Pergamon

www.elsevier.com / locate / solener

PII:

Solar Energy Vol. 66, No. 6, pp. 483490, 1999 1999 Elsevier Science Ltd S 0 0 3 8 0 9 2 X ( 9 9 ) 0 0 0 4 5 6 All rights reserved. Printed in Great Britain 0038-092X / 99 / $ - see front matter

ACCELERATED THERMAL CYCLE TEST OF LATENT HEAT-STORAGE MATERIALS

S. D. SHARMA, D. BUDDHI and R. L. SAWHNEY
Thermal Energy Storage Laboratory, School of Energy and Environmental Studies, Khandwa Road Campus, Devi Ahilya University, Indore 452 017, India Received 15 June 1998; revised version accepted 1 April 1999 Communicated by ERICH HAHNE

AbstractAccelerated laboratory experiments have been conducted to study the change in latent heat of fusion, melting temperature and specic heat of commercial-grade stearic acid, acetamide and parafn wax subjected to repeated 300 melt / freeze cycles. The latent heat of fusion, melting temperature and specic heat of the samples were measured after 0, 20, 50, 70, 100, 150, 200, 250 and 300 thermal cycles using a differential scanning calorimeter. Acetamide and parafn wax were found to be more stable phase change materials (PCMs). However, acetamide absorbs moisture from the surrounding atmosphere. 1999 Elsevier Science Ltd. All rights reserved.

1. INTRODUCTION

In recent years, the use of phase change material (PCM) for thermal energy storage has received considerable attention because of its high storage density and the isothermal nature of the storage process. Abhat et al. (1981), Bansal and Buddhi (1992a) and Buddhi (1997) have studied the use of PCMs in cylindrical heat-exchanger geometries in solar water heating and industrial waste heat recovery systems. Experimental and theoretical efforts have been made to incorporate PCMs into at plate collectors for storing solar energy by Bansal and Buddhi (1992b) and Buddhi et al. (1987). Phase change materials have also been used in solar green houses for curing and drying processes and for plant production by Green and Vliet (1981), Huang et al. (1975) and Jaffrin and Cadier (1982). Morrison and Adbel Khalik (1978), Ghoneim (1989) and Theunissen and Buchlin (1983) have used PCMs in air-based solar systems. A solar thermal system with latent heat storage undergoes one melt / freeze cycle per day. This can be called a normal cycle, however, a repeated melt / freeze cycles test, conducted in the laboratory with a hot plate or similar system, is called an accelerated thermal cycle test. The effects of melting temperature and of the latent heat of

fusion on the performance of a phase-change energy-storage system have also been studied by Bansal and Buddhi (1992a). Ting et al. (1987) conducted accelerated cycle tests on a PCM unit having (Na 2 SO 4 .n H 2 O) at different ratios by weight. They studied the effect of 1000 thermal cycles on the container tube, but did not analyze its effect on the thermophysical properties of the PCM. Fernanda (1988) has also studied the thermal reliability of salt hydrate PCMs with melting temperatures between 15 and 328C by measuring latent heat of fusion and melting temperature after subjection to repeated cycles. For latent heat storage, commercial-grade PCMs with a purity of about 95% are preferred due to their large-scale availability and low cost. In general, the thermophysical properties and behavior of commercial-grade materials are found to be very different from those quoted in the literature for laboratory-grade materials (purity more than 99%). Since limited data are available on the effect of thermal cycling on commercialgrade PCMs, it is important to study the effects of thermal cycling on the melting temperature, latent heat of fusion and the specic heat of commercial-grade PCMs. The present paper is an effort in this direction.

