Demand has arisen rapidly for smart materials in the world of the need to develop and understand new functional products like plastics, rubber, adhesives, fibers, and coatings. Such products are essentially composed of polymers, large molecules of high molecular weight with homogeneous or various repeating units, which researchers term “macromolecules” that engender specific structural, morphological, and physical and mechanical properties. Those polymers with the capacity to change their configuration in accordance with environmental alteration are specifically referred to as shape memory polymers (SMPs), attracting much interest of study both academically and industrially. Herein, this dissertation aims at design, fabrication, and characterization of novel crosslinkable semicrystalline polymeric materials utilizing different techniques and mechanisms in order to explore their special thermomechanical features as well as the possibilities for potential industrial application based on shape memory (SM) effects. Key aspects include use of modern polymer synthesis to tailor thermal and shape memory properties and the adoption of electrospinning processing techniques to form continuous, fine fibers that allow unique molecular modifications, study of enzymatic degradation behavior involving physical form and microstructural state, and unprecedented approaches of making new kinds of shape memory assisted self-healing (SMASH) materials and thermal-responsive self-reversible actuators that require no human intervention. In the following is described the dissertation scope and organization.

Chapter 1 goes over background relating to material science within the scope of SM material, self-healing (SH) material, and actuators.

Chapter 2 outlines research conducted to achieve new compositions of matter and post- synthesis process, along with supporting characterization for the development of novel SMP materials with featuring tunable reversible actuation capability under ambient stimulus. We prepared a family of crosslinkable (unsaturated), semicrystalline cyclooctene (CO)-based copolymers with varying second monomer and composition via ring opening metathesis polymerization (ROMP). The unsaturation enables covalent crosslinking of polymer chains, in the presence of select thermal initiator through compression molding, allowing subsequent formation of a temperature-responsive network that shows a reversible two-way shape memory (2WSM) effect, indicative of crystallization-induced elongation upon cooling and melting-induced contraction upon heating when a constant, external stress is applied. Molecular, thermomechanical, and SM experiments were performed to investigate and tune the reversible actuation of aforementioned copolymers for the purpose of yielding quantitative guidelines for tailoring material and actuation performance through variations in composition and process.

Chapter 3 seeks a latent-crosslinkable, mechanically flexible, fully thermoplastic shape memory polymer. Towards this end, we have developed a simple but effective macromolecular design that includes pendent crosslinking sites via the chain extender of a polyurethane architecture bearing semicrystalline poly(ε-caprolactone) (PCL) soft segment. This new composition was used to prepare fibrous mats by electrospinning and films by solvent casting, each containing thermal initiators for chemical crosslinking. Relevant to medical applications, in vitro enzymatic degradation experiments were carried out to understand the effect of crosslinking state and crystalline structure on degradation behavior of the materials.

Chapter 4 builds upon the results of Chapter 3, reporting on the design, fabrication and characterization of a novel, electrospun SMASH polymer blend that incorporates theaforementioned latent-crosslinkable polyurethane. This unique blend system has been unprecedentedly developed by employing a solution in which crosslinkable polyurethane and linear polyurethane are mixed homogeneously for electrospinning. After preparing a family of blends with varying compositions, comprehensive characterizations and various healing tests were done to determine optimal healing performance. Further, the effect of different damage types and molecular anisotropy (nanofibers aligned in high speeds during electrospinning process) were studied for their effect on healing performance.

Chapter 5 continues along the line of Chapter 3, presenting the fabrication and testing of novel, electrospun SMP composites that were designed to exploit molecular and geometric anisotropy in reversible actuation under external stress-free condition upon change in ambient temperature. More specifically, the SMP composites consist of two electrospinnable constituents, one being the aforementioned latent crosslinkable polyurethane that serves to shape fixing and recovery (SM properties), and the other being a thermoplastic elastomer known as Pellethane that provides the internal stress field needed for 2WSM to occur. Multiple designs were developed and investigated in this chapter, in particular, including uniaxial actuator, bending actuator, and twisting actuator along with their bench demonstration of self-reversible actuation.

Chapter 6 discusses the overall dissertation conclusions, followed descriptions of suggestions for future work, some of which are sub-sectioned at the end of this dissertation.