external lacquer ®nishes are not applied properly to the mild steel metal cans.

Table 2. Latent heat storage materials and their temperature ranges

Temperature Range (8C) Material Transition Temperature (8C) Heat of Fusion (kJ/kg)
0±100 Water 0 335
Paran 20±60 140±280
Salt hydrate 30±50 170±270
100±400 AlC13 192 280
LiNO3 250 370
Na2O2 360 314
400±800 50LiOH/50LiF 427 512
KC1O4 527 1253
LiH 699 2678
800±1500 LiF 868 932
NaF 993 750
MgF2 1271 936
Si 1415 1654
 1132

Table 3. Melting temperatures and latent heat of fusion of selected technical grade phase change materials (PCM) using DSC-2 instrument [38]
DHf exper: ÿDHf litrat: 100
Original phase change materials Chemical Suppliers Melting temperature Tm (8C) DTm=Tmexper.ÿTmlitrat. (8C) Heat of fusion DHf (J/g) d…DHf † ˆ DHf litrat:

Litrat. Exper.
Onset Peak Onset Peak Litrat. Exper. (%)
Paran Wax BDH chemicals 49 44.16 51.64 ÿ4.84 2.64 210 186 ÿ11.43
Calcium chloride hexahydrate BDH chemicals 29 27.45 30.05 ÿ1.55 1.05 170 161.15 ÿ5.2
Disodium hydrogen phosphate Johnson Mathey 36 38.65 41.55 2.65 5.55 280 269.7 ÿ3.68
dodecahydrate chemicals
Sodium thiosulphate pentahydrate BDH chemicals 48 49.85 51.35 1.85 3.35 200 217.2 8.6
Litrat. = Literature values; Exper. = Experimental values; BDH = British Drug Houses

Table 4. Thermophysical properties of salt hydrates materials

Melting point range (8C) Heat of fusion (kJ/kg)
Material literature measured average literature measured average Density (kg/m3)
Calcium chloride hexahydrate 29.7 [36] 28.5±30.2 [36] 29 [36] 171 [36] 140±180 [36] 160 [36] 1634
(CaC12
6H2O) 29* 27.45±30.05 [38] 170* 161.15 [38] 1630*s 1500*l
Sodium carbonate decahydrate (Na2CO3
10H2O) 32±36 ± ± 247 ± ± 1442
Disodium phosphate dodecahydrate 34±37 265 1522*s
(Na2HPO4
12H2O) 36** 38±41.5 [38] 280** 269.7 [38] 1520** 1442**
Sodium sulfate decahydrate (Na2SO4
10H2O) 31±32 ± ± 251 ± ± 1534 s
Sodium thiosulfate pentahydrate 48 48.5±49 [36] 48.7 [36] 201 190±200 [36] 195 [36] 1666 s
(Na2S2O3
5H2O) 48 * 49.8±51.3 [38] 200* 217.2 [38] 1730*s 1660*l
S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY

*British Drug Houses (BDH) Chemicals.

**Johnsons±Mathey Chemicals
s = solid; l = liquid.
References in square brackets
 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY 1133

