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Access Type
WSU Access
Date of Award
January 2023
Degree Type
Dissertation
Degree Name
Ph.D.
Department
Chemical Engineering and Materials Science
First Advisor
Yingxi E. Zhu
Abstract
Hybrid complexations between macroions with different chemistries and properties have achieved great impact in the scientific community. Among the variety of complexes known for charged macromolecules to form, coacervate complexes are one main point of focus in this thesis. Conventional coacervate complexes have been used in food, pharmaceutical and cosmetic products for decades, and recent developments with synthetic polyelectrolytes have opened the door for them as novel functional materials with a wider field of application. The fascinating properties and plausible applications for the complexes can be expanded even more with the careful design of the starting components and polyelectrolyte-like behavior. Chapter 2 investigates the effect of net charge of zwitterionic polymers on the phase behavior and viscoelastic properties of hybrid polyampholyte–polyoxometalate (POM) complexes in salted aqueous solutions, with polyampholyte copolymers consisting of both positively and negatively charged monomers. The mechanical and morphological properties of the intriguing organic-inorganic complex was explored, revealing a new tuning parameter to fine control the macroionic interactions and material properties of biomimetic complex coacervates. Along with the more fundamental understanding of the hybrid coacervate complex, the use of these complexes as an extraction media is investigated as well in Chapter 3. Firstly, the anionic core of the polyampholyte-polyoxometalate complex benefited the extraction of multiple toxic cationic industrial dyes. Secondly, the design of a hydrogen bond-driven coacervate complex using biocompatible polymers was used to remove toxic cyanotoxins commonly present in the Midwest’s Great Lakes.
The unusual coacervate formation between polyoxometalate and neutral polymer, PEO, inspired the study of the charging state of PEO and its effect on the conformational structure of the polymer chain at the single molecule level. Literature reports on the unusual polyelectrolyte-like behavior of PEO in certain solvents, raised the question of the charging state and structure of the neutral polymer in solvents of varied polarity. In chapter 4, the impact of simple and macro ions on the structural and charging behavior of neutral polymer, PEO, is explored in mixed solvents at the nano and micro scale.
One of the applications of the multifaceted PEO is explored in the interest-rising field of energy storage. The search of a safer and energy-denser solid-state electrolyte have pointed the use of hybrid ceramic-polymer electrolytes as a great candidate. However, an inherent incompatibility at the interface level between the two materials that generates a large interfacial resistance has been a challenge over the years. Chapter 5 explores the introduction of a copolymer interfacial layer between a ceramic-LLZO and a polymer-PEO solid state electrolyte to enhance their wetting and performance. The facile and rapid polymerization process of dopamine to form a copolymer with PEO was used to benefit from dopamine great adhesion properties and increase the compatibility with both PEO and LLZO.
Recommended Citation
Ferreira Borras, Manuela, "Design Of Hybrid Macroion Complexes With Tunable Properties" (2023). Wayne State University Dissertations. 3778.
https://digitalcommons.wayne.edu/oa_dissertations/3778