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Serghei A.,CNRS Laboratory for Polymer Materials Engineering | Zhao W.,University of Massachusetts Amherst | Miranda D.,University of Massachusetts Amherst | Russell T.P.,University of Massachusetts Amherst
Nano Letters | Year: 2013

Polymer systems having one, two, or three dimensions on the nanometer length scale can exhibit physical properties different from the bulk. The degree of disorder characteristic for large amounts of matter is strongly reduced and changes in symmetry are imposed by means of geometrical confinement. This could be used to induce - through orientation and order - enhancement in the material properties. Experiments on extremely small amounts of matter, however, are naturally characterized by large fluctuations in the measured signals, especially in the case of polymer objects having three dimensions on the nanometer length scale. This imposes the necessity of repeating the measurements until a statistical distribution is obtained. Here we show that investigations on statistical ensembles of attograms of material (1 ag = 10-18 g) are possible in a single experiment by employing highly ordered arrays of identical, independent, additive nanocontainers. Phase transitions corresponding to attograms of a ferroelectric polymer are measured by this approach. As compared to one- or two-dimensional confinement, significant changes in the Curie transitions are found. © 2013 American Chemical Society. Source

Ghadban A.,Joseph Fourier University | Ghadban A.,CNRS Laboratory for Polymer Materials Engineering | Reynaud E.,Joseph Fourier University | Albertin L.,Joseph Fourier University
Polymer Chemistry | Year: 2013

The aqueous RAFT copolymerization of methacrylamide- and methacrylate-functionalized (1→4)-α-l-guluronan and (1→4)-β-d-mannuronan macromonomers with N-(2-hydroxyethyl) methacrylamide afforded synthetic-g-polysaccharide copolymers with a predetermined and well-defined molar mass (grafting through approach). One such polymer featuring guluronan graft chains of Xn = 21 was able to undergo ionotropic gelation in the presence of Ca2+ ions and to form a soft hydrogel in spite of the fairly low molar mass (Mn = 77000 Da). The high yield synthesis of a new methacrylate-functionalized (1→4)-α-l-guluronan is also reported. © 2013 The Royal Society of Chemistry. Source

Taguet A.,Ecole des Mines dAles | Cassagnau P.,CNRS Laboratory for Polymer Materials Engineering | Lopez-Cuesta J.-M.,Ecole des Mines dAles
Progress in Polymer Science | Year: 2014

Hybrid ternary blends comprising two polymers and one mineral (nano)filler are increasingly studied because they are starting to be widely used to respond to industrial issues. The objective of this review is to gather information on these particular systems. Concerning first thermodynamic effects of fillers on the phase separation of an immiscible polymer blend, Flory-Huggins theory demonstrate stabilization. This theory was particularly taken up and developed for the case of two polymers and one filler by Lipatov and Nesterov in the 90s. More recently, Ginzburg generalized this theory to the case of unfavorable enthalpic interactions between a particle and the two polymers. They showed that the amount of particles had to attain a certain threshold to stabilize the system and the lower the particle radius, the higher the stable zone area. Generally speaking, all the phenomena regarding the morphology of polymer blends are governed by thermodynamics and/or kinetic effects, as well as the localization of nanoparticles. The main discussed thermodynamically controlling parameter of the localization is the wetting parameter ωAB. However, because of the viscosity of the system, the equilibrium dictated by ωABmay never be reached. Hence, concerning the kinetic effects, the final localization of fillers in a polymer pair is guided by the sequence of mixing of the components, the viscosity ratio, the composition, the temperature, the shear rate and the time of mixing. When the particles are placed at the interface between two polymers, coalescence can be suppressed or/and interfacial tension can be reduced. In that case, particles are known to play the role of a compatibilizer. In a ternary system, (i) the shape of the particle (spheres, rods or "onions-shape"), (ii) the particle radius (Rp) versus the radius of gyration of the polymers (Rg) and (iii) the surface chemistry of the particles affect the final localization of the particles (thus, the compatibilizing effect) and the final properties of the material, such as mechanical, conductive, magnetic and thermal properties. This review details recent works for which those four above mentioned properties are improved by incorporating different kind of fillers in polymer blends. © 2014 Elsevier Ltd. Source

