This thesis focuses on the generation of fine cell polymer foams using a heterogeneous nucleating agent (nanoclay), appropriate polymer blending strategies and accurate control of foam processing parameters. Foaming behaviour of HMSPP/ clay nanocomposites and HMS-PP/EVA/clay nanocomposite blends is studied using a batch and a continuous foam injection moulding system. Morphological studies using TEM and SEM led to a few interesting deductions. It is very difficult to attain complete exfoliation in case of HMS-PP/clay nanocomposites even at low clay loadings due to a non polar nature and low graft efficiencies of HMS-PP matrix. The addition of clay to an immiscible blend of HMS-PP/EVA results in compatibilization between the dispersed and the continuous phase. Nanocellular foams (290 nm) were subsequently generated in the batch process at a foaming temperature of 147oC and 25 seconds foaming time. The addition of immiscible EVA-28 to the HMS-PP matrix in presence of clay particles further results in reduction of foam cell sizes to 100 nm. The effect of gas concentration, foaming temperature, injection pressure, and foaming time on foam cell size was studied. It was found that the foam cell size was highly sensitive to the injection pressure at the mould gate (hence pressure drop rate) and foaming temperature. The cell size linearly decreased with increase in gas concentration and foaming time. The sensitivity of foam cell sizes to changes in processing parameters decreases with increase in clay concentration. The effect of addition of clay particle on gas solubility was modelled using the Guggenheims contact fraction approach and subsequently a new model to predict gas solubility was developed using statistical thermodynamic tools. Additionally the effect of shear and extensional rheology on foam cell morphology was modelled. It was found that the viscoelasticity of the polymer matrix greatly affects cell sizes as compared to extensional viscosity.

The asymmetrical arrangement of cellular structure allows for an accurate functional adaptation at all levels of hierarchy, which derives excellent features for the development of new materials. The main objective of introducing a hierarchy into cellular structures is to improve the mechanical behaviour of the material while maintaining its elastic properties. A part of this work is devoted to the literature review related to the lightened cellular polymeric materials with hierarchical cellular structure. The rest is focused on the preparation of PLA based polymer structures using 3D printing, followed by a saturation in CO2 and a foaming in a silicon oil at elevated temperature. Samples were prepared from natural and white PLA filaments. Based on a series of experiments, optimal conditions for the saturation and foaming process were identified. Through 3D printing and foaming, a one-, two- and three-level hierarchy was introduced into the beam-shaped samples and the effect of the internal cell arrangement on the strain response of the material was examined by the means of a mechanical three-point bending test. Increasing the level of the hierarchy led to an increase in material resistance, which resulted in high values of strength and strain energy (toughness) based on the samples density. The best results were achieved by samples with “sandwich” structure with three levels of hierarchy and 30% filling. Despite the shorter plateau, there was a significant increase in strength and strain energy compared to gradient structures. At the same time, the contribution of the polymer structures prepared in this field of research was demonstrated by comparison with the theoretical model.

Decreasing the carbon footprint through use of renewable materials has environmental and societal impact. Foams are a valuable constituent in buildings by themselves or as a core in sandwich composites. Kenaf is a Southeast USA plant that provides renewable filler. The core of the kenaf is porous with a cell size in a 5-10 micrometer range. The use of kenaf core in foams represents a novel multiscalar cellular structural composite. Rigid polyurethane foams were made using free foaming expansion with kenaf core as filler with loadings of 5, 10 and 15 %. Free foaming was found to negatively affect the mechanical properties. An innovative process was developed to introduce a constraint to expansion during foaming. Two expansion ratios were examined: 40 and 60 % (decreasing expansion ratio). MicroCT and SEM analysis showed a varying structure of open and closed cell pores. The mechanical, thermal insulation, acoustic properties were measured. Pure PU foam showed improved cell size uniformity. Introducing kenaf core resulted in decreasing the PU performance in the free expansion case. This was reversed by introducing constraints. To understand the combined impact of having a mixed close cell and open cell architecture, finite element modeling was done using ANSYS. Models were created with varying percentages of open, closed, and bulk cells to encompass entire range of foam porosities. Net zero energy building information modelling was conducted using EnergyPlus was conducted using natural fiber composite skins. Environmental impacts for instance global warming potential, acidification, eutrophication, fossil fuel consumption, ozone depletion, and smog potential of the materials used in construction was studied using life cycle assessment. The results showed improvement on energy consumption and carbon footprint.

No description available.

