Arantxa Eceiza

Enhancing water repellence and mechanical properties of gelatin films by tannin addition

In order to reduce pollution caused by traditional non-biodegradable plastic films, renewable raw materials from plants and wastes of meat industries have been employed in this work. A hydrolysable chestnut-tree tannin was used for gelatin modification. Films of gelatin and gelatin-tannin were obtained by casting at room conditions. Transition temperatures of both gelatin and gelatin-tannin systems were determined by differential scanning calorimetry (DSC). Glass transition temperatures of modified gelatin occurred at higher temperatures than for neat gelatin. Enthalpy and temperature of helix-coil transition decreased when tannin content increased due to variations in the helical structure of gelatin as a consequence of tannin presence in agreement with X-ray analysis. Mechanical and thermal behaviour varied as a function of the content of tannin, showing optimum values for films modified with 10 wt% tannin. The transparency of films was maintained after modification with tannin. Solubility and swelling tests of the films revealed that the presence of tannin reduced the water affinity of gelatin.

Phase separation in polysulfone-modified epoxy mixtures. Relationships between curing conditions, morphology and ultimate behavior

Chemorheology of curing as well as the phase separation behavior of polysulfone (PSU)-modified diaminodiphenylmethane-cured diglycidylether of bisphenol-A epoxy mixtures have been studied using several techniques. The delay in polymerization for the modified mixtures with respect to that of the neat epoxy can be explained by dilution and viscosity effects. The immiscibility of these mixtures has been proved for various PSU contents and as a function of the precuring conditions used as well. The control of the generated morphologies can be performed only by varying the processing temperature. The thermal and dynamic viscoelastic behavior of the modified matrices has been examined and compared to the parent epoxy matrix. Finally, the mechanical properties, including fracture toughness, have been discussed in terms of the morphological behavior for an epoxy matrix modified with various amounts of PSU and for a 15 wt.% PSU-containing matrix precured at different temperatures.

The effect of stoichiometry and thermal history during cure on structure and properties of epoxy networks

Abstract An investigation was carried out into the effect of amine/epoxy stoichiometry and thermal history during cure on physical and mechanical properties of epoxy networks. The formulation studied consisted of a diglycidyl ether of bisphenol A epoxy resin and 4,4′-diaminodiphenyl sulfone curing agent. The experimental matrix was based upon three amine/epoxy ratios and seven different thermal histories during cure. Techniques used included dynamic mechanical and fracture analysis, and Fourier transform infra-red (FTi.r.) spectroscopy. The highest glass transition temperature (Tg) was observed in the stoichiometric formulation and the lowest in the epoxy-rich mixture. For a given stoichiometry, the value of Tg, infinity was not a function of thermal history during cure except, interestingly, in the case when the initial temperature was 180°C. The highest rubbery state modulus and the lowest average molecular weight between crosslinks were also found in the stoichiometric formulation. Our findings were rationalized in terms of the varying degrees of crosslinking in different networks. The opposite trend was observed in the glassy state at 20°C, where the lowest flexular modulus belonged to the stoichiometric formulation. An explanation for those results was offered in terms of the free volume concept. FTi.r. analysis established clearly the existence of residual epoxy groups in all formulations, even after post-cure. Etherification reaction between epoxy and hydroxyl groups takes place during post-cure, but a complete conversion of epoxy groups cannot be attained owing to the topological constraints within the three-dimensional network in the later stages of cure. This finding is of particular significance in mechanistic kinetic models based upon the absolute value of epoxy concentration at all stages of cure.

Bioinspired antimicrobial and biocompatible bacterial cellulose membranes obtained by surface functionalization with aminoalkyl groups.

There has been a great deal of interest in the use of nanostructured bacterial cellulose membranes for biomedical applications, including tissue implants, wound healing, and drug delivery. However, as bacterial cellulose does not intrinsically present antimicrobial properties, in the present study, antimicrobial bacterial cellulose membranes were obtained by chemical grafting of aminoalkyl groups onto the surface of its nanofibrillar network. This approach intends to mimic intrinsic antimicrobial properties of chitosan. Interestingly, these novel grafted bacterial cellulose membranes (BC-NH2) are simultaneously lethal against S. aureus and E. coli and nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus may be useful for biomedical applications. In addition to these biological properties, the bioactive nanostructured BC-NH2 membranes also present improved mechanical and thermal properties.

Cellulose nanocrystals/polyurethane nanocomposites. Study from the viewpoint of microphase separated structure

Cellulose nanocrystals (CNC) successfully obtained from microcrystalline cellulose (MCC) were dispersed in a thermoplastic polyurethane as matrix. Nanocomposites containing 1.5, 5, 10 and 30 wt% CNC were prepared by solvent casting procedure and properties of the resulting films were evaluated from the viewpoint of polyurethane microphase separated structure, soft and hard domains. CNC were effectively dispersed in the segmented thermoplastic elastomeric polyurethane (STPUE) matrix due to the favorable matrix-nanocrystals interactions through hydrogen bonding. Cellulose nanocrystals interacted with both soft and hard segments, enhancing stiffness and stability versus temperature of the nanocomposites. Thermal and mechanical properties of STPUE/CNC nanocomposites have been associated to the generated morphologies investigated by AFM images.

