The ultimate goal of this research was to develop a “self-fitting” shape memory polymer (SMP) scaffold for the repair of craniomaxillofacial (CMF) bone defects. CMF defects may be caused by trauma, tumor removal or congenital abnormalities and represent a major class of bone defects. Their repair with autografts is limited by availability, donor site morbidity and complex surgical procedures. In addition, shaping and positioning of these rigid grafts into irregular defects is difficult. Herein, we have developed SMP scaffolds which soften at T > ~56 °C, allowing them to conformally fit into a bone defect. Upon cooling to body temperature, the scaffold becomes rigid and mechanically locks in place. This research was comprised of four major studies. In the first study, photocrosslinkable acrylated (AcO) SMP macromers containing a poly(ε-caprolactone) (PCL) segment and polydimethylsiloxane (PDMS) segments were synthesized with the general formula: AcO-PCL40-block-PDMSm-block-PCL40-OAc. By varying the PDMS segment length (m), solid SMPs with highly tunable mechanical properties and excellent shape memory abilities were prepared. In the second study, porous SMP scaffolds were fabricated based on AcO-PCL40-block-PDMS37-block-PCL40-OAc via a revised solvent casting particulate leaching (SCPL) method. By tailoring scaffold parameters including salt fusion, macromer concentration and salt size, scaffold properties (e.g. pore features, compressive modulus and shape memory behavior) were tuned. In the third study, porous SMP scaffolds were produced from macromers with variable PDMS segment lengths (m = 0 – 130) via an optimized SCPL method. The impact on pore features, thermal, mechanical, and shape memory properties as well as degradation rates were investigated. In the final study, a bioactive polydopamine coating was applied onto pore surfaces of the SMP scaffold prepared from PCL diacrylate. The thin coating did not affect intrinsic bulk properties of the scaffold. However, the coating significantly increased its bioactivity, giving rise to the formation of “bone-bonding” hydroxyapatite (HAp) when exposed to simulated body fluid (SBF). It was also shown that the coating largely enhanced the scaffold’s capacities to support osteoblasts adhesion, proliferation and osteogenesis. Thus, the polydopamine coating should enhance the performance of the “self-fitting” SMP scaffolds for the repair of bone defects.

New materials always have the possibility of revolutionizing manufacturing processes and the way we live. Bronze, steel alloys, vulcanized rubber, ceramics, and fiber optic cables are just of few of the materials man has discovered which improved his quality of life. One of the more recent additions to the field of material science are materials that exhibit what is known as the shape memory effect. Both metals and synthetic polymers can acquire this property through processing and chemistry. However while shape memory polymers hold a lot of promise, it will require more research and development to make them affordable and useful in large scale applications. / text

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Yes / The shrinkage force exerted by restrained shape memory polymers can potentially be used to close cracks in structural concrete. This paper describes the physical processing and experimental work undertaken to develop high shrinkage die-drawn Polyethylene Terephthalate (PET) shape memory polymer tendons for use within a crack closure system. The extrusion and die-drawing procedure used to manufacture a series of PET tendon samples is described. The results from a set of restrained shrinkage tests, undertaken at differing activation temperatures, are also presented along with the mechanical properties of the most promising samples. The stress developed within the tendons is found to be related to the activation temperature, the cross-sectional area and to the draw rate used during manufacture. Comparisons with commercially-available PET strip samples used in previous research are made, demonstrating an increase in restrained shrinkage stress by a factor of two for manufactured PET filament samples. / Thanks must go to the EPSRC for their funding of the Materials for Life (M4L) project (EP/K026631/1) and to Costain Group PLC. for their industrial sponsorship of the project and author.

