PhD programmes - Science and Technology
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Development of insulating materials with thermal energy storage/release capability


Nowadays the environmental sustainability and the limitation of the energy consumption of buildings is of substantial importance in order to reduce greenhouse gases emissions and mitigate the consequences of climate change. Thermal energy storage (TES) allows to store thermal energy when available in order to use it when and where necessary. The use of insulating materials with TES capability may results in the compensation of energy absorption peaks caused by air conditioning or by space heating with a consequent reduction of energy consumption and related CO2 emissions. This work aims at the development and characterization of composite materials based on polymeric foams and containing a phase change material providing the TES capability. The production procedures were optimized in order to maximize the quality of the samples and the main properties of the resulting materials were then investigated. Different matrices were considered in this work: thermosetting, thermoplastic and elastomeric ones. As thermosetting matrix, a polyurethane foam was considered: this foam was filled, during the production process, with increasing amounts (from 10 to 40 wt%) of a microencapsulated PCM with a melting point of 24 °C.

The addition of the PCM caused the disruption of the regular close cell morphology of the foams with a consequent increase of the thermal conductivity and a reduction of the mechanical properties. On the other hand, the addition of the PCM led to interesting TES properties, measured both through differential scanning calorimetry and infrared thermography (up to 54 J/g). Polyethylene was chosen as thermoplastic matrix and the technology of salt leaching was used to obtain foams without the use of chemical foaming agents. Foams containing different amounts (up to 56 wt%) of a microencapsulated PCM with a melting point of 24 °C were prepared. The addition of the PCM led to a decrease of the connectivity and porosity values of the prepared foams with a consequent decrease of the mechanical properties and increase of the thermal conductivity. Despite the rupture of a certain part of the PCM capsules due to the production process, good TES properties (up to 50 J/g) were measured. Elastomeric foams were prepared using an EPDM rubber as matrix and different foaming agents for the expansion process: foams obtained using two different commercial foaming agents were compared with foams obtained using the salt leaching technique. In the first case, a shape-stabilized PCM was added during the production process, while in the second one the foams were impregnated with a liquid PCM without the necessity of a shape stabilization.

Salt leaching foams were able to retain higher PCM loads with respect to foams produced using commercial foaming agents and were therefore characterized by higher TES capability (up to 129 J/g). Infrared thermography tests highlighted that the time required to reach a reference temperature during heating/cooling cycles was three times longer for samples with a PCM amount of about 55 wt%. These foams evidenced a general decrease of the mechanical properties upon PCM addition. Moreover, a strong influence of the temperature on the mechanical behaviour of these foams was highlighted, with the PCM acting as softener above its melting point and as hardener below. In order to consider practical applications, elastomeric panels made of an ethylene propylene diene monomer (EPDM) rubber filled with a shape stabilized PCM and covered with a nitrile-butadiene rubber (NBR) envelope were prepared. It was possible to verify the absence of leakage, the uniform distribution of the PCM and the influence of temperature on the mechanical properties of the samples. From rheological tests it was also possible to observe the plasticizing effect of the PCM that hindered the vulcanization process of the EPDM/PCM compound. In the second part of this work larger samples were prepared and used for the internal insulation of wood boxes that were subjected to heating/cooling cycles, simulating thus real summer conditions in north Italy.

The beneficial effect of the PCM resulted in a consistent reduction of the temperature peak with respect to a reference box insulated with elastomeric panels without PCM. Moreover, the fire behaviour of the produced samples was studied and the effect of the addition of different flame retardants was deeply investigated. The addition of a flame retardant based on ammonium polyphosphate and aluminium diethyl phosphinate as synergistic agents allowed a strong reduction of the peak of heat release rate measured through cone calorimeter tests, with a significant improvement of the fire behaviour. Fire tests allowed also to point out the significant role, in improving the fire performances of the samples, of the interactions between ammonium polyphosphate and the mineral fillers present in the EPDM/PCM compound (clay) and in the envelope (talc, kaolin and silica). A better comprehension of the combustion mechanisms and of the flame retardant efficacy was achieved through the analysis of the combustion residues. Finally, the specific enthalpy of the different systems was evaluated with respect to the cost of the raw materials used in the production stages in order to classify them on the basis of their melting enthalpy and on the economical aspects.