Starch and cellulose nanocrystals together into thermoplastic starch bionanocomposites.

In the present work, thermoplastic maize starch based bionanocomposites were prepared as transparent films, plasticized with 35% of glycerol and reinforced with both waxy starch (WSNC) and cellulose nanocrystals (CNC), previously extracted by acidic hydrolysis. The influence of the nanofiller content was evaluated at 1 wt.%, 2.5 wt.% and 5 wt.% of WSNC. The effect of adding the two different nanoparticles at 1 wt.% was also investigated. As determined by tensile measurements, mechanical properties were improved at any composition of WSNC. Water vapour permeance values maintained constant, whereas barrier properties to oxygen reduced in a 70%, indicating the effectiveness of hydrogen bonding at the interphase. The use of CNC or CNC and WSNC upgraded mechanical results, but no significant differences in barrier properties were obtained. A homogeneous distribution of the nanofillers was demonstrated by atomic force microscopy, and a shift of the two relaxation peaks to higher temperatures was detected by dynamic mechanical analysis.

Biocompatible hydrogel nanocomposite with covalently embedded silver nanoparticles.

Bionanocomposite materials, combining the properties of biopolymers and nanostructured materials, are attracting interest of the wider scientific community due to their potential application in design of implants, drug delivery systems, and tissue design platforms. Herein, we report on the use of maleimide-coated silver nanoparticles (Ag NPs) as cocross-linkers for the preparation of a bionanocomposite gelatin based hydrogel. Diels-Alder cycloaddition of benzotriazole maleimide (BTM) functionalized Ag NPs and furan containing gelatin in combination with additional amide coupling resulted in stable and biocompatible hybrid nanocomposite. The storage moduli values for the hydrogel are nearly three times higher than that of control hydrogel without NPs indicating a stabilizing role of the covalently bound NPs. Finally, the swelling and drug release properties of the materials as well as the biocompatibility and toxicity tests indicate the biomedical potential of this type of material.

Shape-Memory Bionanocomposites Based on Chitin Nanocrystals and Thermoplastic Polyurethane with a Highly Crystalline Soft Segment

Shape-memory bionanocomposites based on a naturally sourced segmented thermoplastic polyurethane and chitin nanocrystals were synthesized, and their mechanical properties and thermally activated shape-memory behavior were studied. The chitin nanocrystals were incorporated during the synthesis of the prepolymer made from a castor oil-based difunctional polyol and hexamethylene diisocyanate. The polymerization was completed by addition of propanediol, as a corn-sugar based chain extender, bringing the weight content of components from renewable resources to >60%. Thermal analysis of the bionanocomposites revealed a phase-separated morphology, which is composed of soft and hard domains, which bestow the material with two melting transitions at 60 and 125 °C, that are exploitable for a shape memory effect. The soft segment is responsible for temporary shape fixing, while the hard segment crystallites are responsible for the permanent shape. The introduction of small amounts (0.25-2 wt %) of chitin nanocrystals was found to increase the crystallinity of the hard segment by way of nucleation, which in turn improves the shape recovery considerably. The thermally activated shape-memory behavior of the synthesized bionancomposites is exploitable with a programming and release temperature of 60 °C. The materials display good in vitro cell response, as shown by short-term cytotoxicity assays, and therefore, the bionanocomposites appear to be potentially useful for biomedical applications.

Kinetic and rheological studies of an unsaturated polyester cured with different catalyst amounts

An unsaturated polyester resin was cured with different catalyst contents. The crosslinking process was followed by static and dynamic viscosimetry and by differential scanning calorimetry (d.s.c.). Activation energies were determined from the gel times obtained by viscosimetry and from the variation in the maximum exotherm temperature obtained by d.s.c. at different heating rates. The existence of a threshold in the amount of catalyst to use is shown by analysis of the gel times. The effect of catalyst content on the glass transition temperatures of the different mixtures has been analysed taking into account the crosslink density, measured by means of the rubber modulus obtained by dynamic mechanical tests.

Morphology and thermal behavior of dicyanate ester-polyetherimide semi-IPNS cured at different conditions

A high-temperature thermosetting bisphenol-A dicyanate, BADCy was modified with polyetherimide, PEI, at various compositions. Phase separation and rheokinetics through curing were studied by optical microscopy, dynamic and isothermal differential scanning calorimetry, and rheological measurements. The PEI phase separated at the early stages of curing, well before gelation, and did not affect the polycyclotrimerization kinetics. The phase structure and thermal properties of the final network were investigated as a function of the PEI content and cure temperature. For this purpose, dynamic mechanical analysis, scanning electron microscopy studies, and thermogravimetrical analysis were carried out. The morphological changes were interpreted in terms of a spinodal decomposition mechanism in the composition range studied.