2. PHASE CHANGE MATERIALS ANALYZED

Author to whom correspondence should be addressed. Tel.: 1 91-731-460-309; fax: 1 91-731-470-372; e-mail: dbuddhi@hotmail.com 483

PCMs, which can be used for low-temperature solar thermal applications like water heating, baking and drying should have a melting / freezing

484

S. D. Sharma et al.

Table 1. Comparison of thermophysical properties and cost of laboratory-grade (L.G.) and commercial-grade (C.G.) PCMs Chemical name Stearic acid CH 3 (CH 2 ) 16 ? COOH L.G. Melting temperature ( 8C) Latent heat of fusion (k J kg 2 1 ) Specic heat (k J kg 2 1 K 2 1 ) Cost (US$)
a b

Acetamide CH 3 CONH 2 L.G. 81 241 1.98 35 / kg b C.G. 82

a

Parafn wax L.G. 54 141 2.04 16 / kg b C.G. 53 a 184 a 2.05 a 2.0 / kg T

C.G. 66
a

69.4 199 2.07 100 / 100g b

155 a 2.46 a 1.0 / kg T

263 a 1.94 a 2.5 / kg T

Measured value at zero cycle. From the price list of Fluka Chemica-Bio Chemical, Switzerland, 19931994. T From the price list of Loba Chemie, India, 19971998.

cycle in the temperature range of 45 to 908C. Commercial-grade stearic acid, acetamide and parafn wax were chosen due to their low cost and large availability on the Indian market. A comparison of their thermo-physical properties with those of laboratory-grade (Hale et al., 1971; Galen and Van den Brink, 1986) materials is given in Table 1.
3. ACCELERATED TEST PROCESS

Experiments have been conducted to study the changes in melting point, latent heat of fusion and in the specic heat of PCMs after a repeated number of melt / freeze cycles. The experimental setup consists of an electric hot plate with a temperature controller. PCM was put in a commercial stainless steel container with a lid. The inner diameter and height of the container were 9.3 and 4.0 cm, respectively. PCM was heated above the melting temperature and then allowed to cool under room conditions. A differential scanning calorimeter (DSC) manufactured by Rheometric Scientic Ltd. UK was used for measuring the latent heat of fusion, the specic heat and the melting temperature of the solidied material. In the DSC, sample and reference materials are heated at a constant rate. The temperature difference between them is proportional to the difference in heat ow between the two materials. Alumina (Al 2 O 3 ), the reference material recommended by the DSC manufacturer, was used. The latent heat of fusion was calculated using the area under the peak of the DSC curve, and the melting temperature was estimated by the tangent at the point of greatest slope on the face portion of the peak, as shown in Fig. 1 (a DSC curve showing variation of heat ow with sample temperature). An isothermalrampisothermal with sapphire method was used to measure the specic heat of the sample. Thermal software (version plus ve),

supplied by the Rheometric Scientic Ltd. UK, was used for calculating all of these parameters. The graphs obtained for latent heat of fusion, melting temperature and specic heat for zero cycle of each material are shown in Figs. 13. From these gures, it can be seen that the melting process for acetamide and parafn wax is quite sharp, whereas, for stearic acid, it is broader. The samples for each material were subjected to 300 accelerated melt / freeze cycles. About 1 g of material was withdrawn after 0, 50, 100, 150, 200, 250 and 300 test cycles to study the change in the latent heat of fusion, melting temperature and specic heat. To minimize the effect of the surrounding moisture, the samples were kept in a desiccator.
4. EXPERIMENTAL, RESULTS AND DISCUSSION

For the repeated tests of thermal cycling, the temperature of the hot plate was maintained at approximately 75, 110 and 658C to melt the stearic acid (melting temperature, 638C), acetamide (melting temperature, 828C) and parafn wax (melting temperature, 538C), respectively. The quantities of stearic acid, acetamide and parafn wax were 90, 130 and 150 g, respectively. The melting times were about 35, 40 and 25 min and, for solidifying, they were about 50, 70 and 40 min, respectively. The measured latent heat of fusion and the melting temperature of stearic acid, acetamide and parafn wax after the thermal cycles mentioned above are given in Tables 24. As one can see from the tables, the latent heat of fusion of stearic acid, acetamide and parafn wax has a variation of 0 to 1 23%, 2 1 to 1 14% and 2 12 to 1 2%, respectively, from their zero cycle values during 300 cycles. For measuring the melting temperature of the 20th test cycle of stearic acid, a tangent was automatically drawn at the largest slope on the face of the

