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ENGINEERING AND TECHNOLOGY (IJARET)
ISSN 0976 - 6480 (Print)
ISSN 0976 - 6499 (Online)
Volume 3, Issue 2, July-December (2012), pp. 214-225
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IJARET
©IAEME
A REVIEW ON PHASE CHANGE MATERIALS & THEIR
APPLICATIONS
Ajeet Kumar RAI, Ashish KUMAR*
Department of Mechanical Engineering, SSET, SHIATS-DU Allahabad-211007, India
*Email id: [email protected] [email protected]
ABSTRACT
The objective of present work is to gather the information from the previous works on the phase change
materials and latent heat storage systems. The use of latent heat storage system incorporating phase
change material is very attractive because of its high energy storage density with small temperature
swing. There are varieties of phase change materials that melt and solidify at a wide range of temperature
making them suitable for number of applications. The different applications in which the phase change
method of heat storage can be applied are also reviewed in this paper.
Keywords- phase change materials, latent heat storage system, solar energy
1. INTRODUCTION
Fast depletion of conventional energy sources and high rise of demand of energy have increased the
problem with high rise of environmental concern due to green house effect. Scientists all over the world
are in search for new & renewable energy source to deal with.
Solar thermal energy is the most available renewable source of energy and is available as direct and
indirect forms [1]. The sun consists of hot gases and has a diameter of 1.39 × 109 m; it has an effective
blackbody temperature of 5762 K [2], the temperature in its central region ranges between 8× 106 and 40
× 106 K [3]. The Sun emits energy at a rate of 3.8 × 1023 kW, of which, approximately 1.8 × 1014 kW is
transmitted to the earth; only 60% of this amount reaches the earth’s surface. The other 40% is reflected
back and absorbed by the atmosphere. If 0.1% of this energy is converted with efficiency of 10%, then it
can generate amount of energy equivalent to four times of the world’s total generated electricity.
Moreover, the total annual solar radiation falling on the earth is more than 7500 times of the world’s total
annual primary energy consumption that is 450 EJ. There is 3,400,000 EJ, approximately, of total annual
solar radiation reaches the surface of the earth which is greater than all the estimated conventional energy
sources [2].
Since these sources of energy are less intensified, unpredictable and intermittent in nature, this requires
efficient thermal energy storage so that the surplus heat collected may be stored for later use. Similar
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problem arises in heat recovery systems where the waste heat, availability and utilization periods are
different, requires some thermal energy storage.
The energy crisis of the late 1970s and early 1980s left a fervent question which was later answered by
the concept of PCM as given in 1940s by Dr Telkes. This concept has given an access to a new gateway
for energy storage devices. However, the first ever known application of PCM is documented by Dr
Telkes [4] for heating and cooling of buildings. Lane [5] has also worked in the same direction. Telkes et.
al [6] published the idea of using PCMs in walls known as Trombe walls.
Thermal energy can be stored as a change in internal energy of a material as sensible heat , latent heat or
combination of these two. In sensible heat storage (SHS), thermal energy is stored by raising the
temperature of a solid or liquid. SHS utilizes the heat capacity and the change in temperature of the
material during the process of charging and discharging. The amount of heat stored depends on the
specific heat of the medium, the temperature change and the amount of storage material [7].
Q= (1)
=
− (2)
LHS is based on the heat absorption or release when a storage material undergoes a phase change from
solid to liquid or liquid to gas or vice versa. The storage capacity of the LHS system with a pcm medium
[7] is given by
Q= + ∆ℎ + (3)
Q=[
− + ∆ℎ + − ]
(4)
2. PHASE CHANGE MATERIALS
Materials that can store latent heat during the phase transition are known as phase change materials. Due
to the compactness of PCMs the latent heat is much higher than the sensible heat. These materials are
still a point of interest for researchers. Lorsch et. al. [8], Lane et. al. [9] and Humphries and Griggs [10]
have suggested a wide range of PCMs that can be selected as a storage media keeping following attributes
under consideration[11]. In order to select the best qualified PCM as a storage media some criterias are
also mentioned by Furbo and Svendsen [15].