In many studies of the side-chain liquid crystalline polymers (SCLCPs) bearing azobenzene mesogens as pendant groups, obtaining the orientation of azobenzene mesogens at a macroscopic scale as well as its control is important, because it impacts many properties related to the cooperative motion characteristic of liquid crystals and the trans-cis photoisomerization of the azobenzene molecules. Various means can be used to align the mesogens in the polymers, including rubbed surface, mechanical stretching or shearing, and electric or magnetic field. In the case of azobenzene-containing SCLCPs, another method consists in using linearly polarized light (LPL) to induce orientation of azobenzene mesogens perpendicular to the polarization direction of the excitation light, and such photoinduced orientation has been the subject of numerous studies. In the first study realized in this thesis (Chapter 1), we carried out the first systematic investigation on the interplay of the mechanically and optically induced orientation of azobenzene mesogens as well as the effect of thermal annealing in a SCLCP and a diblock copolymer comprising two SCLCPs bearing azobenzene and biphenyl mesogens, respectively. Using a supporting-film approach previously developed by our group, a given polymer film can be first stretched in either the nematic or smectic phase to yield orientation of azobenzene mesogens either parallel or perpendicular to the strain direction, then exposed to unpolarized UV light to erase the mechanically induced orientation upon the trans–cis isomerization, followed by linearly polarized visible light for photoinduced reorientation as a result of the cis–trans backisomerization, and finally heated to different LC phases for thermal annealing. Using infrared dichroism to monitor the change in orientation degree, the results of this study have unveiled complex and different orientational behavior and coupling effects for the homopolymer of poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate} (PAzMA) and the diblock copolymer of PAzMA-block- poly{6-[4-(4-cyanophenyl) phenoxy]hexyl methacrylate} (PAzMA-PBiPh). Most notably for the homopolymer, the stretching-induced orientation exerts no memory effect on the photoinduced reorientation, the direction of which is determined by the polarization of the visible light regardless of the mechanically induced orientation direction in the stretched film. Moreover, subsequent thermal annealing in the nematic phase leads to parallel orientation independently of the initial mechanically or photoinduced orientation direction. By contrast, the diblock copolymer displays a strong orientation memory effect. Regardless of the condition used, either for photoinduced reorientation or thermal annealing in the liquid crystalline phase, only the initial stretching-induced perpendicular orientation of azobenzene mesogens can be recovered. The reported findings provide new insight into the different orientation mechanisms, and help understand the important issue of orientation induction and control in azobenzene-containing SCLCPs. The second study presented in this thesis (Chapter 2) deals with supramolecular side-chain liquid crystalline polymers (S-SCLCPs), in which side-group mesogens are linked to the chain backbone through non-covalent interactions such as hydrogen bonding. Little is known about the mechanically induced orientation of mesogens in S-SCLCPs. In contrast to covalent SCLCPs, free-standing, solution-cast thin films of a S-SCLCP, built up with 4-(4’-heptylphenyl) azophenol (7PAP) H-bonded to poly(4-vinyl pyridine) (P4VP), display excellent stretchability. Taking advantage of this finding, we investigated the stretching-induced orientation and the viscoelastic behavior of this S-SCLCP, and the results revealed major differences between supramolecular and covalent SCLCPs. For covalent SCLCPs, the strong coupling between chain backbone and side-group mesogens means that the two constituents can mutually influence each other; the lack of chain entanglements is a manifestation of this coupling effect, which accounts for the difficulty in obtaining freestanding and mechanically stretchable films. Upon elongation of a covalent SCLCP film cast on a supporting film, the mechanical force acts on the coupled polymer backbone and mesogenic side groups, and the latter orients cooperatively and efficiently (high orientation degree), which, in turn, imposes an anisotropic conformation of the chain backbone (low orientation degree). In the case of the S-SCLCP of P4VP-7PAP, the coupling between the side-group mesogens and the chain backbone is much weakened owing to the dynamic dissociation/association of the H-bonds linking the two constituents. The consequence of this decoupling is readily observable from the viscoelastic behavior. The average molecular weight between entanglements is basically unchanged in both the smectic and isotropic phase, and is similar to non-liquid crystalline samples. As a result, the S-SCLCP can easily form freestanding and stretchable films. Furthermore, the stretching induced orientation behavior of P4VP-7PAP is totally different. Stretching in the smectic phase results in a very low degree of orientation of the side-group mesogens even at a large strain (500%), while the orientation of the main chain backbone develops steadily with increasing the strain, much the same way as amorphous polymers. The results imply that upon stretching, the mechanical force is mostly coupled to the polymer backbone and leads to its orientation, while the main chain orientation exerts little effect on orienting the H-bonded mesogenic side groups. This surprising finding is explained by the likelihood that during stretching in the smectic phase (at relatively higher temperatures) the dynamic dissociation of the H-bonds allow the side-group mesogens to be decoupled from the chain backbone and relax quickly. In the third project (Chapter 3), we investigated the shape memory properties of a S-SCLCP prepared by tethering two azobenzene mesogens, namely, 7PAP and 4-(4'-ethoxyphenyl) azophenol (2OPAP), to P4VP through H-bonding. The results revealed that, despite the dynamic nature of the linking H-bonds, the supramolecular SCLCP behaves similarly to covalent SCLCP by exhibiting a two-stage thermally triggered shape recovery process governed by both the glass transition and the LC-isotropic phase transition. The ability for the supramolecular SCLCP to store part of the strain energy above T[subscript g] in the LC phase enables the triple-shape memory property. Moreover, thanks to the azobenzene mesogens used, which can undergo trans-cis photoisomerization, exposure the supramolecular SCLCP to UV light can also trigger the shape recovery process, thus enabling the remote activation and the spatiotemporal control of the shape memory. By measuring the generated contractile force and its removal upon turning on and off the UV light, respectively, on an elongated film under constant strain, it seems that the optically triggered shape recovery stems from a combination of a photothermal effect and an effect of photoplasticization or of an order-disorder phase transition resulting from the trans-cis photoisomerization of azobenzene mesogens.

