We review previous works on polymer confined crystallization employing strategies that allow confinement to go from the micron to the nanometer scale: droplets, blends, block copolymers and infiltration into alumina nanopores. We also present novel results, reporting homogeneous nucleation and first order crystallization kinetics, for the first time, in a homopolymer and a diblock copolymer infiltrated within alumina nanopores. Confinement can produce fractionated crystallization or exclusive crystallization at much higher supercoolings as compared to bulk polymers, as the degree of confinement increases. For highly confined heterogeneity free micro or nano-domains, the overall crystallization kinetics is dominated by nucleation and therefore becomes first order. The nucleation mechanism changes from heterogeneous nucleation for the bulk polymer to surface or homogeneous nucleation for ensembles of confined and isolated heterogeneity free micro or nanodomains. Surface nucleation is more commonly found than homogenous nucleation, although this fact is not frequently recognized in the literature.Peer Reviewe

The development of bio-based materials has been a consequence of the environmental awareness generated over time. The versatility of native starch is a promising starting point for manufacturing environmentally friendly materials. This work aims to compile information on the advancements in research on thermoplastic starch (TPS) nanocomposites after the addition of mainly these four nanofillers: natural montmorillonite (MMT), organically modified montmorillonite (O-MMT), cellulose nanocrystals (CNC), and cellulose nanofibers (CNF). The analyzed properties of nanocomposites were mechanical, barrier, optical, and degradability. The most important results were that as the nanofiller increases, the TPS modulus and strength increase; however, the elongation decreases. Furthermore, the barrier properties indicate that that the incorporation of nanofillers confers superior hydrophobicity. However, the optical properties (transparency and luminosity) are mostly reduced, and the color variation is more evident with the addition of these fillers. The biodegradability rate increases with these nanocompounds, as demonstrated by the study of the method of burial in the soil. The results of this compilation show that the compatibility, proper dispersion, and distribution of nanofiller through the TPS matrix are critical factors in overcoming the limitations of starch when extending the applications of these biomaterials. TPS nanocomposites are materials with great potential for improvement. Exploring new sources of starch and natural nano-reinforcement could lead to a genuinely eco-friendly material that can replace traditional polymers in applications such as packaging.