1. High latent heat of fusion per unit volume so that a lesser amount of material stores a given
amount of energy.
2. High specific heat that provides additional sensible heat storage effect and also avoid sub-cooling.
3. High thermal conductivity so that the temperature gradient required for charging the storage
material is small.
4. High density so that a smaller container volume holds the material.
5. A melting point is desired operating temperature range.
6. The PCM should be non-poisonous, non-flammable and non-explosive
7. No chemical decomposition so that the system life is assured.
8. No corrosiveness to construction material.
9. PCM should exhibit little or no sub-cooling during freezing.
10. Also, it should be economically viable to make the system cost effective.
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2.1.
Working of PCMs
Any material can dwell into three basic forms viz solid, liquid and gas. A material changes its state on the
expenses of its latent heat.
Kuznik et. al [12] has given a good explanation of how PCM stores and releases latent heat. The external
heat supplied to a PCM is spent in breaking the internal bonds of lattice and thereby it absorbs a huge
amount of latent heat at phase temperature. Now, when the PCM cools down, temperature goes below
phase change temperature (known as sub-cooling or under-cooling) to overcome the energy barrier
required for nucleation of second phase. Once phase reversal starts, temperature of P.C.M. rises (due to
release of latent heat) and subsequent phase reversal takes place at phase change temperature by releasing
back the latent heat to environment. Requirement of sub-cooling or under-cooling for phase reversal is an
important property of P.C.M. governing its applicability in particular application.
Latent heat of P.C.M. is many orders higher than the specific heat of materials. Therefore P.C.M. can
share 2-3 times more heat or cold per volume or per mass as can be stored as sensible heat in water in a
temperature interval of 20oC. As heat exchange takes place in narrow band of temperature the
phenomenon can be used for temperature smoothening also.
2.2. PCM classification
Abhat et.al.[13] has given a detailed classification of PCMs along with their properties. Lane [5], Dinser
and Rosen [14] have also exercised the same. A large number of phase change materials (organic,
inorganic and eutectic) are available in any required temperature range. A classification of PCMs is given
in Fig.1.
Figure 1: Classification of Phase Change (Latent Heat Storage) Materials
2.2.1. Organic phase change materials
Organic materials are categorized as paraffin and non-paraffin materials. These materials include
congruent melting, means melt and freeze repeatedly without phase segregation and consequent
degradation of their latent heat of fusion.
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Melting
point (oC)
Latent
Heat
(kJ/kg)
Melting
point (oC)
Latent
Heat
(kJ/kg)
Category
Category
n-Dodecane
-12
n.a.
P.
N-Pentacosane
53.7
164
P.
n-Tridecane
-6
n.a.
P.
Myristic acid
54
199
N.p.
n-Tetradecane
5.5
226
P.
Oxolate
54.3
178
N.p.
Formic acid
7.8
247
N.p.
Tristearin
O-Xylene
dichloride
54.5
191
N.p.
N-Pentadecane
10
205
P.
55
121
N.p.
Oleic acid
13.5-16.3
n.a.
N.p.
n-Hexacosane
56
257
P.
Acetic acid
16.7
273
N.p.
β Chloroacetic acid
56
147
N.p.
N-Hexadecane
16.7
237
P.
N-hexaacosane
56.3
255
P.
n-Heptadecane
22
215
P.
Nitro naphthalene
56.7
103
N.p.
D-Lactic acid
26
184
N.p.
α Chloracetic acid
61.2
130
N.p.
n-Octadecance
28.2
245
P.
N-Octacosane
61.4
134
P.
n-Nonadecane
31.9
222
P.
Palmitic acid
61.8
164
N.p.
Paraffin wax
32
251
P.
Bees wax
61.8
177
N.p.
Capric acid
32
152.7
N.p.
63
109
N.p.
n-Eicosane
37
247
P.
P-Bromophenol
63.5
86
N.p.
Caprilone
40
260
N.p.
Azobenzene
67.1
121
N.p.