Polymer foams belong to the solid foams family which are versatile materials, extensively used for a large number of applications such as automotive, packaging, sport products, thermal and acoustic insulators, tissue engineering or liquid absorbents. Composed of air bubbles entrapped in a continuous solid network, they combine the properties of the polymer with those of the foam to create an intriguing and complex material. Incorporating a foam into a polymer network not only allows one to use the wide range of interesting properties that the polymer offers, but also permits to profit from the advantageous properties of foam including lightness, low density, compressibility and high surface-to-volume ratio. Generally, the properties of polymer foams are strongly related to their density and their structure (bubble size and size distribution, bubble arrangement, open vs closed cells). Having a good control over foam properties is thus achieved by first controlling its density and structure.We developed a technique in which solid foams are generated essentially in a two-step process: a sufficiently stable liquid foam with well-controlled structural properties is generated in a first step, and then solidified in a second one. With such a two-step approach, the generation of solid foams can be divided into a number of well-separated sub-tasks which can be controlled and optimised separately. The transition from liquid to solid state is a sensitive issue of a great importance and therefore needs to be controlled with sufficient accuracy. It is essentially composed of three key steps: foam generation, mixing of reactants and foam solidification and requires the optimisation of foam stability in conjunction with an appropriate choice of both foaming time and solidification time. Furthermore, a good homogeneity of the polymer foam calls for a good mixing of the different reactants involved in the foaming and the polymerisation.A particularly powerful demonstration of the advantages of this approach is given by solidifying monodisperse liquid foams generated using millifluidic technique, in which all bubbles have the same size. In a liquid foam, equal-volume bubbles self-order into periodic, close-packed structures under gravity or confinement. As such, monodisperse foams provide simultaneous control over the size and the organisation of the pores in the final solid with an accuracy which is expected to give rise to a better understanding of the structure-property relationship of porous solids and to the development of new porous materials.We therefore aim to explore the new spectrum of properties, which polymer foams offer when we introduce an ordered structure into them since the most widely used polymer foams nowadays have disordered structures. The goal of our study is to demonstrate the feasibility of this two-step approach for different classes of polymers, including biomolecular hydrogel, superabsorbent polymer and polyurethane.For the generation of the structured polymer foams we use Lab-on-a-Chip technologies which allow the "shrinking" of large-scale set-ups to micro/millimetic scale. It permits also to perform "flow chemistry" in which the various liquid and gaseous ingredients of the foam are injected and mixed in a purpose-designed network of the micro- and millifluidic Lab-on-a-Chip. We adjust this approach according to the requirements of each polymer system, i.e. the foaming and the mixing techniques are chosen to fit the properties of each system, and can be exchanged to fit the properties of the studied systems.

