A. C. Trindade

Cellulose-based composite films

The mechanical and optical properties of cellulose-based composite films are investigated.It is shown that the use of toluene diisocyanate as a coupling agent and Avicel fibers as reinforcing elements give films with the highest mechanical characteristics. Using differential scanning calorimetry, it is also found that the glass transition temperature Tg of all the materials studied is below the room temperature and that the Tg increased with cross-linking and introduction of Avicel.

Hierarchical wrinkling on elastomeric Janus spheres

Hierarchical wrinkling on elastomeric Janus spheres is permanently imprinted by swelling, for different lengths of time, followed by drying the particles in an appropriate solvent. First-order buckling with a spatial periodicity (λ11) of the order of a few microns and hierarchical structures comprising of 2nd order buckling with a spatial periodicity (λ12) of the order of hundreds of nanometers have been obtained. The 2nd order buckling features result from a Grinfeld surface instability due to the diffusion of the solvent and the presence of sol molecules.

Staphylococcus epidermidis adhesion on modified urea/urethane elastomers

Block urea/urethane co-polymer films present elastomeric properties with the possible tuning of their surface properties within a wide range and are therefore considered relevant surfaces for possible medical applications. In particular, thin free standing films of urea/urethane elastomers with two soft segments, polypropylene oxide and more hydrophobic polybutadiene, develop multi-stable states with surface topography features with remarkable regularity. Moreover, complex surface structures may be obtained by UV radiation treatment followed by suitable mechanical action and also by extraction of the elastomer with a suitable solvent. In the present work, different modified elastomer samples were assayed for Staphylococcus epidermidis adhesion during 2 h and the extent of bacterial adhesion was evaluated by automatic cell enumeration. Bacterial adhesion assays demonstrate that the typical trend relating the increase in the number of adhered bacteria with the increase of the surface roughness does not hold for all materials. Results may be interpreted taking into account both the surface topography and the different types of micro-phase segregation of hydrophobic and hydrophilic parts of the elastomer.

Perversions with a twist.

Perversions connecting two helices with symmetric handedness are a common occurrence in nature, for example in tendrils. These defects can be found in our day life decorating ribbon gifts or when plants use tendrils to attach to a support. Perversions arise when clamped elastic filaments coil into a helical shape but have to conserve zero overall twist. We investigate whether other types of perversions exist and if they display different properties. Here we show mathematically and experimentally that a continuous range of different perversions can exist and present different geometries. Experimentally, different perversions were generated using micro electrospun fibres. Our experimental results also confirm that these perversions behave differently upon release and adopt different final configurations. These results also demonstrate that it is possible to control on demand the formation and shape of microfilaments, in particular, of electrospun fibres by using ultraviolet light.

3D Soft Microlithography in Segmented Anisotropic Urethane/Urea Elastomers

ABSTRACT In this work we describe a way to readily transfer 2D pictures from a mask to 3D structures on flexible free standing urethane/urea substrates. The resultant 3D picture can easily be erased/rewritten or permanently imprinted in the elastomer. The 3D microstructures are induced by UV radiation and can be revealed by application of a mechanical field or by immersing and drying the elastomer in an appropriate solvent. The film casting conditions induces an orientational order of the segregated soft and hard parts of the copolymer that is enhanced by UV radiation which is thought to make up the anisotropic structure that is responsible for the features observed. The copolymer is prepared by extending a poly(propylene oxide)-based triisocyanate terminated prepolymer (PU) with poly(butadienediol) (PBDO; 40% wt). Polarising Optical Microscopy (POM), Small Angle Light Scattering (SALS) and Atomic Force Microscopy (AFM) were used to evidence the different nano and micromodulated structures that develop in urethane/urea elastomer. The measurements were performed before and after applying a mechanical field and after immersion and drying the sample on toluene.

Luminescent elastomeric Janus particles.

We report on a low-cost and low-tech method for the preparation of luminescent micro- and millimeter elastomeric particles with asymmetric morphology. The method of fabrication consists in UV-irradiating soft urethane/urea fluorescent spheres, which are then extracted in toluene and dried. Wrinkles appear on the irradiated portions of the particles surfaces, and the spatial periodicity can be controlled with variation in UV irradiation time and the amount of the luminescent compound. The spheres are thus composed of an urethane/urea network in which the tris(8-hydroxyquinolinato)aluminum (Alq3) fluorescent compound was incorporated. The asymmetric morphology and the optical properties of the resultant particles have been confirmed by scanning electron microscopy, atomic force microscopy, optical microscopy, and UV-Vis spectrophotometry. The system shows negligible leaching, and the encapsulation of the Alq3 without recourse to covalent bonding to the polymeric matrix has the advantage of allowing the tuning of the spheres morphology and fluorescence.