Thermal conductivity and multiferroics of electroactive polymers and polymer composites.

摘要

Electronically conducting polymers and electromechanical polymers are the two important branches of the cutting-edge electroactive polymers. They have shown significant impact on many modern technologies such as flat panel display, energy transport, energy conversion, sensors and actuators. To utilize conducting polymers in microelectronics, optoelectronics and thermoelectrics, it is necessary to have a comprehensive study of their thermal conductivity since thermal conductivity is a fundamental materials property that is particularly important and sometimes a determining factor of the device performance. For electromechanical polymers, larger piezoelectric effect will contribute to the improvement of magnetoelectric (ME) coupling efficiency in their multiferroic composites. This dissertation is devoted to characterizing electronically conducting polymers for their electrical and thermal conductivity, and developing new classes of electromechanical polymers and strain-mediated electromechanical polymer-based multiferroic ME composites.;Conducting polymers opened up new possibilities for devices combining novel electrical and thermal properties, but there has been limited understanding of the length-scale effect of the electrical and thermal conductivity, and the mechanism underlying the electricity and heat transport behavior. In this dissertation, the analytical model and experimental technique are presented to measure the in-plane thermal conductivity of polyaniline thin films. For camphorsulfonic acid doped polyaniline patterned on silicon oxide/silicon substrate using photolithography and reactive ion etching, the thermal conductivity of the film with thickness of 20 nm is measured to be 0.0406 W/m˙K, which significantly deviates from their bulk (> 0.26 W/m˙K). The size effect on thermal conductivity at this scale is attributed to the significant phonon boundary scattering. When the film goes up to 130 nm thick, the thermal conductivity increases to 0.166 W/m˙K, greatly affected by the phonon-phonon scattering and phonon boundary scattering. When the films are thicker than 130 nm, heat capacity also plays an important role in thermal conduction in polyaniline.;The same technique is extended to measure the electrical and thermal conductivity of 55 nm thick polyaniline thin films doped with different levels of camphorsulfonic acid. Results indicate that the effect of the doping level (camphorsulfonic acid/polyaniline ratio) is more pronounced on electrical conductivity than on thermal conductivity, thereby greatly affecting their ratio that determines the thermoelectric efficiency. At the 60% doping level, polyaniline thin film exhibits the maximum electrical and thermal conductivity due to the formation of mostly delocalized polaron structures. It is suggested that polarons are the charge carriers responsible for the electrical conduction, while phonons play a dominant role in the heat conduction in doped polyaniline thin films.;Multiferroic materials combine unusual elastic, magnetic and electric properties, and have promising applications in many areas, such as sensors, transducers and read/write memory devices. For strain-mediated multiferroic ME composites, their ME effect are generated as a product property of the piezoelectric phase and magnetostrictive phase. In this dissertation, new multiferroic composites are developed and presented. One of them is based on chain-end cross-linked ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE). With a low dc bias magnetic field, the ME coefficient of this composite is 17.7 V/cm Oe at non-resonance and 383 V/cm Oe at resonance, well above the reported ME voltage coefficient of polymer based ME composite in current literature.;ME composite based on poly(vinylidene fluoride-co-hexafluoropropylene) P(VDF-HFP) are also developed in this dissertation. Crystalline beta phase structure in P(VDF-HFP) is produced by uniaxially stretching of pre-melted and quenched films. ME voltage coefficient as a function of dc magnetic field at different poling fields is measured. It is found that there is a linear relationship between the ME voltage coefficient of the composite and the poling field. Moreover, an electric field-induced phase transition is observed in P(VDF-HFP), manifested by the evolution of a double hysteresis D-E loop at intermediate poling field to a single loop at high poling field. The double hysteresis loop is due to the antiferroelectric phase that will transform into the ferroelectric phase when poled at high electric field. It is also found that in antiferroelectric-like and ferroelectric P(VDF-HFP), there is a linear relationship among piezoelectric strain coefficient, remanent polarization and the poling field.;P(VDF-HFP) copolymer is further investigated for its use in multiferroic ME composite, and various chemical modifications and processing methods are utilized to alter the crystalline structure. (Abstract shortened by UMI.).