Taking advantage of their inherent abrasion resistant, weather resistant, and outstanding mechanical strength, film-grade thermoplastic polyurethanes (TPU) are currently being used as paint protective films but are also being considered for paint replacement within the automotive industry. Special grades of TPU with shape memory behaviour offer an additional feature of self-healing to decorative coatings but there are concerns of shape fixity at service temperatures which are above their glass transition temperature (Tg). In this study, the shape memory behaviour of a developmental TPU film with Tg around room temperature was investigated. In order to understand the shape memory behaviour, the TPU film was laminated to a rigid polymer substrate of either polypropylene (PP) or acrylonitrile butadiene styrene (ABS). Three different acrylic based pressure sensitive adhesives were tested to bond the film to the substrate, namely a commercial high shear strength transfer tape and two solvent based adhesives of high and low shear strength that were manually cast. The influence of the adhesive was given significant attention as a variable of study in this thesis. The characterization of all the polymeric films and substrates was based on a series of thermo-mechanical tests (tensile test, stress relaxation test, DSC and DMA). The adhesives were characterized by lap-shear test, peel test, and parallel plate rheometry. The results of material characterization were used to support the analysis and interpretation of shape memory behaviour. The TPU based laminate was deformed by a matched mold thermoforming process with a pair of arched matched molds. The recovery behaviour of formed samples was quantified with a newly designed measurement method and the results were reported as recovery ratio and recovery rate. During recovery, the surrounding temperature was considered to be an important variable. The recovery behaviour of specimens was investigated in a controlled environment at setpoint temperatures of 15oC, 45oC or 65oC. No shape memory effect was found at 15oC (below TPU’s Tg), and yet both recovery ratio and recovery rate increased with temperature, from 45oC to 65oC (both above the TPU’s Tg). Since the recovery process was related to the elastic response of the hard segment phase within the TPU, the recovery stress was strongly related to strain conditions. By varying the draw depth into the mold from 6 mm, to 10 mm or 12 mm (8.86%, 15.90% or 19.88% strain, respectively), the recovery measurement results showed that the shape memory effect was weaker with lower strain as less recovery stresses were generated in the TPU film. With the draw depth of 10 mm, the highest recovery ratio and recovery rate were observed, and yet an inexplicable decrease in the recovery ratio and recovery rate occurred as the draw depth increased further from 10mm to 12mm. In regards to the influence by a substrate, TPU/PP laminate showed a more significant recovery behaviour than TPU/ABS laminates at both 45oC and 65oC. The elastic modulus of the substrate was found to have a key role on the recovery process; the recovery nature of formed laminate decreased with stiffer substrate. Three adhesives with differing rheological and adhesion properties were tested to bond the TPU film to a substrate. The formed laminates with “strongest” adhesive (transfer tape) in terms of stiffness and adhesion strength showed the highest recovery ratio/rate over laminates made with “weaker” solvent cast adhesives, at both 45oC and 65oC. A finite element analysis (FEA) was employed to simulate the stress transfer within a multilayer structure bonded by a viscoelastic adhesive layer of varying stiffness; the simulated result showed that the relatively low stiffness adhesive could reduce the stress transfer efficiency within layers of a laminate. It suggested that more recovery stresses were transferred from TPU to substrate with a stiffer adhesive layer (transfer tape) and hence increased the recovery ratio and recovery rate. Therefore, adhesive with relatively low stiffness and adhesion strength could be a better choice to reduce the recovery effect of TPU laminate after forming. However, TPU was found to slide at the unsealed edge of formed laminate when the solvent based adhesives were used; the sliding behavior reduced the recovery by releasing stored recovery stress. In the case of HS and LS adhesives at high temperature (65oC), cohesive failure was observed when the edge of specimen was sealed led to a higher bending moment thus increased the recovery ratio over 24 hours investigations. Therefore, adhesives of weaker shear strength do not necessarily overcome the nature of shape recovery by the TPU when formed part shape needs to be preserved. / Thesis / Master of Applied Science (MASc) / Nowadays, smart materials in particular shape-memory polymers have been widely used in the industrial and medical applications. Thermoplastic polyurethane (TPU) is one of the significant shape memory polymer groups. The two-phase morphology of a typical TPU gives a unique shape memory behaviour over a defined temperature range. However, this shape memory effect affects the shape fixity of formed TPU. In this study, a special-grade TPU film was laminated to a rigid polymer substrate using selected pressure sensitive adhesives (PSAs). In order to investigate the effect of adhesive layer on the shape memory behaviour of this TPU based laminate, three PSAs with varying properties were applied. The laminate was thermoformed, quenched and processed in a temperature-controlled chamber with a designed recovery measurement method. The shape memory effect was observed at temperatures above the transition temperature of TPU, and this recovery effect was enhanced at higher temperature. Furthermore, the mechanical property of the substrate material was considered as a key factor on the recovery behaviour of the laminate; the recovery of the formed laminate was restricted with a stiffer substrate. The most significant discovery from the recovery results indicated that the shape memory effect was reduced with the adhesive with relatively low adhesion strength, however, the delamination of the laminate occurs with weaker adhesives.