Docasyle bromide
40
201
N.p.
Acrylic acid
68
115
N.p.
40.5
161
P.
Stearic acid
69
202.5
N.p.
Phenol
41
120
N.p.
Dintro toluene(2,4)
70
111
N.p.
N-Lauric acid
43
183
N.p.
n-Tritricontane
71
189
P.
P-Joluidine
43.3
167
N.p.
Phenylacetic acid
76.7
102
N.p.
Cynamide
44
209
N.p.
Thiosinamine
77
140
N.p.
N-Docosane
44.5
157
P.
Benzylamine
78
174
N.p.
N-Tricosane
47.6
130
P.
Acetamide
81
241
N.p.
48
118
N.p.
Alpha napthol
96
163
N.p.
Cetyl alcohol
49.3
141
N.p.
Quinone
115
171
N.p.
O-Nitroaniline
50
93
N.p.
Succinic anhydride
119
204
N.p.
Camphene
50
239
N.p.
Benzoic acid
121.7
142.8
N.p.
Diphenyle amine
52.9
107
N.p.
Benzamide
127.2
169.4
N.p.
P-Dicchlorobenzene
53.1
121
N.p.
Alpha glucose
141
174
N.p.
Material
N-henicosane
Hydrocinnamic acid
Material
Glyolic acid
P. Paraffin
N.P. Non paraffin
n.a. Not available
Table 1: List of Organic Materials [7] [11] [13] [17] [18]
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Paraffin are chemically known as hydrocarbons which are generally found to be as wax at room
temperature whereas non-paraffin encompasses fatty acids, glycols, esters and alcohols etc. Paraffin
consists of a mixture of mostly straight chain n-alkanes CH3–(CH2)–CH3. The crystallization of the
(CH3)- chain release a large amount of latent heat. Both, the melting point and latent heat of fusion,
increase with chain length. Paraffin qualifies as heat of fusion storage materials due to their availability in
a large temperature range. System-using paraffin usually has very long freeze–melt cycle. Apart from
some several favorable characteristic of paraffin, such as congruent melting and good nucleating
properties, they show some undesirable properties such as:
(i)
(ii)
(iii)
low thermal conductivity,
non- compatible with the plastic container and
moderately flammable.
All these undesirable effects can be partly eliminated by slightly modifying the wax and the storage unit.
Non-paraffin materials are flammable and should not be exposed to excessively high temperature, flames
or oxidizing agents.
Some of the features of these organic materials are as follows:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
high heat of fusion,
inflammability,
low thermal conductivity,
low flash points,
varying level of toxicity, and
instability at high temperatures.
Fatty acids have high heat of fusion values comparable to that of paraffin’s. Fatty acids also show
reproducible melting and freezing behavior and freeze with no supercooling. The general formula
describing all the fatty acid is given by CH3(CH2)2n COOH Their major drawback, however, is their
cost, which are 2–2.5 times greater than that of technical grade paraffin’s. They are also mild corrosive.
Some fatty acids are of interest to low temperature latent heat thermal energy storage applications.
2.2.2.
Inorganic phase change materials
Inorganic materials are further classified as salt hydrate and metallics. These PCMs do not super cool
appreciably and their heats of fusion do not degrade with cycling.
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Name
Melting
point (0C)
Latent
Heat
(kJ/kg)
POCl3
1
85
FeBr3.6H2O
318
Cs
33
CaCl2.6H2O
253
Ga
D2O
3.7
SbCl5
4
LiClO3.3H2O
8
H2SO4
Name
Melting
point (0C)
Latent
Heat
(kJ/kg)
27
105
28.3
15
29-30
170-192
30
80
10.4
100
AsBr3
30
38
NH4Cl.Na2SO4.10H2O
11
163
BI3
31.8
10
K2HO4.6H2O
14
108
TiBr4
38.2
23
50
H4P2O6
55
213
286
SbCl3
73.4
25
MOF6
17
NaCl.Na2SO4.10H2O
18
KF.4H2O
18
330
NaNO3
307
17-199
K2HO4.4H2O
18.5
231
KNO3
333-380
116-266
P4O3
23.7
64
KOH
380
149
148
MgCl2
714-800
452-492
289
KF
857
452
147
K2CO3
897
235
Mn(NO3)2.6H2O
25
LiBO2.8H2O
25.7
H3PO4
26
Table 2: List of Inroganic Materials [7] [11] [13] [17] [18]
Salt hydrates may be regarded as alloys of inorganic salts and water forming a typical crystalline solid of
general formula M.nH2O. The solid–liquid transformation of salt hydrates is actually a dehydration of
hydration of the salt, although this process resembles melting or freezing thermodynamically. A salt
hydrates usually melts to either to a salt hydrate with fewer moles of water, i.e.