This work focuses on the thermomechanical characterization and constitutive model calibration of shape memory polymers (SMPs). These polymers have the ability to recover seemingly permanent large deformations under the appropriate thermomechanical load path. In this work, a contribution is made to both existing experimental and modeling efforts. First, an experimental investigation is conducted which subjects SMPs to a thermomechanical load path that includes varying the value of applied deformations and temperature rates. Specifically, SMPs are deformed to tensile extensions of 10% to 100% at temperature rates varying from 1 degree C /min to 5 degree C/min, and the complete shape recovery profile is captured. The results from this experimental investigation show that the SMP in question can recover approximately 95% of the value of the applied deformation, independent of the temperature rate during the test. The data obtained in the experimental investigation are then used to calibrate, in one-dimension, two constitutive models which have been developed to describe and predict the material response of SMPs. The models include a model in terms of general deformation gradients, thus making it capable of handling large deformations. In addition, the data are used to calibrate a linearized version of the constitutive model for small deformations. The material properties required for calibrating the constitutive models are derived from portions of the experimental results, and the model is then used to predict the shape memory effect for an SMP undergoing various levels of deformation. The model predictions are shown to match well with the experimental data.

A series of segmented poly (epsilon-caprolactone) polyurethane-ureas (PCLUUs) were prepared from poly (epsilon-caprolactone) (PCL) diol, different dissociates and chain extenders to improve the recovery stress of shape memory polymers. NMR and FT-IR were used to identify the structure of the synthesized shape memory polyurethane-ureas. Parameters such as soft segment content (molecular weight and content), chain extender and the rigidity of the main chain were investigated to understand the structure-property relationships of the shape memory polymer systems through DSC, DMA, physical property test, etc. Cyclic thermal mechanic tests were applied to measure the shape memory properties which showed that the recovery stress can be improved above 200% simply by modifying the chain extender. Meanwhile, the synthesis process was optimized to be similar to that of Spandex /LYCRA®. Continuous fibers were made from a wet spinning process, which indicated excellent spinnability of the polymer solution. Small angle neutron scattering (SANS) was used to study the morphology of the hard segment at different temperatures and stretch rates and found that the monodisperse rigid cylinder model fit the SANS data quite well. From the cylinder model, the radius of the cylinder increases with the increasing hard segment content. The SANS results revealed phase separation of hard and soft segments into nano scale domains.