Parans. Parans have been found to exhibit many desirable characteristics as PCMs for sto-
rage applications, such as high heat of fusion, negligible supercooling, low vapor pressure in the
melt, chemically inert and stable, self nucleating, no phase segregation and commercial avail-
ability at reasonable cost [20, 34, 36±38]. However, in spite of their many desirable properties,
they have some undesirable properties, such as low thermal conductivity and large volume
change during phase transition. Metallic ®llers, metal matrix structures, ®nned tube and alu-
minium shavings were used to improve their thermal conductivity [38, 40]. To overcome the
volume change on melting and freezing, plastic containers and di€erent geometry of containers
were used. Pure paran waxes are very expensive, therefore only technical grade parans can
be used for latent heat storage. Technical grade parans are mixtures of many hydrocarbons
and, therefore, have a melting temperature range rather than a sharp melting point. Some of the
parans investigated for heat storage applications include commercial waxes, n-eicosane and n-
octadecane [37, 38, 40±42]. Degradation of commercial grade paran wax was checked using
Di€erential Scanning Calorimetry (DSC) analysis after the completion of thermal cycling of wax
in di€erent types of tubes [38]. Some of the results obtained from this study are reproduced in
Table 5. Quantitatively, the results of this study show that the addition of extended surfaces
(aluminium honeycomb) in a tube reduces the melting temperature range by 0.238C, but the as-
sociated heat contents of the solid±liquid transition are increased by 2.3% as compared to the
original sample. The reason for this distortion could be the presence of impurities in the sample
and, after extensive thermal cycling of the wax with metallic surfaces, might create hetero-
geneous nucleation. Nevertheless, the (DSC) results with the technical grade paran wax did
not show any indication that thermal cycling or contact with metal could degrade its thermal
performance appreciably. The reported results showed [37, 38] that one can not simply consider
any available data on technical grade PCMs for designing an e€ective heat storage device, as
thermophysical properties vary from manufacturer to manufacturer, mainly due to di€erent
levels of impurities in technical grade PCMs. It is, therefore, recommended by Hasnain [38] to
measure thermophysical properties of technical grade PCMs and not rely on published data
unless at least the name of the supplier and purity level of the PCM are speci®ed.
Non-paran organics. The non-paran organics include a wide variety of organic materials
such as fatty acids, esters, alcohols and glycols. Hale et al. [22] reported about 70 non-paran
organics that have melting points in the range of 7 to 1878C and heats of fusion in the range of
42 to 250 kJ/kg. Fatty acids have melting points suitable for heating applications and have heat
of fusion values comparable to those of parans and salt hydrates [43±45]. They exhibit excel-
lent melting/freezing characteristics without any supercooling. Their major drawback is their
cost which is about three times greater than parans. Feldman et al. [46, 47], Galen and
Brink [48], Hasan and Sayigh [49] and Hasan [50] performed investigations on a number of
fatty acids by DSC measurement techniques. Some of the experimentally tested fatty acids are
listed in Table 6. This table reveals the di€erent melting range of the same compound, probably
due to di€erent suppliers and di€erent purity levels. The names of the suppliers and purity levels
of the tested compounds are lacking in the literature. Fatty acid esters such as butyl stearate,
vinyl stearate and methyl±12 hydroxystearate, can be considered suitable for passive heat sto-
rage. The compatibility of fatty acids with conventional materials of construction is another
area which requires further investigation.
Eutectics. Eutectics are mixtures of two or more salts which have de®nite melting/freezing
points. Their behavior is analogous to congruent melting salt hydrates and have great potential
for thermal energy storage applications. A large number of eutectics of inorganic and organic
compounds have been reported in [7, 34, 39], and they can be classi®ed as inorganic eutectics, or-
ganic eutectics and organic±inorganic eutectics. Some of the eutectics are listed in Table 7.
These eutectics can be used for cool and passive solar storage with low or medium temperature
¯at plate collectors, according to their melting point.
Solid±solid PCMs, such as pentaerythritol (C5 H12 O4), pentaglycerine (CH3±C±(CH2±OH3),
neopentyl glycol ((CH3)2±C±(CH2OH)2) and their mixtures, were used as potential candidates
for space heating and process heat applications [34]. A highly crystalline polymer, such as high
density polyethylene (HDPE) o€ers de®nite advantages as a potential thermal energy storage
material if it is rendered form stable by crosslinking. Salyer and Botham [51] demonstrated the
 1134

Table 5. DSC results on paran wax after completing 150 thermal cycles in di€erent tubes [38]
Range of
Technical On set melting Primary peak melting
grade temperature temperature temperature Solid to solid Solid to liquid Phase transition
paran wax (average) (8C) (average) (8C) (8C) phase transition phase transition enthalpy
Proportions %
Total
Temp. range Enthalpy Temp. range Enthalpy [DH = DH1+DH2]
DH1 DH2
Melting Freezing (8C) [DH1] (J/g) (8C) [DH2] (J/g) (J/g) DH DH

PG 43.95 51.25 49.95 7.3 15.85±43.95 55.7 43.95±52.1 135.3 191 29.2 70.8
PSS 44.25 51.4 50.4 7.15 15.85±44.25 61.7 44.25±52.08 132.1 193.8 31.8 68.2
PSSH 43.85 51.5 50.15 7.25 15.85±43.85 60 43.85±52.05 136.9 196.9 30.5 69.5
PG = paran wax in glass cylinder.
PSS = paran wax in stainless steel cylinder.
PSSH = paran wax in stainless steel cylinder, containing aluminum honeycomb structure
S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY
 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY 1135

