Evolution of the Study of Phase Diagram of Binary and Ternary Mixtures Involving Fatty Acid Esters.

Interest in phase change materials keeps on rising as thermal energy storage grows in popularity in the scientific community as a promising complement for renewable energies in the future. Extending the possibilities beyond pure compounds, the use of mixtures (especially eutectics) widens the range of suitable phase change materials (PCM) available in the market. However, a precise knowledge of the mixtures' phase behavior is required, making phase diagrams the most appropriate tools to follow. The aim of this work is to collect and analyze published literature concerning the phase diagrams of fatty acid esters mixtures, which constitute promising candidates as PCM due to their attractive properties, such as high latent heat, chemical stability and the possibility of extracting them from vegetable and animal oils. The topic appears as a still open scientific field, where further studies need to be performed to complete, complement and perfect the currently available information.

Triglycerides as Novel Phase-Change Materials: A Review and Assessment of Their Thermal Properties.

Latent Heat Storage (LHS) with Phase-Change Materials (PCMs) represents a high energy density storage technology which could be applied in a variety of applications such as waste heat recovery and integration of renewable energy technologies in energy systems. To increase the sustainability of these storage solutions, PCMs have to be developed with particular regard to bio-origin and biodegradability. Triglycerides represent an interesting class of esters as the main constituents of animal and vegetable fats, with attractive thermal properties. In order to be used as PCMs, the thermal behaviour of triglycerides has to be fully understood, as in some cases they have been reported to show polymorphism and supercooling. This study assesses the suitability of triglycerides as PCMs by reviewing the literature published so far on their behaviour and properties. In particular, melting points, enthalpies of fusion, polymorphism, thermal conductivities, heat capacities and thermal cycling stabilities are considered, with a focus on LHS and thermal energy storage applications. In addition, the efforts conducted regarding modelling and the prediction of melting points and enthalpies based on chemical structures are summarized and assessed.

Investigation of the Thermal Properties of Diesters from Methanol, 1-Pentanol, and 1-Decanol as Sustainable Phase Change Materials.

Esters present several advantages when compared to traditional materials used for thermal energy storage, amongst which are better sustainability and greater chemical stability. However, at present, their thermal properties remain mostly unknown or not well documented. In this study, 12 diesters from four dicarboxylic acids (oxalic, succinic, suberic, sebacic) and three alcohols (methanol, 1-pentanol, 1-decanol) have been assessed as bio-based phase change materials for thermal energy storage. All diesters have been synthesized via Fischer esterification to high purities, and their chemical structures, as well as thermal properties, have been fully characterized. The diesters investigated show phase change transitions in a low-mid temperature range between -32 and 46 °C with maximum enthalpies of 172 J/g and show higher degrees of supercooling compared to fatty monoesters. Similarly to other esters classes, some trends correlating the chemical structures to the thermal properties were identified, which would allow for the development of property prediction tools.

Investigation of Lactones as Innovative Bio-Sourced Phase Change Materials for Latent Heat Storage.

In the presented work, five bio-based and bio-degradable cyclic esters, i.e. lactones, have been investigated as possible phase change materials for applications in latent heat storage systems. Commercial natural lactones such as ε-caprolactone and γ-valerolactone were easily purchased through chemical suppliers, while 1,2-campholide, oxa-adamantanone and dibenzochromen-6-one were synthesized through Baeyer-Villiger oxidation. The compounds were characterized with respect to attenuated total reflectance spectroscopy and gas chromatography coupled with mass spectroscopy, in order to confirm their chemical structures and identity. Subsequently, thermogravimetric analysis and differential scanning calorimetry were used to measure the phase change temperatures, enthalpies of fusion, degradation temperatures, as well to estimate the degree of supercooling. The lactones showed a wide range of phase change temperatures from -40 °C to 290 °C, making them a high interest for both low and high temperature latent heat storage applications, given the lack of organic phase change materials covering phase change temperature ranges below 0 °C and above 80 °C. However, low enthalpies of fusion, high degrees of supercooling and thermal degradations at low temperatures were registered for all samples, rendering them unsuitable as phase change materials.