Electronic Thesis/Dissertation


High-Pressure Study of Bio-inspired Multi-Functional Nanocomposites Using Atomic Force Microscopy Methods Open Access

Bioinspired design has been crucial in the development of new types of hierarchical nanocomposites. Particularly, the nacre-mimetic brick-and-mortar structure has shown excellent mechanical properties as well as gas barrier properties and optical transparency. Along with these intrinsic properties, the layered structure has been designed to serve as sensing devices. Here we expand the multi-functionality of nacre-mimetics by designing an optically transparent and electron conductive coating that reacts to high-pressure based on PEDOT:PSS and nanoclay. The main objectives of this project are: (i) to develop a multifunctional nanocomposite and evaluate the effect of high-pressure applied at the surface and (ii) to establish protocols for the morphological and structural characterization, and electro-mechanical testing of the nanocomposites based on a combination of atomic force microscopy (AFM), scanning electron microscopy (SEM) and transmittance spectroscopy.The synthesis of the nanocomposite, containing PEDOT:PSS (conductive polymer) and nanoclay, was achieved using the self-assembly of core/shell platelets. Two different types of nanoclay, Cloisite Na+ and Laponite RD, are used and their properties compared. The reduction of thickness in PEDOT:PSS has been shown to increase the light transmittance across a film. Similarly, the thickness of the nanocomposite was reduced and compared to PEDOT:PSS. The measured optical transmittance for both nanocomposites is comparable to the bare polymer, demonstrating that the addition of the nanoclay does not affect the transparency of PEDOT:PSS significantly. The layered structure of the nanocomposites is investigated by imaging the fracture surface with SEM. The fracture surface of the Laponite RD based nanocomposite is much flatter than the Cloisite Na+ nanocomposite, since the particle size in Cloisite Na+ is about 10 times larger than Laponite RD. The characterization of electro-mechanical properties of the nanocomposites was performed using the correlation of conductive atomic force microscopy and contact resonance force microscopy to measure the local variations. The analysis shows that in thin and transparent films, there is segregation in the response of Cloisite Na+ based nanocomposites compared to the bare polymer or Laponite RD nanocomposite, hence the investigation focuses on Laponite RD.For Laponite RD, we investigate the 3-D distribution of nanoclay in the coating. The distribution of nanoclay at the surface is elucidated by mapping the dissipative and conservative interactions between tip and sample in bimodal AFM. Measuring the strain produced by the tip, the 3-D structure is inferred using models for mechanical properties of nanocomposites. Single platelet measurements are used to infer the inter-platelet distance. It is known that the free amplitude of the higher eigenmode can be modulated to produce large forces in bimodal AFM. The pressure estimated for the typical cantilever parameters used are in the range 1.2-3.3 GPa, which is used to apply high-pressure to the subsurface structure of the nanocomposite.We show that the tip-surface interaction modifies the subsurface morphology of the nanocomposite and results in changes of the out-of-plane current. Also, the structural modification caused by the bimodal AFM treatment results in local changes in mechanical properties. This behavior is obtained for the Laponite RD nanocomposite, but it is not observed for the Cloisite Na+ nanocomposite or the bare polymer. Laponite RD has a platelet size similar to the tip, while Cloisite Na+ is much larger leading to a reduction in pressure. By modelling the transmission probability of electrons, geometrical changes in the structure are examined and shown to modify the tunneling of the electrons through the coating. Specifically, parallel compression of the nanoclay (modelled as barriers for electrons) leads to a change in the transmission probability of the electrons. Depending on the kinetic energy of the electrons, the transmission probability could either increase or decrease.

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