is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. AbstractThe thermo-oxidative degradation of polylactide (PLA) films was studied between 70 and 150°C. It was shown that the oxidative degradation of PLA leads to a random chain scission responsible for a reduction of the molar mass. These molar mass changes affect Tg and the degree of crystalllinity, and it was found that Tg decreases according to the Fox-Flory theory whereas the degree of crystalllinity increases due to a chemicrystallization process. A correlation between molar mass and strain at break during oxidation has been established:PLA displays a brittle behaviour when M n falls below 40 kg.mol -1 in agreement with relationships linking the critical value for embrittlement with the molar mass between entanglements.

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New hydrophobically modified hydrogels have been designed in order to obtain a series of gels with identical elastic moduli but variable dissipative properties. The synthesis of these systems has been realized following a three-step procedure: (1) introduction of double bonds onto a poly(acrylic acid) backbone [PAA],(2) hydrophobic modification of the PAA with dodecylamine, and (3) cross-linking of double bonds using dithiol. The characterization of gel precursors shows that hydrophobically modified polymers self-assemble in semidilute solution forming physical gels with temporary hydrophobic clusters. The gelation mechanism induced by reacting pendant double bonds with dithiol was studied by DSC, specific titrations, and rheology. The gelation process was not perturbed by the presence of the hydrophobic groups, and the kinetics follows a first-order dependence on thiol. In the entangled regime, the thiol conversion reaches around 80%, but only about 10% of the thiols effectively promote the formation of chemical cross-links while the other 90% are incorporated into the gel as loops or dangling chains. Once the gels are formed, NMR and SANS clearly demonstrate that hydrophobic side chains continue to form micelles within the network and that these micelles display a much better long-range order than their un-cross-linked precursors in aqueous solutions. All gels, both hydrophilic and hydrophobically modified, display a storage modulus G′ which only depends on total polymer concentration and can be described on the basis of the percolation theory (G′ ∼ 2.6 ) with , the reduced concentration defined from a fixed concentration at the gel point C g ) 2%. On the other hand, the loss modulus G′′ increases dramatically relative to the corresponding hydrophilic gel, when hydrophobic groups which formed reversible associations are introduced.

is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible.This is an author-deposited version published in: http://sam.ensam.eu Handle

3D printing (additive manufacturing (AM)) has enormous potential for rapid tooling and mass production due to its design flexibility and significant reduction of the timeline from design to manufacturing. The current state-of-the-art in 3D printing focuses on material manufacturability and engineering applications. However, there still exists the bottleneck of low printing resolution and processing rates, especially when nanomaterials need tailorable orders at different scales. An interesting phenomenon is the preferential alignment of nanoparticles that enhance material properties. Therefore, this review emphasizes the landscape of nanoparticle alignment in the context of 3D printing. Herein, a brief overview of 3D printing is provided, followed by a comprehensive summary of the 3D printing-enabled nanoparticle alignment in wellestablished and in-house customized 3D printing mechanisms that can lead to selective deposition and preferential orientation of nanoparticles. Subsequently, it is listed that typical applications that utilized the properties of ordered nanoparticles (e.g., structural composites, heat conductors, chemo-resistive sensors, engineered surfaces, tissue scaffolds, and actuators based on structural and functional property improvement). This review's emphasis is on the particle alignment methodology and the performance of composites incorporating aligned nanoparticles. In the end, significant limitations of current 3D printing techniques are identified together with future perspectives.

An experimental study was carried out to investigate the existence of a critical layer thickness in nanolayer coextrusion, under which no continuous layer is observed. Polymer films containing thousands of layers of alternating polymers with individual layer thicknesses below 100 nm have been prepared by coextrusion through a series of layer multiplying elements. Different films composed of alternating layers of poly(methyl methacrylate) (PMMA) and polystyrene (PS) were fabricated with the aim to reach individual layer thicknesses as small as possible, varying the number of layers, the

Systematic large strain compression measurements have been performed on polyelectrolyte hydrogels based on modified PAA crosslinked by bifunctional thiols. For compressive strains larger than a critical value depending on polymer concentration, we observed a significant hysteresis, strain-hardening and a stress plateau during unloading. This was attributed to strain-induced ionic clustering due to electrostatic interactions that can become attractive if chains are close enough to each other. This phenomenon is dynamic and reversible but a long lifetime for the clusters has been identified. Although clustering between like-charge chains has been reported for hydrogels, it is the first time that this phenomenon is caused by deformation. This effect is potentially important as we strive to understand the behaviour of all polyelectrolyte hydrogels at large strains which are highly relevant for fracture properties.

is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. t r a c tA potential advantage of platelet-like nanofillers as nanocomposite reinforcements is the possibility of achieving two-dimensional stiffening through planar orientation of the platelets. The ability to achieve improved properties through in-plane orientation of the platelets is a challenge and, here, we present the first results of using forced assembly to orient graphene nanoplatelets in poly(methyl methacrylate)/ polystyrene (PMMA/PS) and PMMA/PMMA multilayer films produced through multilayer coextrusion. The films exhibited a multilayer structure made of alternating layers of polymer and polymer containing graphene as evidenced by electron microscopy. Significant single layer reinforcement of 118% at a concentration of 2 wt % graphene was achieveddhigher than previously reported reinforcement for randomly dispersed graphene. The large reinforcement is attributed to the planar orientation of the graphene in the individual polymer layers. Anisotropy of the stiffening was also observed and attributed to imperfect planar orientation of the graphene lateral to the extrusion flow. Ó