Tailoring the structure-property of segmented ionenes through analysis of thermomechanical and electrical properties

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2022-12
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Taghavimehr, Mehrnoosh
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Montazami, Reza RM
Ommen, Danica
Hashemi, Nicole
Xiang, Chunhui
Pint, Cary
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Ionenes are ion-containing polymers with ions located on the polymer backbone. This characteristic of ionenes can be used to tailor the structure of polymers for a variety of applications. In this dissertation, we have investigated the effects of ionene microstructure on the properties of elastomeric samples. Placement of charge density in segmented ionenes can be controlled through the selection of soft/hard segments, changing the ratio of soft/hard segments, the molecular weight alteration of the soft segment, and microphase separation. The influences of these parameters were investigated through the synthesis of ionenes with various properties, while the structure-property relationships were scrutinized. In the first study, the results from molecular dynamics (MD) simulations of the ionene structure were compared with the experimental tests to evaluate the effect of microphase separation and ionic aggregation of ionene on their properties. The results of this study are discussed in detail in Chapter 3. The second study focused on using poly(ethylene glycol) (PEG) as the soft segment component of segmented block ionenes with two types of aliphatic hard segments (linear aliphatic and DABCO). All PEG samples created crystallized structures, and the highest melting temperature was obtained for PEG50/DD-ionene in both hard segment types, which confirms the effect of phase mixing on limiting the crystallinity in PEG75/DD-ionenes. The results of this study are discussed in detail in Chapter 4. The third study was based on the previous investigated to compare the effect of soft segment type on final properties using PTMO monomer as the soft segment. In this set of samples, the aromatic configuration of the hard segment created a more phase segregated 16 structure, particularly in DABCO-based PTMO25/DD-ionenes. This sample showed a broad rubbery plateau which is related to a high fraction of ionic aggregates and the formation of a stable network. The results of this study are discussed in detail in Chapter 5. In Chapter 6, two molecular weight of PEG soft segment (1000 and 4000 g/mol) were selected to study the effect of spacer length. From XRD results, it was evident that PEG1k/DD-ionenes formed an amorphous morphology and the crystalline structure occurred by increasing the molecular weight of PEG to 4000 g/mol. This significant change in crystalline structure resulted in an obvious difference in mechanical properties. Due to the versatility of the ionene design, a variety of potential applications for well-defined ionenes can be suggested. In Chapter 7, we focused on designing the composite components to change the electrical properties as a function of soft to hard segment ratios of aliphatic ionenes. We integrated carbon nanofibers (CNFs) and modified CNFs to create electrically conductive networks. The sensitivity of ionene composites under strain and recovery of the structure after unloading were selected as effective measures to identify the optimum components of the composite for sensing applications.
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