M.nH2O M.mH2O + (n - m) H2 O
(5)
or to its anhydrous form
M.nH2O M+ nH2O
(6)
At the melting point the hydrate crystals breakup into anhydrous salt and water, or into a lower hydrate
and water. One problem with most salt hydrates is that of incongruent melting caused by the fact that the
released water of crystallization is not sufficient to dissolve all the solid phase present. Due to density
difference, the lower hydrate (or anhydrous salt) settles down at the bottom of the container.
The most attractive properties of salt hydrates are:
(i)
(ii)
(iii)
high latent heat of fusion per unit volume,
relatively high thermal conductivity (almost double of the paraffin’s), and
Small volume changes on melting.
They are not very corrosive, compatible with plastics and only slightly toxic. Many
sufficiently inexpensive for the use in storage.
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salt hydrates are
International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 –
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Disadvantages:
(i)
(ii)
(iii)
(iv)
(v)
Incongruent melting
Irreversible melting-freezing cycle
Poor nucleating properties
Supercooling.
Phase segregation
Metallic includes the low melting metals and metal eutectics. Because of its larger weight, metallic’s are
not of prime importance However, when volume is a consideration, they are likely candidates because of
the high heat of fusion per unit volume. They have high thermal conductivities. A major difference
between the metallics and other PCMs is their high thermal conductivity. A list of some selected materials
is listed in table 2. Some of the features of these materials are as follows:
(i)
(ii)
(iii)
(iv)
(v)
low heat of fusion per unit weight
high heat of fusion per unit volume,
high thermal conductivity,
low specific heat and
relatively low vapor pressure
2.2.3.
Eutectics
A eutectic is a minimum-melting composition of two or more components, each of which melts and
freeze congruently forming a mixture of the component crystals during crystallization. Eutectic always
melts and freezes without segregation since they freeze to an intimate mixture of crystals, leaving little
opportunity for the components to separate. On melting both components liquefy simultaneously, again
with separation unlikely.
Name
Composition
Melting
Point
Latent
Heat
of
Fusion
(kj/kg)
Na2SO4+NaCl+KCl+H2O
31+13+16+40
4
234
Na2SO4+NaCl+NH4Cl+H2O
32+14+12+42
11
C5H5C6H5+ (C6H5)2O
26.5+73.5
Na2SO4+NaCl+H2O
Ca(NO)3.4H2O
Mg(NO)3.6H2O
NH2CONH2 + NH4 NO3
Composition
Melting
Point
Latent
Heat
of
Fusion
(kj/kg)
Mg(NO3)2.6H2O +
NH4 NO3
61.5+38.4
52
125.5
n.a.
Mg(NO3)2.6H2O +
MgCl2.6H2O
58.7+41.3
59
132.2
12
97.9
Mg(NO3)2.6H2O +
Al(NO3)2.9H2O
53+47
61
148
37+17+46
18
n.a.
Mg(NO3)2.6H2O +
MgBr2.6H2O
59+41
66
168
47+53
30
136
Napthalene
Benzoic Acid
67.1+ 32.9
67
123.4
n.a.