Les mousses polymères appartiennent à la famille des mousses solides qui sont des matériaux polyvalents, largement utilisés dans un grand nombre d'applications telles que l'automobile, l'emballage, produits de sport, isolants thermiques et acoustiques ou l'ingénierie tissulaire. Composé de bulles d'air piégées dans un réseau continu solide, elles allient les propriétés du polymère avec ceux de la mousse pour créer un matériau intéressant et complexe. L'intégration d'une mousse dans un réseau de polymère permet non seulement d'utiliser la vaste gamme de propriétés intéressantes offertes par les polymères, mais permet aussi de profiter des propriétés avantageuses des mousse telles que la légèreté, la faible densité, la compressibilité et un rapport surface/volume grande surface élevé. En général, les propriétés des mousses polymères sont fortement liées à leur densité et leur structure (la taille des bulles, l’arrangement des bulles dans l’espace, la structure des cellules ouvertes ou fermées). Le contrôle des propriétés finales de ces mousses est donc régi par le contrôle de sa densité et sa structure.Nous avons développé une technique dans laquelle des mousses solides sont générées essentiellement suivant un processus à deux étapes dans lequel une mousse liquide suffisamment stable ayant des propriétés bien contrôlées est générée dans une première étape, puis solidifiée. Avec une telle approche, la production des mousses solides peut être divisé en un certain nombre de sous-tâches qui peuvent être contrôlées et optimisées séparément.Le passage de l'état liquide à l'état solide est essentiellement composé de trois étapes principales: la production de la mousse, le mélange des réactifs et la solidification de la mousse. Ce dernier nécessite l'optimisation de la stabilité de la mousse et des paramètres expérimentaux tels que le choix du temps de moussage et de solidification. En outre, une bonne homogénéité de la mousse polymère appelle à un bon mélange des différents réactifs impliqués dans la formulation de la mousse et de la polymérisation.Une illustration des avantages de cette approche est donnée par la solidification de mousses liquides monodisperses générées à l’aide de la technique millifluidique. Dans une telle mousse, des bulles de volume égal, s’auto-organisent sous l’effet de la gravité et du confinement pour former des structures cristallines. Ainsi, les mousses monodisperses permettent d’avoir un contrôle simultanément sur la taille et la distribution des bulles du matériau poreux final, ce qui donne lieu à une meilleure compréhension de la corrélation entre sa structure et ses propriétés. L’objectif de cette étude est donc d'explorer le nouveau spectre de propriétés, que des mousses polymère offrent lorsque l’on y introduit une structure ordonnée et de démontrer la faisabilité de cette approche à deux étapes pour différentes classes de polymères (hydrogel, polymère super-absorbant et polyuréthane).La génération de ces mousses polymères structurées a été réalisée à l’aide d’un laboratoire sur puce qui permet le rétrécissement des dispositifs expérimentaux à l'échelle micro / millimétrique. Il permet également l’injection et le mélange divers ingrédients liquides et gazeux de la mousse. / Polymer foams belong to the solid foams family which are versatile materials, extensively used for a large number of applications such as automotive, packaging, sport products, thermal and acoustic insulators, tissue engineering or liquid absorbents. Composed of air bubbles entrapped in a continuous solid network, they combine the properties of the polymer with those of the foam to create an intriguing and complex material. Incorporating a foam into a polymer network not only allows one to use the wide range of interesting properties that the polymer offers, but also permits to profit from the advantageous properties of foam including lightness, low density, compressibility and high surface-to-volume ratio. Generally, the properties of polymer foams are strongly related to their density and their structure (bubble size and size distribution, bubble arrangement, open vs closed cells). Having a good control over foam properties is thus achieved by first controlling its density and structure.We developed a technique in which solid foams are generated essentially in a two-step process: a sufficiently stable liquid foam with well-controlled structural properties is generated in a first step, and then solidified in a second one. With such a two-step approach, the generation of solid foams can be divided into a number of well-separated sub-tasks which can be controlled and optimised separately. The transition from liquid to solid state is a sensitive issue of a great importance and therefore needs to be controlled with sufficient accuracy. It is essentially composed of three key steps: foam generation, mixing of reactants and foam solidification and requires the optimisation of foam stability in conjunction with an appropriate choice of both foaming time and solidification time. Furthermore, a good homogeneity of the polymer foam calls for a good mixing of the different reactants involved in the foaming and the polymerisation.A particularly powerful demonstration of the advantages of this approach is given by solidifying monodisperse liquid foams generated using millifluidic technique, in which all bubbles have the same size. In a liquid foam, equal-volume bubbles self-order into periodic, close-packed structures under gravity or confinement. As such, monodisperse foams provide simultaneous control over the size and the organisation of the pores in the final solid with an accuracy which is expected to give rise to a better understanding of the structure-property relationship of porous solids and to the development of new porous materials.We therefore aim to explore the new spectrum of properties, which polymer foams offer when we introduce an ordered structure into them since the most widely used polymer foams nowadays have disordered structures. The goal of our study is to demonstrate the feasibility of this two-step approach for different classes of polymers, including biomolecular hydrogel, superabsorbent polymer and polyurethane.For the generation of the structured polymer foams we use Lab-on-a-Chip technologies which allow the “shrinking” of large-scale set-ups to micro/millimetic scale. It permits also to perform “flow chemistry” in which the various liquid and gaseous ingredients of the foam are injected and mixed in a purpose-designed network of the micro- and millifluidic Lab-on-a-Chip. We adjust this approach according to the requirements of each polymer system, i.e. the foaming and the mixing techniques are chosen to fit the properties of each system, and can be exchanged to fit the properties of the studied systems.

<div>This body of work examines analytical and numerical models to simulate the response of structures in shock absorption applications. Specifically, the work examines the prediction of cushion curves of polymer foams, and a topological examination of a $\chi$ shape unit cell found in architected mechanical elastomeric metamaterials. The $\chi$ unit cell exhibits the same effective stress-strain relationship as a closed cell polymer foam. Polymer foams are commonly used in the protective packaging of fragile products. Cushion curves are used within the packaging industry to characterize a foam's impact performance. These curves are two-dimensional representations of the deceleration of an impacting mass versus static stress. The main drawback with cushion curves is that they are currently generated from an exhaustive set of experimental test data. This work examines modeling the shock response using a continuous rod approximation with a given impact velocity in order to generate cushion curves without the need of extensive testing. In examining the $\chi$ unit cell, this work focuses on the effects of topological changes on constitutive behavior and shock absorbing performance. Particular emphasis is placed on developing models to predict the onset of regions of quasi-zero-modulus (QZM), the length of the QZM region and the cushion curve produced by impacting the unit cell. The unit cell's topology is reduced to examining a characteristic angle, defining the internal geometry with the cell, and examining the effects of changing this angle.</div><div>However, the characteristic angle cannot be increased without tradeoffs; the cell's effective constitutive behavior evolves from long regions to shortened regions of quasi-zero modulus. Finally, this work shows that the basic $\chi$ unit cell can be tessellated to produce a nearly equivalent force deflection relationship in two directions. The analysis and results in this work can be viewed as new framework in analyzing programmable elastomeric metamaterials that exhibit this type of nonlinear behavior for shock absorption.</div>