Isothermal crystallization kinetics in a limited volume. A geometrical approach based on Evans' theory

A new theoretical approach of the isothermal crystallization of a thin polymer film is proposed. This model, derived from Evans' theory, is in very good agreement with a previous one, but is much more interesting because it makes it possible to calculate the transformed volume fraction anywhere in the film. The main effects of decreasing thickness are a slower average crystallization of the film and a decrease in the Avrami exponent caused by a slower crystallization of the polymer close to the surfaces.A slight modification of the model allows us to calculate the isothermal crystallization kinetics at any point of the film when it contains two identical transcrystalline regions on its surfaces.All the models are well verified by computer simulations.     

Influence of transcrystallinity on DSC analysis of polymers

Intense parasitic nucleation has been observed at the surface of differential scanning calorimetry samples for various polymers, whereas their crystallization traces exhibit complex shapes. Revisited overall kinetics theories and computer simulation, taking into account small thickness of samples and transcrystallinity effects, allow to explain and reproduce experimental ‘double peaks’, currently observed with polyamide 6-6. The beginning of the transformation and the main peak are attributed to surface and bulk nucleations, respectively. As a consequence, any DSC experiment should be followed by a microscopic observation and more accurate models including thermal gradients and resistances should be developed for their interpretation.     

Versatile functional poly(3‐hexylthiophene) for hybrid particles synthesis by the grafting onto technique: Core@shell ZnO nanorods

We demonstrate an efficient strategy to anchor poly(3‐hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces. Synthesis of a novel triethoxysilane‐terminated regioregular P3HT is herein reported and supported by thorough characterization. Three triethoxysilane‐terminated P3HTs of different molar masses were prepared via a hydrosilylation reaction from allyl‐terminated P3HT. MALDI‐TOF and ¹H NMR were performed to characterize the polymer and show that around 80% of the chains are end‐functionalized. These polymers were then grafted onto the ZnO nanorods to create a macromolecular self‐assembled monolayer. This versatile technique could be subsequently applied to different metal oxide surfaces, such as silicon, titanium, or indium‐tin oxide, and represents a new one‐pot strategy based on triethoxysilane coupling reaction. Importantly, the influence of the molar mass on the grafting density and the polymer shell thickness was studied via thermo gravimetric analysis and transmission electron microscopy. The optical properties of the hybrid materials were determined by UV–visible absorption and photoluminescence to show a quenching effect of P3HT fluorescence by ZnO when grafted. This electronic transfer associated with an improved miscibility of the ZnO@P3HT, makes these hybrid materials suitable candidates for photovoltaic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 30–38     

The well-defined bootstrap effect in the macroinitiator-mediated pseudoliving radical copolymerization of styrene and acrylic acid

The bootstrap effect is observed in the pseudoliving radical copolymerization of styrene and acrylic acid mediated by a macroinitiator: the adduct of poly(acrylic acid) with a nitroxide radical. In this case, the macroinitiator serves as a peculiar “microreactor” with an increased local concentration of acrylic acid; as a result, the apparent activity of acrylic acid is higher than that in copolymerization mediated by low-molecular-mass initiators.     

Biomimetic Mussel Adhesive Inspired Anchor to Design ZnO@Poly(3‐Hexylthiophene) Hybrid Core@Corona Nanoparticles

The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.

     

Development of a compact alpha and beta camera for dismantlement applications

Journal of Radioanalytical and Nuclear Chemistry - A new method has been developed to image surface contamination on-site by short range radiation emitters (such as alpha or beta particle...     

New efficient method for activation of dormant chains in pseudoliving radical polymerization

With the use of the competitive inhibition method and ESR spectroscopy, it is shown that, in pseudoliving radical polymerization, the rate constant of decomposition of PS and poly(acrylic acid) adducts with nitroxide radicals significantly increases as the polarity of a medium increases. This phenomenon opens a new approach to the activation of chains in nitroxide-mediated polymerization.     

Instabilités de l'écoulement produisant le bruit de fenteFlow instabilities producing the slot-tone

The nature of the instability governing the self-sustained tones produced by a low Mach number plane jet impinging on a slotted plate, known as slot-tone, is identified experimentally. For a given Reynolds number, the natural shear-layer and the jet column mode frequencies of the free jet delimit the values of the measured slot-tone operating frequencies. The oscillations at lower frequencies are the result of the amplification of the jet column mode, and those at higher frequencies correspond to the shear layer instabilities. To cite this article: A. Billon et al., C. R. Mecanique 332 (2004).