Accelerated thermal cycle test of latent heat-storage materials

485

Fig. 1. DSC measurement of the latent heat of fusion and of the melting temperature of stearic acid of the zero cycle.

selected peak acd (Fig. 4). The resulting melting temperature is 528C, which is very low in comparison to the zero cycle and far from the extreme lower peak point c. To determine the melting point with reference to this extreme lower peak,

the bcd curve was selected and the melting temperature was 668C. Similar types of curves were observed in up to 250 test cycles and the resulting two melting temperatures obtained in a similar manner are tabulated in Table 2. The

Fig. 2. DSC measurement of the latent heat of fusion and melting temperature of acetamide of the zero cycle.

486

S. D. Sharma et al.

Fig. 3. DSC measurement of the latent heat of fusion and melting temperature of parafn wax of the zero cycle.

Table 2. Latent heat of fusion, melting temperature and specic heat of stearic acid with test cycles Number of test cycles 0 20 50 70 75 100 150 200 250 300 Laboratorygrade material
a

Melting temperature ( 8C) 1 63 66 65 65 64 65 64 63 64 63 69.4 2 NA 52 56 50 51 50 51 50 48 NA

Latent heat of fusion (kJ kg 2 1 ) 155 169 170 190 167 188 175 156 180 159 199

Specic heat (kJ kg 2 1 K 2 1 ) 2. 46 a 2 2 2 2 2.38 a 2 2.00 a 2 2.03 a 2.07 a

At 328C. 1, corresponding to the extreme lower peak. 2, corresponding to other than the extreme lower peak.

Table 3. Latent heat of fusion, melting temperature and specic heat of acetamide with test cycles Number of test cycles 0 10 50 75 100 150 200 300 Laboratory-grade material
a

Melting temperature ( 8C) 82 84 82 83 83 83 82 82 81

Latent heat of fusion (kJ kg 2 1 ) 263 284 260 299 287 277 289 268 241

Specic heat (kJ kg 2 1 K 2 1 ) 1.94 a 2 2 2 1.84 a 2 2.01 a 1.74 a 1.98

At 508C.

Accelerated thermal cycle test of latent heat-storage materials Table 4. Latent heat of fusion, melting temperature and specic heat of parafn wax with test cycles Number of test cycles 0 20 50 100 200 300 Laboratory-grade material
a

487

Melting temperature ( 8C) 53 54 54 52 54 53 54

Latent Heat of fusion (kJ kg 2 1) 184 172 176 188 162 165 146

Specic heat (kJ kg 2 1 K 2 1 ) 2.05 a 2 2 2.16 a 2.07 a 2.01 a 2.04 a

At 408C.

major change in the melting temperature of stearic acid was noticed after twenty cycles, when the melting temperature was reduced to 528C. After 300 cycles, the melting temperature and the latent heat of fusion of the zeroth cycle were almost repeated. As one can see from Tables 3 and 4, no major change in the melting temperatures of acetamide and parafn wax were noticed. DSC curves (showing variation of the heat ow-rate with temperature) for each of the test cycles of stearic acid, acetamide and parafn wax are shown in Figs. 57. From Fig. 5 and Table 2, it is seen that the latent heat and melting temperature of the stearic acid, although erratic, show no regular degradation with melting / freezing cycles. After the 0th, 100th, 200th and 300th test cycles, the specic heat of stearic acid, acetamide and

parafn wax was also measured. These values are tabulated in Tables 24, respectively. In Table 2, it can be seen that the specic heat of stearic acid decreases as the number of cycles increases and that it is nearly constant after 200 cycles. In Tables 3 and 4, one sees that no major change in the values of the specic heat of acetamide and parafn wax, even after 300 cycles, were observed in cycling tests. Also of note is the observation that the color of the stearic acid changed from white to light yellow after 175 cycles. Furthermore, it was observed that acetamide absorbs moisture from the surroundings and its melting behavior changes signicantly, as shown in Fig. 8. Therefore, the samples of acetamide under test cycles were kept in a desiccator to eliminate the effect of surrounding

Fig. 4. DSC measurement of the latent heat of fusion and melting temperature of stearic acid of the 20th cycle.

