The objective of this PhD thesis is to present the most performing EAP-based materials, technologies and devices developed by our lab (Ch.4, 5 and 6) also in collaboration with other research groups (Ch.1 and 2) for sensing, actuating and energy harvesting, with reference to their already demonstrated or potential applicability to electronic textiles and wearable technologies in general.
Over the last decade great strides have been made in the field of wearable technology: thanks to new discoveries in materials science and miniaturized electronics, tissues and "smart" devices for monitoring vital parameters, rehabilitation and tele-assistance were born. However, a complete and self-powered system, able to exchange information with the external environment, to generate power using the usual movements of the human body (walking, work, sport) and to drive wearable devices, is not yet available on the market and it would find a considerable number of applications (monitoring physiological parameters for athletes and special forces officers in emergency situations, etc.).
After a first survey of the state of the art concerning the so-called "smart materials” and technologies currently available for " wearable " activities, the work has developed on three major directives consisting in: energy generation and storage, sensing and actuation.
Energy generation and storage. An experimental study, conducted mainly during the first year of PhD, has identified possible candidate materials (piezoelectric PVDF, electret PP) for the energy harvesting and subsequent generation of power from movement and gestures by exploiting the piezoelectric properties of selected materials. These materials have been either found on the market or processed in laboratory. In collaboration with the University of Pavia, a circuit for the storage of electric charges generated was made. Both the commercial materials and those obtained in laboratory were electromechanically tested and the generation of electric charges has been used to develop a demonstrator generator-LED embedded in a shoe.
Sensing. During the first and second year, different sensor configurations of "dry" piezoelectric PVDF sensors were tested for the monitoring of vital parameters (heart and breathing rate). Such sensors, prepared in collaboration with the University of Lodz (TUL, Poland), our partners in the PROETEX European project (6th FP 2006-2009), were woven into fabrics to be easily integrated into clothing, and their response was studied. Signal intensities comparable to those of common 3M medical electrodes have been observed. A further development of these materials should be turn to reduce noise, while a computational study might deal with the signal filtering and elimination of motion artifacts.
Along with the study of piezoelectric sensors mentioned above, during the third PhD year the production and characterization of dielectric elastomers for sensing applications (artificial skin) was developed too, in collaboration with the Genoa DIST (Dipartimento di Informatica, Sistemistica e Telematica). Such elastomers, characterised by high dielectric constants and restrained compressive elastic moduli, were develop in order to act as dielectric medium in piezocapacitive sensing devices. The obtained materials will be used as artificial skin in robotic systems.
Actuating. In parallel with the two lines described above, the activity was concentrated, throughout the period of PhD, on the development of new dielectric elastomer actuators, to be used as high dielectric constant, low elastic modulus and, especially, low electric driving fields devices so that they can be used once inserted inside the clothing (simplified prototype actuators able to change the porosity / texture of different textiles were developed during the first year of activity for the FLEXIFUNBAR European project (6th FP 2005-2008)). The "blend" approach has been privileged over the "composite" approach, previously studied in the master thesis, and has led to promising results both from the applicative point of view, with an increase in the electromechanical performance, and on a fundamental level, for the implications emerging from the interaction between different phases in the study of dielectric response of partially heterogeneous systems.
Electromechanical encouraging results were then obtained during the second year of activity with the development of silicone/polyurethane (SI/PU) blends prepared by appropriate volume fractions. Further improvements have also been achieved during the third year of doctoral studies, when it was introduced in the same mixtures a third component, the conjugated polymer poly-(3-hexylthiophene-2,5-dyil) (P3HT), already used by our group for its high polarizability in order to increase the dielectric constant of silicon actuators. The obtained samples, dielectrically, mechanically and electromechanically tested, showed that the conjugated polymer leads to a further significant increase in the electromechanical response of the blend only when added at levels of 1 wt%. This polymer shows, in fact, a certain influence on the microscopic distribution of the SI and PU "phases" in the blend. This effect is maximized for the 1 wt% concentration at which the presence of interfaces is maximized and thus a larger surface polarization, combined with the characteristic high polarizability of P3HT, leads to dielectric constant and strain further implementations. Similar increases in performance, compared to pure components, were also found in mixtures prepared using other polyurethanes and silicones adopting, when necessary, appropriate steps to modify the kinetics of reaction (addition of solvents).
The results obtained with this "blending" approach are supported by the Intephase Theory (IT), recently introduced to complete the well known Effective Medium Theory (EMT) which, although applicable to a variety of particle composite structures, is not suitable to describe the behaviour of systems where the presence of an interphase between filler and matrix is significant. The EFT demonstrates that border regions, showing dielectric characteristics different from those of the starting components, can strongly influence the system performance. Through theoretical and experimental evidence, in fact, it is known that, while the inner parts of the matrix polymer chains are able to adopt a configuration that minimizes spontaneous conformational energy, at the interface they are linked or otherwise conditioned in their movements, giving rise to a region where the electrical properties (in some cases also thermal and mechanical) are different from those of both the pure material composing the mixture.
During the third year, the production and characterization of elastomeric foams with dielectric properties suitable for sensing (artificial skin) and actuating applications were also developed. The electromechanical performance of these polyurethane-based foams, after appropriate polarization under very high electric fields (Corona poling), were compared with those of two commercial products, which were also subjected to corona poling. Studies have been conducted also on the life of the induced polarization produced by poling in the foam and on the influence of electric field exposure time on the final response of the material.
The slightly positive results obtained in terms of increased dielectric constants and strains have opened a new line of activity that represents an innovation in the field of dielectric elastomers, that is the preparation of elastomeric foams with electret properties.