Table 6. Melting temperature and latent heat of some of the fatty acids
Melting range (8C) Latent heat (kJ/kg)
Speci®c heat Speci®c heat
Compound measured literature measured literature (CPs) (kJ/kg 8C) (Cpl) (kJ/kg 8C)
Capric acid ± 31.3 [43] ± 163 [43] ± ±
Lauric acid 40±43 [36] 42±44 [43, 44] 167±171 [36] 178 [45] ± ±
Myristic acid 50.4±53.6 [49, 50] 54 [5] 58 [43] 189 [49, 50] 190 [5] 200 [43] ± ±
Palmitic acid 57.8±61.8 [49, 50] 62 [43] 63 [45] 201 [49, 50] 164 [43] 212 [45] 2.20 [48] 1.70 [48]
60±61 [36] ± 194±198 [36] ± ± ±
55±63 [48] ± 193 [48] ± ± ±
Stearic acid 65.2±68.5 [49, 50] 69 [43] 70 [5] 210 [49, 50] 199 [22] 209 [22] ± ±
55±71 [48] ± 191 [49, 50] ± 2.07 [48] 1.90 [48]
s = solid; l = liquid.
References in square brackets

suitability of crosslinked HDPE as thermal energy storage material. Researchers at the

Electrotechnical Laboratory peformed several investigations to demonstrate the suitability of
crosslinked HDPE for thermal energy storage systems. Kamimoto et al. [52] concluded that
crosslinked HDPE is an excellent thermal energy storage material and can be used in direct ther-
mal contact with ethylene glycol and silicone oil.
Salt mixtures. The composite salt/ceramic thermal energy storage media concept o€ers the po-
tential of using phase change materials via direct contact heat exchange and, therefore, the po-
tential of signi®cant cost improvement through elimination of heat exchanger material,
reduction of storage materials and containment vessel size. This salt/ceramic approach may be
explained as micro-encapsulation of a PCM within the submicron pores of a ceramic matrix.
The liquid salt is retained within the solid ceramic network by surface tension and capillary
forces. Heat storage occurs as latent heat of the PCM and as sensible heat of the basic ceramic
material and the PCM. Therefore, the use of salt/ceramic materials represents not a pure latent
heat but a latent/sensible hybrid storage concept.
PCM has been successfully impregnated in gypsum wall board to enhance the thermal energy
storage capacity of buildings with particular interest in peak load shifting [53]. Some composites
have been prepared from abundantly available low cost materials, like coarse aggregates, sand,
gypsum, cement, vermiculite and polyester resin. Six potential implementations of thermal
energy storage by PCM have been identi®ed for energy conservation in buildings. A number of
modes of implementation PCMs technology are given in Table 8. All potential implementations
of PCM technology are not equally advanced: experimental prototypes of PCM wall boards
have been produced, but most other technologies are still at a conceptual stage [54, 55].

Heat exchanger
A LHTES system must possess a heat exchanger for transferring heat from the heat source to
the heat storage substance and from the latter to the heat sink. The type of heat exchanging sur-
face itself plays an important role in the design of a LHTES system, as it strongly in¯uences the
temperature gradients for charging and discharging of the storage. Proper designing of a
LHTES system requires quantitative information about the heat transfer and phase change pro-

Table 7. List of some of the Eutectics

Melting Latent heat of
S. No. Inorganic Eutectics point (8C) fusion (kJ/kg) Reference
1 49.3% MgC1
6H2O + 50.7% Mg (NO3)2
6H2O 58 132.3 34
2 Na2SO4 (32.5%) H2O (41.4%), NaCl (6.66%), NH4Cl (6.16%) 13 146 34
3 61.5% Mg (NO3) 6H2O + 38.5% NH4NO3 51 131.3 39
4 58.3% Mg (NO3) 6H2O + 41.7% MgCl2
6H2O 58 106 39
5 CaCl2
6H2O + CaBr2
6H2O 14 140 39
Organic Eutectics
6 Lauric±capric acid 18 120 47
7 Lauric±palmitic 33 145 47
8 Lauric±stearic 34 150 47
9 Palmitic±stearic 51 160 47
1136 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY

