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A shape memory polymer (SMP) is stimuli-responsive with the fantastic capacity to “memorize” a temporary shape under certain conditions and to recover to its permanent shape upon exposure to certain external stimulus (e.g. heat, light, electromagnetic field). In the past few decades, various SMPs have been investigated and applied in the area of aerospace, biomedicine, and textiles, etc. Recently, a special type of SMP called a ‘two-way reversible shape memory polymer’ or ‘reversible shape memory polymer’ (RSMP) capable of transitioning between two temporary shapes without the need for reprogramming after each change has attracted the attention of many researchers. In this class of polymer, the semicrystalline RSMP was studied considerably due to the various chain structures produced by relatively simple synthesis routes. The crystallization-induced elongation (CIE) and melting-induced contraction (MIC) of the oriented crystal domains has been theorized as the main mechanism of semicrystalline RSMP. However, most RSMPs are predominantly thermosets, which implies significant drawbacks regarding reprocessing and recycling. This thesis focuses on the development of RSMP based on polyolefin materials, especially novel high-performance polyolefin elastomers, due to the advantages of high crystallizability, varying chain structures, tunable and broad melting transitions, and low cost. The thesis starts off by demonstrating the reversible shape memory effect (RSME) of the thermoplastic ethylene/1-octene diblock copolymer, which contains the ethylene-rich hard segments and the 1-octene-rich soft segments. The delicately designed chain structure exhibited a broad melting transition and strong physical crosslinks, which contributed to the resulting RSME and the CIE/MIC effect at load-free conditions. Furthermore, the commercially available polyolefin elastomer blends demonstrated the RSME. The utilization of commercial products and simple processing method to achieve a thermoplastic RSMP offers easy production in large scale and low costs. The second part of the thesis developed a polyolefin-based RSMP with reconfigurable network by introducing a transesterification catalyst into a crosslinked poly(ethylene-co-vinyl acetate). The network reconfiguration achieved a dynamic covalent polymer network by breaking the ester bonds and reconnecting. The third part of the thesis explored a new RSMP foam material developed by utilizing polyolefins. The polyolefin elastomers of differing compositions were blended and foamed to fabricate the porous structure. The RSME in a load-free condition was then demonstrated successfully. This thesis represents significant progress in the development of polyolefin-based RSMPs, outlining new structural design, processability improvements, and potential applications. / Thesis / Doctor of Philosophy (PhD) / Shape memory polymer (SMP) is stimuli-responsive capable of “memorizing” a temporary shape and yet recovering to its permanent shape upon a certain external trigger. SMPs are widely studied and applied in the areas of aerospace, biomedicine, textile, etc. On the other hand, a reversible shape memory polymer (RSMP) is a new type of SMP that can shift back and forth between two different temporary shapes without the need of reprogramming between transitions, and has been applied in soft actuators, microrobotics, and artificial muscles. In this thesis, unique polyolefin-based RSMP were developed with good reprocessability and shown in new application scenarios. Firstly, a thermoplastic semicrystalline polymer was demonstrated to exhibit the reversible shape memory effect (RSME) by using a lab-designed ethylene/1-octene diblock copolymer and commercial polyolefin elastomer blends. Subsequently, the reprocessability of a crosslinked poly(ethylene-co-vinyl acetate) (PEVA) RSMP was improved by introducing a dynamic covalent polymer network. Finally, transitional changes between shapes was amplified by developing a RSMP foam by utilizing polyolefin elastomer blends. This thesis represents significant progress in the study of polyolefin-based RSMPs.

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The aim of this work is to demonstrate a Helmholtz potential based approach for the development of the constitutive equations for a shape memory polymer undergoing a thermomechanical cycle. The approach is motivated by the use of a simple spring-dashpot type analogy and the resulting equations are classified as state-equations and suitable kinetic equations for the recoverable-energy elements and the dissipative elements in the model respectively. These elements have mechanical properties which vary with temperature. The governing equations of the model are developed starting from the basic conservation laws together with the laws of thermodynamics. The entire set of equations are written in a state-evolution form as a set of ordinary differential equations to be solved using Matlab. It is shown that the results of the simulation in Matlab are in qualitative and quantitative agreement with experiments performed on polyurethane. Subsequently, we study the dependence of the yield-stress on temperature to be similar and different functions of heating or cooling processes.

The effect of moisture absorption on the glass transition temperature (Tg) and stress/strain behavior of network polyurethane shape memory polymer (SMP) foams has been investigated. With our ultimate goal of engineering polyurethane SMP foams for use in blood contacting environments, we have investigated the effects of moisture exposure on the physical properties of polyurethane foams. To our best knowledge, this study is the first to investigate the effects of moisture absorption at varying humidity levels (non-immersion and immersion) on the physical properties of polyurethane SMP foams. The SMP foams were exposed to differing humidity levels for varying lengths of time, and they exhibited a maximum water uptake of 8.0 percent (by mass) after exposure to 100 percent relative humidity for 96 h. Differential scanning calorimetry results demonstrated that water absorption significantly decreased the Tg of the foam, with a maximum water uptake shifting the Tg from 67 °C to 5 °C. Samples that were immersed in water for 96 h and immediately subjected to tensile testing exhibited 100 percent increases in failure strains and 500 percent decreases in failure stresses; however, in all cases of time and humidity exposure, the plasticization effect was reversible upon placing moisture-saturated samples in 40 percent humidity environments for 24 h.

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Yes / Formation of cracks represents one of the major causes of concrete deterioration, which can lead to durability and safety issues. In this work, a novel crack closure system is developed, using polyethylene terephthalate (PET) polymer fibres embedded in a mortar mix. The PET polymer has shape memory properties and shrinks upon thermal activation, if free to do so, or otherwise exerts shrinkage restraint forces. A single knot was manufactured at each end of the PET fibres to provide mechanical anchorage into the mortar matrix. Mortar samples with embedded knotted fibres were pre-cracked and subsequently placed in an oven to thermally activate the polymers and induce the shrinkage mechanism into the fibres. Crack closure was measured in the range 45–100%, depending on the geometry, dimension and distribution of the fibres, and the size of the initial crack. / This work is supported by UKRI-EPSRC (Grant No. EP/P02081X/1, Resilient Materials 4 Life, RM4L).