Shape memory polymers (SMPs) are a relatively new class of active materials that can store a temporary shape and return to the original configuration upon application of a stimulus such as temperature. This shape changing ability has led to increased interest in their use for biomedical and aerospace applications. A major challenge, however, in the advancement of these applications is the ability to accurately predict the material behavior for complex geometries and boundary conditions. This work addresses this challenge by developing an experimentally calibrated and validated constitutive model that is implemented as a user material subroutine in Abaqus ? a commercially available finite element software package. The model is formulated in terms of finite deformations and assumes the SMP behaves as a thermoelastic material, for which the response is modeled using a compressible neo-Hookean constitutive equation. An internal state variable, the glassy volume fraction, is introduced to account for the phase transformation and associated stored deformation upon cooling from the rubbery phase to the glassy phase and subsequently recovered upon heating. The numerical implementation is performed such that a system of equations is solved using a Newton-Raphson method to find the updated stress in the material. The conductive heat transfer is incorporated through solving Fourier's law simultaneously with the constitutive equations. To calibrate and validate the model parameters, thermomechanical experiments are performed on an amorphous, thermosetting polyurethane shape memory polymer. Strains of 10-25% are applied and both free recovery (zero load) and constrained displacement recovery boundary conditions are considered for each value of applied strain. Using the uniaxial experimental data, the model is then calibrated and compared to the 1-D experimental results. The validated finite element analysis tool is then used to model biomedical devices, including cardiovascular tubes and thrombectomy devices, fabricated from shape memory polymers. The effects of heat transfer and complex thermal boundary conditions are evaluated using coupled thermal-displacement analysis, for which the thermal material properties were experimentally calibrated.

Nowadays, to diagnose a lung cancer, a bronchoscopy is performed and a biological sample is extracted and analyzed by the anatomical pathology department of the hospital. Currently, there are no commercially available techniques allowing a real-time, in vivo, label-free diagnosis of lung cancer. The PREDICTION project aims to develop a biosensing tool gathering all the attributes mentioned above by combining optics, biochemistry and mechanics. The role of my research is to focus on the mechanics and to develop an instrumented catheter, acting as a shield of the biosensor. The choice of the material and the design were made based on the optical properties (visible under fluoroscopy) and the mechanical characteristics (trade-off between rigidity and compliance). In order to provide a stable measurement, the distal extremity of the instrumented catheter was shaped in the form of a conical needle. A window was patterned on the side of the instrumented catheter to expose the biosensor to the targeted tissue. The instrumented catheter was designed to be able to embed one biosensor and one control fibre. Its measurement integrity has been validated through in vitro and ex vivo experiments. In order to improve navigation outside the scope of the working channel of the bronchoscope, i.e. add one degree of freedom to the catheter, Shape Memory Polymers were investigated. Two prototypes were designed. The first prototype combines a soft pneumatic actuator with a shape memory polymer strip acting as a stiffness tuner. The Shape Memory Polymer structure proved to be efficient to fix the shape of the soft pneumatic actuator and also to increase the force it can provide. The second prototype combines a catheter with a Shape Memory Polymer strip. The experimental results proved the ability of the Shape Memory Polymer strip to develop a force high enough to bend a catheter with an adequate bending angle for in vivo lung navigation. To conclude, the work produced during this PhD resulted in the development of an instrumented catheter allowing real time, ex vivo, label-free diagnosis of lung cancer. Further work should be done on the instrumented catheter dimensions and sterilization to apply these results to in vivo diagnosis. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

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