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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: raiajeet@rediffmail.com ashish.05408@gmail.com
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 earths 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 worlds total generated electricity. Moreover, the total annual solar radiation falling on the earth is more than 7500 times of the worlds 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 byQ= Q= [ + + + + ] (3) (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. 215

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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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Latent Heat (kJ/kg) n.a. n.a. 226 247 205 n.a. 273 237 215 184 245 222 251 152.7 247 260 201 161 120 183 167 209 157 130 118 141 93 239 107 121 Latent Heat (kJ/kg) 164 199 178 191 121 257 147 255 103 130 134 164 177 109 86 121 115 202.5 111 189 102 140 174 241 163 171 204 142.8 169.4 174

Material n-Dodecane n-Tridecane n-Tetradecane Formic acid N-Pentadecane Oleic acid Acetic acid N-Hexadecane n-Heptadecane D-Lactic acid n-Octadecance n-Nonadecane Paraffin wax Capric acid n-Eicosane Caprilone Docasyle bromide N-henicosane Phenol N-Lauric acid P-Joluidine Cynamide N-Docosane N-Tricosane Hydrocinnamic acid Cetyl alcohol O-Nitroaniline Camphene Diphenyle amine P-Dicchlorobenzene P. Paraffin N.P. Non paraffin n.a. Not available

Melting point (oC) -12 -6 5.5 7.8 10 13.5-16.3 16.7 16.7 22 26 28.2 31.9 32 32 37 40 40 40.5 41 43 43.3 44 44.5 47.6 48 49.3 50 50 52.9 53.1

Category P. P. P. N.p. P. N.p. N.p. P. P. N.p. P. P. P. N.p. P. N.p. N.p. P. N.p. N.p. N.p. N.p. P. P. N.p. N.p. N.p. N.p. N.p. N.p.

Material N-Pentacosane Myristic acid Oxolate Tristearin O-Xylene dichloride n-Hexacosane Chloroacetic acid N-hexaacosane Nitro naphthalene Chloracetic acid N-Octacosane Palmitic acid Bees wax Glyolic acid P-Bromophenol Azobenzene Acrylic acid Stearic acid Dintro toluene(2,4) n-Tritricontane Phenylacetic acid Thiosinamine Benzylamine Acetamide Alpha napthol Quinone Succinic anhydride Benzoic acid Benzamide Alpha glucose

Melting point (oC) 53.7 54 54.3 54.5 55 56 56 56.3 56.7 61.2 61.4 61.8 61.8 63 63.5 67.1 68 69 70 71 76.7 77 78 81 96 115 119 121.7 127.2 141

Category P. N.p. N.p. N.p. N.p. P. N.p. P. N.p. N.p. P. N.p. N.p. N.p. N.p. N.p. N.p. N.p. N.p. P. N.p. N.p. N.p. N.p. N.p. N.p. N.p. N.p. N.p. N.p.

Table 1: List of Organic Materials [7] [11] [13] [17] [18] 217

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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 freezemelt 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 paraffins. 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 22.5 times greater than that of technical grade paraffins. 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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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 3, Number 2, July-December (2012), IAEME Melting point (0C) 1 3.7 4 8 10.4 11 14 17 18 18 18.5 23.7 25 25.7 26 Latent Heat (kJ/kg) 85 318 33 253 100 163 108 50 286 330 231 64 148 289 147 Melting point (0C) 27 28.3 29-30 30 30 31.8 38.2 55 73.4 307 333-380 380 714-800 857 897 Latent Heat (kJ/kg) 105 15 170-192 80 38 10 23 213 25 17-199 116-266 149 452-492 452 235

Name POCl3 D2O SbCl5 LiClO3.3H2O H2SO4 NH4Cl.Na2SO4.10H2O K2HO4.6H2O MOF6 NaCl.Na2SO4.10H2O KF.4H2O K2HO4.4H2O P4O3 Mn(NO3)2.6H2O LiBO2.8H2O H3PO4

Name FeBr3.6H2O Cs CaCl2.6H2O Ga AsBr3 BI3 TiBr4 H4P2O6 SbCl3 NaNO3 KNO3 KOH MgCl2 KF K2CO3

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 solidliquid 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 paraffins), and Small volume changes on melting. salt hydrates are

They are not very corrosive, compatible with plastics and only slightly toxic. Many sufficiently inexpensive for the use in storage.

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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, metallics 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.
Latent Heat of Fusion (kj/kg) 234 n.a. 97.9 n.a. 136 95 Latent Heat of Fusion (kj/kg) 125.5 132.2 148 168 123.4 234

Name

Composition

Melting Point

Name

Composition

Melting Point

Na2SO4+NaCl+KCl+H2O Na2SO4+NaCl+NH4Cl+H2O C5H5C6H5+ (C6H5)2O Na2SO4+NaCl+H2O Ca(NO)3.4H2O Mg(NO)3.6H2O NH2CONH2 + NH4 NO3
n.a. Not available

31+13+16+40 32+14+12+42 26.5+73.5 37+17+46 + 47+53 n.a.

4 11 12 18 30 46

Mg(NO3)2.6H2O + NH4 NO3 Mg(NO3)2.6H2O + MgCl2.6H2O Mg(NO3)2.6H2O + Al(NO3)2.9H2O Mg(NO3)2.6H2O + MgBr2.6H2O Napthalene Benzoic Acid +

61.5+38.4 58.7+41.3 53+47 59+41 67.1+ 32.9 79+17+4

52 59 61 66 67 68

AlCl3+NaCl+ZrCl2

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, 220

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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 90100% 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 (250400 kg/dm3) than the organic compounds (128200 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 faade 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 222

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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 leadacid 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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