46
95
AlCl3+NaCl+ZrCl2
79+17+4
68
234
+
Name
+
n.a. Not available
Table 3: Melting point and latent heat of some Eutectics material. [7] [11] [13] [17] [18]
Some segregation PCM compositions have sometimes been incorrectly called eutectics, since they are
minimum melting. Because of the components undergoes a peritectic reaction during phase transition,
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however, they should more properly be termed peritectics. Th eutectic point of laboratory grade
hexadecane– tetradecane mixture occurs at approximately 91.67% of tetradecane.
3. SOLUTION TO GENERAL PROBLEM RELATED WITH PCMS
Various drawbacks associated with different classes of PCM necessitate some preventive measures.
Various scholars Bauer and Wirtz [19], Mehling et. al. [20], py et. al [21] Stark [22] and Morcos [23] etc.
have remarkable contribution in this field. Few of such techniques are discussed as under:
The problem of incongruent melting can be tackled by one of the following means:
(i)
(ii)
(iii)
(iv)
(v)
by mechanical stirring,
by encapsulating the PCM to reduce separation,
by adding of the thickening agents which prevent setting of the solid salts by holding it in
suspension,
by use of excess of water so that melted crystals do not produce supersaturated solution,
by modifying the chemical composition of the system and making incongruent material
congruent .
To overcome the problem of phase segregation and supercooling of salt hydrates, scientists of General
Electric Co., NY suggested a rolling cylinder heat storage system. The system consists of a cylindrical
vessel mounted horizontally with two sets of rollers. A rotation rate of 3 rpm produced sufficient motion
of the solid content
(i)
(ii)
(iii)
to create effective chemical equilibrium,
to prevent nucleation of solid crystals on the walls, and
to assume rapid attainment of axial equilibrium in long cylinders.
Some of the advantages of the rolling cylinder method are:
(i)
(ii)
(iii)
(iv)
(v)
complete phase change,
Melting point and latent heat of fusion: salt hydrates latent heat released was in the
range of 90–100% of the theoretical latent heat,
Repeatable performance over 200
cycles,
high internal heat transfer rates,
Freezing occurred uniformly.
As a single PCM cannot have all the desired properties viz thermophysical, chemical, kinetics, and at the
same time economical, one has to go for designing a suitable system to compensate for the
aforementioned inadequacy [16]. For example metallic fins can be used to compensate the poor thermal
conductivity of PCMs, supercooling may be suppressed by introducing a nucleating agent or a ‘cold
finger’ in the storage material and thickness of the PCM can be optimized to compensate the poor meltfreeze cycle of the material.
In general inorganic compounds have almost double volumetric latent heat storage capacity (250–400
kg/dm3) than the organic compounds (128–200 kg/dm3). For their very different thermal and chemical
behavior, the properties of each subgroup which affects the design of latent heat thermal energy storage
systems using PCMs of that subgroup are discussed in detail below.
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4. APPLICATIONS
Ravankar [24] presented a new testing method for satellite power using latent heat storage. PCM becomes
liquid under high temperature, which then freezes during hours of cold darkness and released its latent
heat. The released heat can used to generate electricity by driving thermoelectric units. John et al. [25]
designed a novel ventilation nighttime cooling system (a novel combination of PCM and heat pipes) as an
alternative to air conditioning. The system offers substantial benefits in terms of reducing or eliminating
the need for air conditioning. Microencapsulated PCMs can be included within textile fibers; composites
and clothing to provide greatly enhanced thermal protection in both hot and cold environments [26].
Cabeza et al. [27] reported that the PCM can be used for transporting temperature sensitive medications
and food because the PCMs capability to store heat and cold in a range of several degrees. Several
companies are engaged in the research of transporting temperature sensitive PCMs for various
applications [28-32].
Vasiliev et al. [33] developed the latent heat storage module for motor vehicle because the heat is stored
when the engine stopped, and can be used to preheat the engine on a new start. It is possible to reach an
optimized working temperature within the engine in a much shorter time using the heat storage than
without heat storage. Pal and Joshi [34] [35] recommended the PCM to restrict the maximum temperature
of electronic components. Tan et al. [36] conducted an experimental study on the cooling of mobile
electronic devices, and computers, using a heat storage unit (HSU) filled with the phase change material
(PCM) of n-eicosane inside the device. The high latent heat of n-eicosane in the HSU absorbs the heat
dissipation from the chips and can maintain the chip temperature below the allowable service temperature
of 50 OC for 2 h of transient operations of the PDA.