Polexe R.C.,Cytosial Biomedic | Delair T.,CNRS Laboratory for Polymer Materials Engineering
Molecules | Year: 2013

In this study, we describe the elaboration of multifunctional positively charged polyelectrolyte complex (PEC) nanoparticles, designed to be stable at physiological salt concentration and pH, for effective targeted delivery. These nanoparticles were obtained by charge neutralization between chitosan (CS) as polycation and hyaluronic acid (HA) as polyanion. We showed that the course of the complexation process and the physico-chemical properties of the resulting colloids were impacted by (i) internal parameters such as the Degree of Acetylation (DA, i.e., the molar ration of acetyl glucosamine residues) and molar mass of CS, the HA molar mass and (ii) external parameters like the charge mixing ratio and the polymer concentrations. As a result, nonstoichiometric colloidal PECs were obtained in water or PBS (pH 7.4) and remained stable over one month. The polymer interactions were characterized by thermal analysis (DSC and TGA) and the morphology was studied by scanning electron microscopy. A model antibody, anti-ovalbumine (OVA) immunoglobulin A (IgA) was sorbed on the particle surface in water and PBS quantitatively in 4 h. The CS-HA/IgA nanoparticles average size was between 425-665 nm with a positive zeta potential. These results pointed out that CS-HA can be effective carriers for use in targeted drug delivery. © 2013 by the authors. Source

Lamnawar K.,University of Lyon | Bousmina M.,Hassan II Academy of Science and Technology | Maazouz A.,University of Lyon | Maazouz A.,Hassan II Academy of Science and Technology | Maazouz A.,CNRS Laboratory for Polymer Materials Engineering
Macromolecules | Year: 2012

The aim of the present work has been to gain a fundamental understanding of the mechanisms governing encapsulation in the multiphase systems as a blend or multilayer structures. The model systems chosen for this study are based on (i) Newtonian poly(dimethylsiloxane) polymers of varying molar masses and (ii) high molecular weight, viscoelastic, and compatible pair polymers of PVDF and PMMA. The same approach was applied to functionalized polymers to investigate the effect of physicochemical affinity on two pairs of asymmetrical reactive polymers based on PE-GMA (glycidyl methacrylate)/PVDF-g-MA (maleic anhydride) and a PE/PVDF as a reference. The linear viscoelastic and surface properties of the neat and bilayer model systems structures have been investigated. The optical obeservations of the encapsulation kinetic of two drops were recorded using a homemade device. Specific experiments were carried out to follow up the kinetic of encapsulation, and the results were rationalized as a function of the effect of the viscosity, elasticity ratios, drop geometry, the interfacial tension, and the physicochemical affinity. Throughout all the experiment, the mechanisms were purposed for each system and discussed based on the theories of molecular forces or Brownian motion governing diffusion and Ostwald ripening, in contrast to the theories of coalescence. The viscosity ratio coupled to the drop geometry of the material was found to be a key parameter and that it has to be linked to the interfacial tension and spreading parameters. Furthermore, the encapsulation appeared to be hindered by the interdiffusion process in the case of compatible pair system despite their elasticity and surface tension contrast. Finally, the encapsulation kinetic could be reduced or eliminated by the creation of a copolymer at the interface for a reactive system. The results obtained by the optical investigation of two drops corroborated the rheological data of the bilayer systems. Hence, the obtained results rendered it possible to decouple the influence of the viscoelastic parameters to flow, interfacial tension, thereby highlighting a number of macroscopic effects that were governed by the interdiffusion or reaction of macromolecular chains at the interface to give a better understanding of encapsulation phenomenon in multiphase systems. © 2011 American Chemical Society. Source

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