Table 8. Potential implementations of thermal storage by phase change materials (PCMs)

Mode of implementation PCMs technology Load Target Objective Sector

Distributed PCM storage in gypsum boards Space heating and Load shifting and All
air-conditioning conservation
Electrical heating units with PCM storage Space heating Load shifting and Residential, commercial
conservation and institutional
Heat and cold PCM storage in air-ducts Space heating and Load shifting Commercial,
air-conditioning institutional and
industrial
PCM air pre-heaters for heat pumps Space heating Load shifting and Residential, commercial
conservation and institutional
Curtain walls with PCM system Space heating Conservation Commercial,
institutional and
industrial
Water heater with PCM storage Water heating Load shifting Residential, commercial
and institutional

cesses in the PCM. Most of the PCMs (especially in solid phase) exhibit insulating character-
istics, thus creating a problem for the heat retrieval cycle. This problem can be overcome by
using metallic extended surfaces with bare heat carrying tubes or heat pipes. Hasnain [38, 59]
and Hasnain and Gibbs [56±58] have used extended surfaces in the form of aluminium honey-
comb discs and aluminium and copper square ®ns that extended to the walls of the storage unit
containing technical grade PCM. They compared quantitative heat transfer data for melting and
freezing of technical grade paran wax around cylindrical ®nned and un®nned heat carrying
tubes and copper heat pipes, oriented either vertically or horizontally. They had experimentally
found that the heat transfer was enhanced by the use of copper square ®ns, leading to a re-
duction in the solidi®cation times of technical grade paran wax up to 11 times. The reported
results [38, 58, 59] also reveal that the heat ¯ux for the ®nned tube/heat pipe was much larger
than that of the bare tube/heat pipe, and the use of the extended surfaces o€set the e€ect of in-
itially subcooled solid PCM. Additionally, a vertically oriented ®nned tube assembly gave a bet-
ter performance with a uniform temperature distribution in the paran bed compared to a
horizontally oriented storage unit.
Heat conduction problems involving melting or solidi®cation of PCM have been studied by a
large number of investigators and extensive literature reviews are available [38, 41, 42, 60±63].
These problems are dicult to solve due to variable properties and moving boundaries. The
methods generally employed in the analysis of heat conduction problems involving phase change
include exact, integral, variational, perturbation, purely numerical and other methods. However,
since the storage systems are regenerative in nature, periodic solutions are desired for actual sys-
tem design. Several papers [64±66] with various simpli®cations and assumptions have appeared
in the literature describing the melting time and temperature distribution in an analytical grade
PCM. Additionally, a detailed heat transfer study is required with technical grade PCMs using
di€erent types of heat carrying tubes with or without types of extended surfaces, at least in a
prototype heat storage unit. This study may provide qualitative and quantitative data for e€ec-
tive design of a heat storage exchanger.

CONCLUDING REMARKS
Sensible heat storage and latent heat storage are the two major techniques for thermal energy
storage considered today for di€erent applications, such as space heating and hot water pro-
duction. Sensible heat storage wherein energy is stored in water or rocks, is presently in an
advanced stage of development. Latent heat storage, on the other hand, is a developing technol-
ogy that has been found very promising in recent times due to the several operational advan-
tages it o€ers. In the development of latent heat storage systems, research is underway in two
directions, namely the investigation of phase change materials and of heat exchangers. PCM,
such as salt hydrates, parans, non-parans, eutectics and solid state PCMs, have good poten-
tial for low temperature thermal energy storage applications. A number of problems still remain
to be tackled before technically and economically favourable latent heat thermal energy storage
systems can be made available for widespread use. In spite of the fact that PCMs have been
 S. M. HASNAIN: REVIEW ON SUSTAINABLE THERMAL ENERGY 1137

investigated by several researchers, their (especially technical grade PCM) thermophysical prop-
erties such as density, speci®c heat and thermal conductivity in the solid and liquid phases are
lacking in the literature. A discrepancy was found even between the literature and measured
thermophysical properties of technical grade PCM. Hence, there is a need to generate exper-
imental data for these thermophysical properties in the solid and liquid phases of PCMs in
order to assist the e€ective and appropriate design of thermal storage units.

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