Climator [37] has developed a cooling vest for the athletes for reducing the body temperature. PCMs also
proposed for cooling the newborn baby [38]. Koschenz et al. [39] developed a thermally activated ceiling
panel for incorporation in lightweight and retrofitted buildings. It was demonstrated, by means of
simulation calculations and laboratory tests, that a 5 cm layer of microencapsulated PCM (25% by
weight) and gypsum surface to maintain a comfortable room temperature in standard office buildings.
Heptadecance were tried as PCM in this prototype set-up. Naim et al. [40] constructed a novel continuous
single-stage solar still with PCM. They reported that the productivity of a solar still can be greatly
enhanced by the use of a PCM integrated to the still. Huang et al. [41] used PCMs for thermal regulation
of building-integrated photovoltaic. Depending on ambient conditions, a PV/PCM system may enable the
PV to operate near its characterizing temperature (25 OC). They developed PV/PCM simulation model
and validated with experimental results. The improvement in the thermal performance achieved by using
metal fins in the PCM container is significant. The fins enable a more uniform temperature distribution
within the PV/PCM system to be maintained. An extensive experimental test has been undertaken on the
thermal behavior of a phase change material, when used to moderate the temperature rise of PV in a
PV/PCM system [42] [43] [44[ Use of PCM with photovoltaic (PV) panels and thermoelectric modules
(TEMs) in the design of a portable vaccine refrigerator for remote villages with no grid electricity was
proposed by Tavaranan et al. [45]. TEMs, which transfer heat from electrical energy via the Peltier effect,
represent good alternatives for environmentally friendly cooling applications, especially for
relatively low cooling loads and when size is a key factor. Thermoelectric refrigeration systems
employing latent heat storage have been investigated experimentally by Omer et al. [46]. Duffy and
Trelles [47] proposed a numerical simulation of a porous latent heat thermal energy storage device for
thermoelectric cooling under different porosities of the aluminum matrix. They used a porous aluminum
matrix as a way of improving the performance of the system, enhancing heat conduction without reducing
significantly the stored energy.
Weinlader et al. [48] used PCM in double-glazing façade panel for day lighting and room heating. A
facade panel with PCM shows about 30% less heat losses in south oriented facades. Solar heat gains are
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also reduced by about 50%. Facade panels with PCM improve thermal comfort considerably in
winter, especially during evenings. In summer, such systems show low heat gains, which reduces peak
cooling loads during the day. Additional heat gains in the evening can be drawn off by nighttime
ventilation. If a PCM with a low melting temperature of up to 300C is used, thermal comfort in summer
will also improve during the day, compared to double glazing without or with inner sun protection. Ying
et al. [49] developed the test standards for PCM fabrics. Three indices have been proposed to characterize
the thermal functional performance of PCM fabrics. The index of thermal regulating capability can
described the thermal regulating performance of PCM fabrics, and is strongly dependent on amount of
PCM. Khateeb et al. [50] designed a lithium-ion battery employing a novel phase change material (PCM)
for thermal management system in electric scooter. Developed Li-ion battery was suggested in order to
replace the existing lead–acid battery in the electric scooter with the Li-ion battery without introducing
any mechanical changes in the battery compartment.
5. SUMMARY
This entire discussion leads to a promising solution for the problem of depleting fuel resources in the
form of latent heat storage materials. As discussed in preceding chapters, an outcome can be drawn to
focus more onto the storing the immensely available energy sources, i.e. solar radiation. This can be
stored into the various phase change materials as stated and suggested into the previous discussion.
Latent heat storage materials can store 5 to 14 times more energy as compared to other conventional
methods. This leads to a higher efficiency and considerable cost reduction in overall setup. Such materials
can store energy isothermally with minimum volume and mass which turns out into the biggest
achievement in the field of energy storage
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