Films and sponges were prepared from a solution of Poly(epsilon-caprolactone) (PCL) in tetrahydrofuran (THF). The porosity, crystallinity, and mechanical properties of the samples were studied. Porosity of around 15% was obtained for the films produced by evaporation of THF at room temperature. A much more porous structure (50-70%) was found for the sponges obtained by cooling the solution at -30 degrees C and subsequently eliminating the solvent by freeze drying. The porosity of the samples was also observed by scanning electron microscopy (SEM). The crystallinity of the samples was studied by the calorimetric technique (DSC) before and after the compression scans. The mechanical properties of the different samples were determined by compression test, and were compared to those corresponding to the PCL in bulk. The compression scans did not affect the crystallinity of the samples. The variations observed in the results of the different scans were attributed to the differences in porosities and crystallinity.

Poly(L-lactic acid)(PLLA)/poly(ε-caprolactone)(PCL)/hydroxyapatite(HAp) composites appear as promising materials for healing large bone defects. Highly porous PLLA/PCL scaffolds, 80/20, 20/80 weight ratios, porosity >85%, were prepared by a dual technique of freeze extraction and porogen leaching, with and without HAp. A double pore structure was obtained, with interconnected macroporosity together with interconnected microporosity. Elastic modulus and yield strength of as-synthesized scaffolds were higher for PLLA rich blends and including the inorganic phase does not lead to a mechanical strengthening in these materials. Subsequent long-term (78 weeks = 1.5 years) hydrolytic degradation behavior was investigated in terms of the samples´ mechanical properties, molecular weight (M w ), mass changes, thermal characteristics, X-ray Diffraction and Thermogravimetric Analysis. Elastic modulus and yield strength of as-synthesized scaffolds were higher for PLLA rich blends and including the inorganic phase does not lead to a mechanical strengthening in these materials. Nevertheless, after 30 weeks of degradation, PLLA rich scaffolds lost more than half of their strength and rigidity. On the contrary, the densification modulus of the PLLA based blends increased with degradation time, whereas PCL-based blends had a relatively constant densification modulus. PCL-based samples showed lower hydrolysis coefficients k than PLLA-based samples, as expected from the higher density of ester bonds in the latter. Interestingly, although including HAp leads to a lower hydrolysis coefficient k in PCL rich samples, it increases k in the PLLAbased sample, which is consistent with the other results obtained.

The effect of enzymatic degradation on poly(e-caprolactone) (PCL) films and sponges was investigated at 37 8C using Pseudomonas lipase. Film samples were prepared by the solution casting method, while sponges were obtained by the freeze extraction method. The porosity was 17 and 60% respectively. Weight loss, morphology, crystallinity and mechanical properties were studied. The kinetic study on the enzymatic degradation of PCL porous samples depends on porosity, suggesting that degradation took place on the surface, not suffering bulk degradation. The nondependence on crystallinity indicates that degradation occurred in both phases, amorphous and crystalline, at the same time.

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Synthetic porous hydrogels are becoming more and more important in the field of biomaterials. Different studies demonstrate that the porous structure promotes the colonisation of living cells and improves the biocompatibility of the implants. The macroporous structure allows not only the control of cellular ingrowth morphology but also the mechanical integration and the regulation of nutrient and hydraulic flow in the hydrogel. In this work poly(ethyl acrylate‐co‐hydroxyethyl methacrylate) (PEA/PHEMA) copolymers were polymerized using 2% of ethylene glycol dimethacrylate as cross‐linking agent and azoiso‐botyronitrile as initiator. Five samples were prepared with the EA/HEMA weight ratios of 75/25, 50/50, 25/75 and pure PEA and PHEMA polymers, obtaining different degrees of hydrophilicity. The macroporous structure was obtained by adding poly(acrylonitrile) fibres to the monomers. After polymerization the fibres were eliminated by dissolution in dimethyl formamide. The holes are cylinders of approximately 40μm diameter and are all, more or less, in the same direction, although they are not uniformly distributed. Water sorption isotherms and diffusion properties of the macroporous samples are compared with the samples without holes.