Ainara Saralegi

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.

In situ polymerization and characterization of elastomeric polyurethane-cellulose nanocrystal nanocomposites. Cell response evaluation

Polyurethane/Cellulose nanocrystal (CNC) nanocomposites have been prepared by means of in situ polymerization using CNCs as precursors of polyurethane chains. Thermal, mechanical and morphological characterization has been analyzed to study the effect of CNC on the micro/nanostructure, which consisted of individualized nanocellulose crystallites covalently bonded to hard and soft segments of polyurethane. The incorporation of low CNC content led to a tough material whereas higher amount of CNC provoked an increase in soft and hard segments crystallization phenomenon. Moreover, from the viewpoint of polyurethane and polyurethane nanocomposites applications focused on biomedical devices, biocompatibility studies can be considered necessary to evaluate the influence of CNC on the biological behaviour. SEM micrographs obtained from cells seeded on top of the materials showed that L-929 fibroblasts massively colonized the materials surface giving rise to good substrates for cell adhesion and proliferation and useful as potential materials for biomedical applications.

Thermoplastic shape-memory polyurethanes based on natural oils

A new family of segmented thermoplastic polyurethanes with thermally activated shape-memory properties was synthesized and characterized. Polyols derived from castor oil with different molecular weights but similar chemical structures and a corn-sugar-based chain extender (propanediol) were used as starting materials in order to maximize the content of carbon from renewable resources in the new materials. The composition was systematically varied to establish a structure–property map and identify compositions with desirable shape-memory properties. The thermal characterization of the new polyurethanes revealed a microphase separated structure, where both the soft (by convention the high molecular weight diol) and the hard phases were highly crystalline. Cyclic thermo-mechanical tensile tests showed that these polymers are excellent candidates for use as thermally activated shape-memory polymers, in which the crystalline soft segments promote high shape fixity values (close to 100%) and the hard segment crystallites ensure high shape recovery values (80–100%, depending on the hard segment content). The high proportion of components from renewable resources used in the polyurethane formulation leads to the synthesis of bio-based polyurethanes with shape-memory properties.

Synthesis of waterborne polyurethane-urea dispersions with chain extension step in homogeneous and heterogeneous media

HYPOTHESIS The possibility of tailoring the final properties of environmentally friendly waterborne polyurethane and polyurethane-urea dispersions and the films they produce makes them attractive for a wide range of applications. Both the reagents content and the synthesis route contribute to the observed final properties. EXPERIMENTS A series of polyurethane-urea and polyurethane aqueous dispersions were synthesized using 1,2-ethanediamine and/or 1,4-butanediol as chain extenders. The diamine content was varied from 0 to 4.5wt%. Its addition was carried out either by the classical heterogeneous reaction medium (after phase inversion step), or else by the alternative homogeneous medium (prior to dispersion formation). Dispersions as well as films prepared from dispersions have been later extensively characterized. FINDINGS 1,2-Ethanediamine addition in heterogeneous medium leads to dispersions with high particle sizes and broad distributions whereas in homogeneous medium, lower particle sizes and narrow distributions were observed, thus leading to higher uniformity and cohesiveness among particles during film formation. Thereby, stress transfer is favored adding the diamine in a homogeneous medium; and thus the obtained films presented quite higher stress and modulus values. Furthermore, the higher uniformity of films tends to hinder water molecules transport through the film, resulting, in general, in a lower water absorption capacity.