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Yes / The presence of cracks has a negative impact on the durability of concrete by providing paths for corrosive materials to the embedded steel reinforcement. Cracks in concrete can be closed using shape memory polymers (SMP) which produce a compressive stress across the crack faces. This stress has been previously found to enhance the load recovery associated with autogenous selfhealing. This paper details the experiments undertaken to incorporate SMP tendons containing polyethylene terephthalate (PET) filaments into reinforced and unreinforced 500 × 100 × 100 mm structural concrete beam samples. These tendons are activated via an electrical supply using a nickelchrome resistance wire heating system. The set-up, methodology and results of restrained shrinkage stress and crack closure experiments are explained. Crack closure of up to 85% in unreinforced beams and 26%–39% in reinforced beams is measured using crack-mouth opening displacement, microscope and digital image correlation equipment. Conclusions are made as to the effectiveness of the system and its potential for application within industry. / EPSRC for their funding of the Materials for Life (M4L) project (EP/K026631/1) and Costain Group PLC for industrial sponsorship of the project and author

Yes / We have performed shrinkage restraint force measurements on three shape memory polymers of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) and a blend of the two at a range of temperatures. Observations are made of the change in stress during temperature rise, hold and cooling. All materials show an increase in stress during rise and hold, but on cooling the three materials behave differently; the PET shows a drop in stress, the PMMA a rise and the blend a much smaller rise. This behaviour correlates with the reversible thermal dimensional change at below the shrinkage threshold temperature; the expansion coefficients are negative for PET, positive for PMMA and positive at a lower order of magnitude for the blend. We model the behaviour by supposing that the shrinkage forces are created by prestressed strains effective at long range within a matrix of shorter chains effective at short range. The total stress is the sum of the shrinkage stress and the thermal stress in the matrix. The drops in stress on cooling are modelled using an elastic analysis based on measured elastic moduli and thermal expansion coefficients. For the blend, downward jumps in temperature produce small transient increases in the total stress, leaving it effectively unchanged. This phenomenon and the results of the elastic model for the stress drops imply that the shrinkage stress from the long-range chain network is largely unaffected by the temperature change, and so is not entropic.

An intracranial aneurysm can be a serious, life-threatening condition which may go undetected until the aneurysm ruptures causing hemorrhaging within the brain. The typical treatment method for large aneurysms is by embolization using platinum coils. However, in about 15% of the cases treated by platinum coils, the aneurysm eventually re-opens. The solution to the problem of aneurysm recurrence may be to develop more bio-active materials, including certain polymers, to use as coil implants. In this research, a shape memory polymer (SMP) was investigated as a potential candidate for aneurysm coils. The benefit of a shape memory polymer is that a small diameter fiber can be fed through a micro-catheter and then change its shape into a three-dimensional configuration when heated to body temperature. The SMP was tested to determine its thermo-mechanical properties and the strength of the shape recovery force. In addition, composite specimens containing tantalum filler were produced and tested to determine the mechanical effect of adding this radio-opaque metal. Thermo-mechanical testing showed that the material exhibited a shape recovery force a few degrees above Tg. The effects of the metal filler were small and included depression of Tg and recovery force. SMP coils deployed inside a simulated aneurysm model demonstrated that typical hemodynamic forces would not hinder the shape recovery process. The x-ray absorption capability the tantalum-filled material was characterized using x-ray diffractometry and clinical fluoroscopy. Diffractometry revealed that x-ray absorption increased with tantalum concentration, however, not as the rule of mixtures would predict. Fluoroscopic imaging of the composite coils in a clinical setting verified the radio-opacity of the material.

This dissertation work focuses on the thermomechanical behaviors of two recent exciting developments in active polymers: shape memory (SM) effects and covalent adaptive network polymers with bond exchange reactions. Both polymers are active in performing prescribed functions when an external stimulus is applied. The goals of the studies are to understand complex thermomechanical behaviors of such smart polymers through experiments, develop constitutive models to describe the behaviors, and use the developed models to assist their development and engineering applications. For the polymer SM effect, we use a multi-branched constitutive model to study the SM effect achieved by polymer glass transition. The major finding of our study is that the “Reduced Time” is identified to be the unique parameter to determine the polymer shape fixity and recovery ratio under different thermo-temporal conditions in an SM cycle. Based on the theoretical knowledge, we also study the energy releasing mechanism within shape memory polymers (SMPs), multi-shape memory effects, as well as the SM properties in various composite systems, such as magnetic particles, carbon black and microvascular reinforced SMP composites. For the covalent adaptive network polymers, we adopt the emerging covalent chemistry BERs to achieve a malleable, reparable, recyclable and yet insoluble thermoset network. After being pulverized into micro-size, and then compressed either at high temperature or just facilitated by the moisture, the polymer powder could be welded on the interfaces, and assembled together into a new sample with comparable mechanical properties to the fresh sample. Theoretical models are developed to gain fundamental understanding of how the processing conditions can affect the quality of reprocessed materials. A molecular model is developed to understand welding kinetics at the interface. Such understanding is then used to develop a multiple length scale interfacial constitutive model, which can be implemented in to finite element simulation software to assist computational study of reprocessing process.

