Applied Thermal Engineering 23 (2003) 16971704

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Thermal performance of sodium acetate trihydrate thickened with dierent materials as phase change energy storage material
Luisa F. Cabeza
b

a,*

, Gustav Svensson b, Stefan Hiebler b, Harald Mehling

b,1

a tica i Eng. Industrial, Universitat de Lleida, Jaume II, 69, 25001 Lleida, Spain Departament dInforma ZAE Bayern, Abt. 1 Energy Conversion and Storage, Walther-Meissner-Str. 6, 85748 Garching, Germany

Abstract The use of phase change materials (PCMs) in energy storage has the advantage of high energy density and isothermal operation. Although the use of only non-segregating PCMs is a good commercial approach, some desirable PCM melting points do not seem attainable with non-segregating salt hydrates at a reasonable price. The addition of gellants and thickeners can avoid segregation of these materials. In this paper, sodium acetate trihydrate is successfully thickened with bentonite and starch. Cellulose gives an even better thickened PCM, but temperatures higher than 65 C give phase separation. The mixtures would show a similar thermal behavior as the salt hydrate, with the same melting point and an enthalpy decrease between 20% and 35%, depending on the type and amount of thickening material used. 2003 Elsevier Ltd. All rights reserved.
Keywords: Phase change material; PCM; Thickening; Sodium acetate trihydrate; Thermal performance

1. Introduction Thermal energy storage has recently become a major interest issue due to the interest in use of renewable energies, such as thermal solar energy, and waste heat. The mismatch between energy demand and energy availability can only be overcome by the use of an energy reservoir. The use of phase change materials (PCMs) in energy storage has the advantage of high energy storage vs. sensible heat storage, such as water. Another advantage of latent heat storage is its isothermal operating characteristics.
*

Corresponding author. Tel.: +34-973-702-742; fax: +34-973-702-702. E-mail addresses: lcabeza@diei.udl.es (L.F. Cabeza), mehling@muc.zae-bayern.de (H. Mehling). 1 Tel.: +49-89-32944222; fax: +49-89-32944212.

1359-4311/03/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S1359-4311(03)00107-8

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Sodium acetate trihydrate has been studied as PCM by several authors [110] because of its large latent heat of fusion (about 240 J/g) which makes it attractive as a latent heat storage material. Its melting temperature (about 58 C) makes it suitable for applications such as solar energy storage for domestic hot water. One of the problems that some salt hydrates exhibit when used as PCMs is phase segregation. This means that under continuously melting and thawing, the dierence in density between the water and the salt components of the salt hydrate, results in segregation. The consequence is a bad crystallization of the compound, and a change in the thermophysical properties of the PCM. Segregation can be prevented changing the properties of the salt hydrate with the addition of another material that can hinder the heavier phases to sink to the bottom. This can be achieved either with gelling or with thickening materials. Gelling means adding a crosslinked material (e.g. polymer) to the salt to create a three dimensional network that holds the salt hydrate together. Thickening means the addition of a material to the salt hydrate that increases the viscosity and hereby holds the salt hydrate together [11]. This is benecial not only for preventing gross segregation of the lower hydrates or anhydrous salts formed in peritectic reactions, but is also helpful in suspending insoluble nucleating agents. In a previous investigation, Svensson [12] showed that gelling salt hydrates with materials like polyacrylic amide, sodium polyacrylate, and polyvinyl alcohol was not successful, so the experiments carried out with sodium acetate trihydrate focused on thickening with starch, cellulose and bentonite. In this study, the thermal performance and storage parameters of sodium acetate trihydrate thickened with four dierent materials were investigated experimentally.

2. Experimental method 2.1. Materials All the experiments here presented were done using NaCH3 COO 3H2 O of ACS quality from Merck. The nucleator used was Na2 HPO4 7H2 O from Merck. As thickeners, starch, cellulose and bentonite were used. The starch used in the experiments was simple wheat our. There are a variety of dierent starches for industrial usage available on the market, but the wheat our should work equally well and is conveniently available. Two dierent celluloses were tested: methylhydroxyethyl-cellulose (MHE-cellulose), and methylcellulose (M-cellulose). These are commercial industrial products and manufactured and sold by Wol Cellulosics, Wahlsrode Germany, under the product name Walocel. d-Chemie, Krefeld Germany, One type of bentonite was tested, manufactured and sold by Su under the name Ceratosil CV, where the cation is calcium, and is activated. 2.2. Methodology The procedure to do the experiments was:

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100 g of sodium acetate trihydrate was mixed with 1 g of nucleator and melted in a water bath at 80 C. Then the liquid was transferred to a beaker and the thickener was added carefully while mixed rapidly. The thermal performance was tested with dierential scanning calorimetry (DSC) on small samples, and with cool down experiments on a larger sample. The cool down experiments were carried out as follows: The thickened PCM was transferred to 14 ml plastic tubes. The tubes were heated up to 80 C in a water bath and then let them cool down at ambient temperature. In a second experiment, the tubes were heated up and let cool down in a styrofoam container for isolation of the samples. With this experiment, the samples can be considered isothermal. To make a comparison, a sample of sodium acetate trihydrate with 1 wt% nucleator was also tested in the DSC.

