ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- All Subjects: chemical engineering
Description
There are limited analyses of the properties of segmented ionenes on the influence of the type, structure, content of soft/hard segments, and type of counterions through direct comparisons, which are needed for a diverse set of applications. This dissertation research focuses on resolving the gaps in the structure-property-function relationship of segmented ionenes. First, the synthesis of novel segmented ionenes using step-growth polymerization via the Menshutkin reaction of ditertiary amines and alkyl dihalides was performed with PEG soft segment with three different content of soft/hard segments, 25, 50, and 75 wt%, and two different hard segments, linear aliphatic and heterocyclic aliphatic hard segments. The content of the soft segment influenced the degree of phase separation and ionic aggregation which affected the thermomechanical properties of segmented ionenes. In addition, the crystallization of the soft segment influenced the mechanical properties of the ionenes. Second, the effect of the type of the soft segment was investigated by analyzing the novel PTMO-based segmented ionenes possessing three different content of soft/hard segments, as well as two different hard segments. The heterocyclic aliphatic hard segment provided a better degree of phase separation compared to the linear aliphatic hard segment irrespective of the type of soft segment, PEG, or PTMO. Moreover, the type and content of hard segments not only affected the thermal and mechanical properties but also the morphology of the segmented ionenes significantly that even inducing an ordered morphology. Third, the counter-anion metathesis was performed with PEG- and PTMO-based segmented ionenes possessing two structurally different hard segments to investigate the effect of the type of counter-anions with a direct comparison of the type of soft and hard segments. The type of counterion significantly influenced the thermomechanical properties of the segmented ionenes, and the degree of phase separation of different types of counter-anions was dependent on the type of soft and hard segments. The results of this dissertation provide fundamental insights into the correlations between each factor that influences the properties of the segmented ionenes and enable the design of segmented ionenes for a diverse range of applications.
ContributorsLee, Jae Sang (Author) / Green, Matthew (Thesis advisor) / Long, Timothy (Committee member) / Holloway, Julianne (Committee member) / Jin, Kailong (Committee member) / Seo, Soyoung (Committee member) / Arizona State University (Publisher)
Created2023
Description
In the search for ever more sustainable manufacturing techniques, additive manufacturing through light driven 3D printing processes is growing rapidly as a field, specifically the production of “living” materials which can be repaired and or reprocessed through the reactivation of polymer chain ends. Currently research in the production of these living materials is largely focused on radical polymerization methods. Cationic polymerizations have been developed for this purpose, although there is still much work to be done. This work seeks to explore a transition-metal free system to produce living materials through cationic reversible addition fragmentation chain-transfer (C-RAFT).Cationic polymerization is known for its rapid propagation. This is due to the highly reactive active center which also readily reacts with nucleophiles in unwanted chain transfer reactions. For this reason, reagents in living cationic polymerizations are subject to rigorous purification steps involving the distillation of monomer and solvent, freeze—pump—thaw cycles, and running the reaction under an inert environment1. These restrictions make living cationic polymerizations unattractive for 3D printing processes. New systems for rapid water tolerant C-RAFT photopolymerization will provide for new materials to be produced through this more sustainable manufacturing process.
In this work, living cationic polymerization of isobutyl vinyl ether (IBVE) is achieved using a synthesized cationic RAFT agent and an initiating system consisting of camphorquinone (CQ), ethyl 4-(dimethylamino)benzoate, and iodonium salt HNu-254. Molecular weights of 12 kg/mol are achieved with a dispersity of 1.4. The polymerization mechanism is probed and shows rapid kinetics consistent with living polymerizations in addition to photo-controllability as indicated by light on-off experiments. Chain extension experiments display re-activation of the trithiocarbonate chain end. This feature is then used to produce block-copolymers using ethyl vinyl ether and cyclohexyl vinyl ether.
ContributorsHawkins, Kade Denver (Author) / Seo, Eileen (Thesis advisor) / Long, Timothy (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2023
Description
The properties of block polymers (BPs) are intricately coupled to the dynamic and rich nature of the nanostructured assemblies which result from the phase separation between blocks. The introduction of strong secondary forces, such as electrostatics and hydrogen bonding, into block polymers greatly influences their self-assembly behavior, and therefore affects their physical and electrochemical properties often in non-trivial ways. The recent surge of work expanding scientific understanding of complex spherical packing in block polymers (BPs) has unlocked new design space for the development of advanced soft materials. The continuous matrix phase which percolates throughout spherical morphologies is ideal for many applications involving transport of ions or other small molecules. Thus, determining the accessible parameter range of such morphologies is desirable. Bulk zwitterion-containing BPs hold great potential within the realm of electroactive materials while remaining relatively untapped. In this work, architecturally and compositionally asymmetric diblock polymers were prepared with the majority block having zwitterions tethered to side chain termini at different ratios. Thermally reversible Frank-Kasper phases are observed in multiple samples with significant signs of kinetic arrest and influence. The kinetic influences are validated and described by the temperature-dependent static permittivity. Polyzwitterions combine the attractive features of zwitterions with the mechanical support and processability of polymeric materials. Among these attractive features is a potential for superior permittivity which is limited by the propensity of zwitterions to pack into strongly associating structures. Block polymer self-assembly embodies a plethora of packing frustration opportunities for optimizing polyzwitterion permittivity. The capabilities of this novel approach are revealed here, where the permittivity of a polyzwitterionic block is enhanced to a level comparable to that of pure liquid zwitterions near room temperature (εs ~ 250), but with less than a third the zwitterion concentration. The mechanistic source of permittivity enhancement from a single zwitterion-tethered block polymer is realized deductively through a series of thermal pathways and control sample experiments. Tethered zwitterions within the mixed block interface are frustrated when subject to segmental segregation under sufficient interfacial tension and packing while non-interfacial zwitterions contribute very little to permittivity, highlighting the potential for improvement by several fold.
ContributorsGrim, Bradley James (Author) / Green, Matthew (Thesis advisor) / Long, Timothy (Committee member) / Richert, Ranko (Committee member) / Jin, Kailong (Committee member) / Seo, S. Eileen (Committee member) / Arizona State University (Publisher)
Created2024