488

S. D. Sharma et al.

Fig. 5. DSC curves for stearic acid of the different test cycles.

moisture. The weights of the stearic acid, acetamide and parafn wax were also measured after each test cycle, to determine if there had been any

loss due to evaporation. For each of these materials, no loss due to evaporation was observed, even after 300 cycles.

Fig. 6. DSC curves for acetamide of the different test cycles.

Accelerated thermal cycle test of latent heat-storage materials

489

Fig. 7. DSC curves for parafn wax of the different test cycles.

Fig. 8. DSC curve of acetamide with moisture.

490

S. D. Sharma et al.

5. CONCLUSION

After 300 thermal cycles, the samples showed no regular degradation in their thermal properties. Acetamide and parafn wax show reasonably good stability throughout the cycling process and can be considered as promising PCMs. Acetamide, however, absorbs moisture from the surrounding environment. Stearic acid melts over a range of temperatures but is also thermally stable after repeated melting / freezing cycles.
Acknowledgements This work was carried out under project no. Engg.-SC-21 / 94 Identication and development of low cost latent heat materials for storage of solar thermal energy for low temperature applications, nanced by Madhya Pradesh Council of Science and Technology, Bhopal, India.

REFERENCES
Abhat A. et al. (1981). Development of a modular heat exchanger with an integral latent heat storage, Report No. BMFT FB T81-050. German Ministry of Science and Technology. Bansal N. K. and Buddhi D. (1992a) An analytical study of a latent heat storage system in a cylinder. Energy Convers. Mgmt. 33(4), 235242. Bansal N. K. and Buddhi D. (1992b) Performance equation of a collector cum storage system using phase change materials. Solar Energy 48, 185194. Buddhi D. (1997) Thermal performance of a shell and tube PCM storage heat exchanger for industrial waste heat recovery. Presented at Solar World Congress, Taejon, Korea. Aug. 2430.

Buddhi D., Kishore J. and Bansal N. K. (1987) An experimental study of a solar collector cum storage system with phase change materials. In Energy Options for the 90 s, pp. 5158, Tata McGraw Hill, New Delhi. Fernanda G. P. (1988) Salt hydrates used for latent heat storage: Corrosion metals and reliability of thermal performance. Solar Energy 41(2), 193197. Galen E. and Van den Brink G. J. (1986) Energy storage in phase change materials for solar applications. International Journal of Ambient Energy 7(1), 3146. Ghoneim A. A. (1989) Comparison of theoretical model of phase change and sensible heat storage for air and water based solar heating system. Solar Energy 42, 209220. Green T. F. and Vliet G. C. (1981) Transient response of a latent heat storage unit: An analytical and experimental investigation. Journal of Solar Energy Engineering 103, 275. Hale D. V., Hoover M. J. and ONeill M. J. (1971). Phase Change Materials Hand Book, Report no. HREC-5183-2 LMSC-HREC D225138. NASA, Marshal Space Flight Center, Alabama. Huang B. K., Albrams Jr. C. F., Coats L. L. and Bowers C. G. (1975) Development of greenhouse bulk systems for solar energy utilization and plantbed mechanization, ASME paper no. 75-1018, Am. Soc. Agric. Eng. Journal. St. Joseph, MI. Jaffrin A. and Cadier P. (1982) Latent heat storage applied to horticulture. Labaronne solar green house. Solar Energy 28, 313321. Morrison D. J. and Adbel Khalik S. I. (1978) Effect of phase change energy storage on the performance of air-based and liquid-based solar heating system. Solar Energy 20, 5767. Theunissen P. H. and Buchlin J. M. (1983) Numerical optimization of a solar air heating system based on encapsulated PCM storage. Solar Energy 31, 271277. Ting K. C., Giannakakas P. N. and Gilbert S. G. (1987) Durability of latent heat storage tube sheets. Solar Energy 39(2), 7985.