Commonly used thermoplastic biodegradable polymers are generally brittle and lack appreciable elasticity at physiological temperature and thereby fail to mimic the elastic nature of many human soft tissues such as blood vessels. Thus, there is a need for biomaterials which exhibit elasticity. Biodegradable elastomers are promising candidates whose elasticity more closely parallels that of soft tissues. In this research, we developed hybrid biodegradable elastomers comprised of organic and inorganic polymer components in a block copolymer system: poly(e-caprolactone) (PCL) and poly(dimethylsiloxane) (PDMS), respectively. A block structure maintains the distinct properties of the PCL and PDMS components. These elastomers may be useful for the tissue engineering of soft tissues as well as for shape memory polymer (SMP) devices. Tri-block macromers of the form PCLn-block-PDMSm-block-PCLn were developed to permit systematic variations to key features including: PDMS block length, PCL block length, PDMS:PCL ratio, and crosslink density. The macromer was capped with acrylating groups (AcO) to permit their photochemical cure to form elastomers. Thus, a series of biodegradable elastomers were prepared by photocrosslinking a series of macromers in which the PCL blocks varied (n = 5, 10, 20, 30, and 40) and the PDMS block was maintained (m = 37). All elastomers displayed hydrophobic surface properties and high thermal stability. These elastomers demonstrated systematic tuning of mechanical properties as a function of PCL block length or crosslink density. Notable was strains at break as high as 814% making them suitable for elastomeric bioapplications. Elastomers with a critical PCL block length (n = 30 or 40) exhibited shape memory properties. Shape memory polymers based on an organic-inorganic, photocurable silicon-containing polymer system is a first of its kind. This SMP demonstrated strain fixity of 100% and strain recovery near 100% after the third thermomechanical cycle. Transition from temporary to permanent shape was quite rapid (2 sec) and at temperatures near body temperature (60 degrees C). Lastly, porous analogues of the biodegradable elastomers were created using a novel porogen - salt leaching technique. Resulting porous elastomers were designed for tissue engineering scaffolds or shape memory foams.

Shape memory alloys and polymers have been extensively researched recently because of their unique ability to recover large deformations. Shape memory polymers (SMPs) are able to recover large deformations compared to shape memory alloys (SMAs), although SMAs have higher strength and are able to generate more stress during recovery. This project focuses on procedure for fabrication and Finite Element Modeling (FEM) of a shape memory composite actuator. First, SMP was characterized to reveal its mechanical properties. Specifically, glass transition temperature, the effects of temperature and strain rate on compressive response and recovery properties of shape memory polymer were studied. Then, shape memory properties of a NiTi wire, including transformation temperatures and stress generation, were investigated. SMC actuator was fabricated by using epoxy based SMP and NiTi SMA wire. Experimental tests confirmed the reversible behavior of fabricated shape memory composites. The Finite Element Method was used to model the shape memory composite by using a pre-written subroutine for SMA and defining the linear elastic and plastic properties of SMP. ABQUS software was used to simulate shape memory behavior. Beside the animated model in ABAQUS, constitutive models for SMA and SMP were also developed in MATLAB® by using the material properties obtained from experiments. The results of FEM simulation of SMC were found to be in good agreement with experimental results.

Shape memory polymers (SMPs) have been candidate materials for morphing applications. However, the SMPs have not been fully tested to work in relevant environments required for Air Force missions. In this study, an epoxy-based SMP was separately exposed to moisture, lubricating oil and UV radiation, which are simulated service environments designed to be reflective of anticipated performance requirements. The thermomechanical properties and shape memory effects were studied by using novel high-temperature nanoindentation technique. Results show that environmental conditions have affected the glass transition temperature and mechanical properties of the SMPs. In most cases, the conditioned SMPs exhibited higher elastic moduli than the unconditioned SMP. The shape recovery ability of the SMP was assessed by creating an indent and then observing the corresponding recovery according to the standard shape memory cycle. It was found that the deformation was mostly recovered for both conditioned and unconditioned SMP samples on heating the material above its glass transition temperature.

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