3. Results Fig. 1 shows the thermal behavior of the cool down experiments in two dierent samples of sodium acetate trihydrate with 1 wt% nucleator thickened with 20 wt% starch. It should be
90 80
styrofoam freezing

air freezing

70

Temperature (C)

60 50 40 30 20 10 0 0:00:00

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Fig. 1. Thermal performance of thickened PCM: sodium acetate trihydrate + 20 wt% starch.

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pointed out that when starch is added to the salt hydrate, it turns out to be a material very dicult to handle, because it becomes very sticky. In the same way, the mixture is a material which behavior is dicult to measure. As it can be seen in Fig. 1, starch seems to change the melting and freezing temperatures of the sodium acetate trihydrate (melting point now is $70 C, and freezing point is 4550 C with 510 C of subcooling), but this behavior was not corroborated in DSC measurements (Table 1). When using bentonite as thickening material, the viscosity does not increase slowly, but there is a sudden change in the sample when a certain amount of bentonite is added. With sodium acetate trihydrate, no change was found with the addition of 40 wt% of bentonite, so 50 wt% addition was necessary. Fig. 2 shows the thermal performance of the thickened material in two dierent samples. It can be seen that the melting and freezing temperature remains to be around 58 C, as with pure sodium acetate trihydrate, but a subcooling of about 10 C occurs.

Table 1 DSC results of sodium acetate trihydrate with 1 wt% Na2 HPO4 7H2 O as nucleator, with dierent thickening materials Compound NaCH3 COO 3H2 O +20 wt% starch +50 wt% bentonite +30 wt% MHE-cellulose Melting temperature (C) 55.656.5 54.7 56.4 55.1 Measured enthalpy (J/g) 237243 180189 153161 165 Extrapolated enthalpy of NaCH3 COO 3H2 O (J/g) 225236 306322 234

90 air freezing 80 70 styrofoam freezing

Temperature (C)

60 50 40 30 20 10 0 0:00:00

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Fig. 2. Thermal performance of thickened PCM: sodium acetate trihydrate + 50 wt% bentonite.

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The use of cellulose seemed to be one of the best chances for thickening of salt hydrates. The viscosity of the sample increases with increasing amounts of cellulose, so dierent concentrations can be used depending on the application. Fig. 3 shows the thermal performance of sodium acetate trihydrate thickened with 30 wt% of MHE-cellulose in two dierent samples, on cool down experiments. As can be seen, the melting temperature decreases by a small amount, to about 55 56 C, but the subcooling is not as severe as with the other materials. Fig. 4 shows the thermal performance of sodium acetate trihydrate thickened with 15 wt% of MHE-cellulose in two dierent samples. The curves are very similar to the one of Fig. 3. The problem with these samples appeared after a few cycles of heating/cooling, when a separation between the salt hydrate and the cellulose occurred. To check if this was due to the cellulose used, a new mixture with methyl cellulose (M-cellulose) was prepared and tested (Fig. 5). Again, after a few cycles the salt hydrate and the cellulose separated. Finally, one fresh sample of sodium acetate trihydrate thickened with 30 wt% of MHE-cellulose and one thickened with 30 wt% of M-cellulose were cycled using a maximum heating temperature of 65 C. The thermal performance is presented in Fig. 6. These samples did not separate after repeated cycling, and the thermal behavior of both samples was very similar. Table 1 presents the results of the DSC measurements done to the dierent materials used in these experiments. As can be seen, the melting temperature of the samples has not changed dramatically with any of the thickening materials used. The entalphy of the mixtures decreases from 240 J/g of the sodium acetate trihydrate to between 155 and 190 J/g in dierent samples. When the enthalpy of the mixtures is extrapolated to see that due to the sodium acetate trihydrate

90 air freezing 80 70 styrofoam freezing

Temperature (C)

60 50 40 30 20 10 0 2:00:00

4:00:00

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Fig. 3. Thermal performance of thickened PCM: sodium acetate trihydrate + 30 wt% MHE-cellulose.

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air freezing 70

styrofoam freezing

Temperature (C)

60 50 40 30 20 10 0 0:00:00

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Fig. 4. Thermal performance of thickened PCM: sodium acetate trihydrate + 15 wt% MHE-cellulose.

90 air freezing 80 70 styrofoam freezing

Temperature (C)

60 50 40 30 20 10 0 2:00:00

4:00:00

6:00:00

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Fig. 5. Thermal performance of thickened PCM: sodium acetate trihydrate + 30 wt% M-cellulose.

in the samples, all of them turn to be close to that of sodium acetate, except in the bentonite sample.

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Fig. 6. Thermal performance of thickened PCM: sodium acetate trihydrate + 30 wt% cellulose.

4. Conclusions The experiments here carried out showed that thickening of salt hydrates is possible. Sodium acetate can be successfully thickened with starch and bentonite. Cellulose gives a better material, but then the mixture can only be heated up to 65 C to avoid separation of the materials. The mixtures would show a similar thermal behavior as the salt hydrate, with the same melting point and an enthalpy decrease between 20% and 35%, depending on the type and amount of thickening material used.

Acknowledgement This project was partially funded by the Vicerectorate of Research of the University of Lleida.

References
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