Low-Stress UV-Curable Hyperbranched Polymer Nanocomposites for High-Precision Devices

The aim of this thesis was to investigate the process-structure-property relationships of UV-curable hyperbranched polymer (HBP)/silica nanocomposites. Special attention was paid to the interplay between photo-conversion, rheological behavior, shrinkage, and stress dynamics. This knowledge was used to maximize the shape fidelity and dimensional stability of imprinted nano-patterns made with these nanocomposites. Two different processing routes, resulting in different nanocomposite morphologies, were compared. The first and more conventional approach was ultrasonic, solvent-assisted mixing with solid silica nanoparticles followed by UV curing, which led to a discrete dispersion of silica particles in the matrix. The second and more novel approach was a dual-cure process combining UV and sol-gel processing with liquid tetraethyl orthosilicate. The sol-gel process, using a low-viscosity organometallic precursor, overcame the potential processing issue of the highly viscous particulate nanocomposites and led to a hybrid material with a homogeneous silica network at nanometer scale. Rheological analysis of silica nanoparticle suspensions up to the concentrated regime in the HBP showed an exponential increase of the viscosity with the particle fraction for well-dispersed discrete particle systems. A liquid-to-solid transition occurred in the 5 to 10 vol% range, which was correlated with an immobilized layer of polymer hydrogen-bonded to the silanol groups on the surface of the particles, as was confirmed by calorimetric analysis. Polymerization kinetics of HBP nanocomposites and hybrids were analyzed by means of photo differential scanning calorimetry using an autocatalytic model. A time-intensity-superposition principle with power-law dependence was established, which invalidated the classic radiation dose equivalence principle. Gelation and modulus build-up were monitored using photo-rheology. The calorimetric and rheological data were combined in the form of time-intensity-transformation diagrams. It was found that gelation was delayed with respect to conversion up to 36% when lower UV intensities were used, which favored reduce polymerization stresses. The dynamics of polymerization shrinkage and internal stress build-up were investigated using photo-hyphenated interferometry and beam-bending methods. The linear shrinkage of the HBP was as low as 4.5%, which was further reduced to 3.3% with the addition of 20 vol% nanoparticles. The residual stress of HBP/SiO2 nanocomposites was below 5.5 MPa. That is well below the level of standard non-reinforced resins, in spite of an increased stiffness. For the sol-gel hybrids with 20 vol% SiO2, stress reduction by 50% with simultaneous stiffness increase by 20% with respect to corresponding particulate composites was demonstrated. The coefficient of thermal expansion was also lowered by 30%. Finally, nanogratings with a period of 360 nm and a step height of 12 nm were fabricated using UV-nanoimprint lithography with a glass or nickel master in a low-pressure (max. 6 bar) and rapid (≈1 min) process. Stable gratings were imprinted in the composite material containing up to 25 vol% of silica nanoparticles, despite the high viscosity of such compositions. Thanks to the exudation of a HBP-rich surface layer, the shape fidelity in terms of period of the replicated patterns was within 98% of the master, with shape distortion increasing with internal stress. The obtained nanogratings were used as a substrate for grated high refractive index TiO2 waveguides and then applied as wavelength-interrogated optical sensors (WIOS). An immunoassay with the polymer WIOS showed the same ultrahigh detection sensitivity as the standard glass-based devices. Therefore, the novel polymer-based sensor should be useful to probe contaminants in liquids with concentrations as low as a few ppb

Conversion and shrinkage analysis of acrylated hyperbranched polymer nanocomposites

The photo-curing behavior of composites containing nanosized SiO2 in an acrylated hyperbranched polymer matrix was investigated by means of photo differential scanning calorimetry. The chemical conversion data were analyzed using an autocatalytic model, paying close attention to the influence of composition and UV intensity. It was shown that the reaction order and the autocatalytic exponent were independent of UV intensity and filler fraction, whereas the rate constant showed strong intensity dependence, but weak filler dependence. Maximum conversion was independent of UV intensity, but was reduced when a filler was present. The dispersion state influenced the gel-point of the composites, but had no influence on the overall cure kinetics. Cure shrinkage reduction of ~33% could be achieved by adding 20 vol% of filler. This was attributed to the reduced double bond conversion of the matrix due to the presence of the filler. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 1954–1963, 200

Time-intensity superposition for photoinitiated polymerization of fluorinated and hyperbranched acrylate nanocomposites

The validity of the time-intensity superposition principle for the photoinitiated polymerization of nanocomposites based on a monofunctional fluorinated acrylate and on a multifunctional hyperbranched polyether acrylate was investigated in this work. Master curves were obtained for the conversion as a function of time, measured by photo differential scanning calorimetry, by shifting on the time axis the curves obtained at different intensities. A power-law dependence of the shift factor on the intensity was found for all materials, with exponents equal to 0.45 +/- 0.03 for the fluorinated acrylates and to 0.71 +/- 0.05 for the hyperbranched polyether acrylates. Consequently it is inferred that the radiant exposure reciprocity law, implying linear dependence of the shift factor on intensity, does not apply to the studied compositions. The kinetics of the photopolymerization of materials based on the fluorinated acrylate was analyzed with the autocatalytic model. The final conversion was independent on intensity and filler content. The rate constants showed for all materials a power-law dependency on intensity, with exponents similar to those of the corresponding shift factors

En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays

The catalytic chemical vapour deposition (c-CVD) technique was applied in the synthesis of vertically aligned arrays of nitrogen-doped carbon nanotubes (N-CNTs). A mixture of toluene (main carbon source), pyrazine (1,4-diazine, nitrogen source) and ferrocene (catalyst precursor) was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C), composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs). As revealed by electron microscopy studies (SEM, TEM), the individual N-CNTs (half as thick as MWCNTs) grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 108 nanotubes per mm2 (100 times more than for MWCNTs grown in the absence of nitrogen precursor). In turn, the internal crystallographic order of the N-CNTs was found to be of a ‘bamboo’-like or ‘membrane’-like (multi-compartmental structure) morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp2-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a ‘mixed base-and-tip’ (primarily of the base-type) type as compared to the purely ‘base’-type for undoped MWCNTs

Accueil des jeunes diabétiques à l’école- Stratégies et recommandations de la SSEDP

L’incidence du diabète de type 1 a augmenté en Europe pendant les deux dernières décennies; en Suisse elle est passée de 8 sur 100000 enfants (≤ 15 ans) en 1991 à 13.1 en 2008, ainsi le diabète touche de plus en plus d’enfants en âge scolaire1). Cet article, préparé par des membres de la Société suisse d’endocrinologie et diabétologie pédiatriques (SSEDP/SGPED), des médecins scolaires ainsi que des infirmières spécialistes cliniques en diabétologie a pour but d’aider à l’intégration complète des enfants diabétiques dans les crèches, jardins d’enfants et écoles, aux activités scolaires, parascolaires et sportives en garantissant le suivi de leur traitement et leur sécurité. Ce document présente un support pour les familles et équipes médico-soignantes qui rencontrent des difficultés dans la prise en charg