Nanoporous polymer fibres are currently attracting increasing interest due to their unique characteristics. Increased specific surface area, improved mechanical properties and improved cellular growth are amongst the advantages that set porous fibres as ideal candidates in applications like catalysis, separation and tissue engineering. This work explores the single step production of porous poly(ε-caprolactone) (PCL) fibres through combinative electrospinning and Non-solvent Induced Phase Separation (NIPS) technique. Theoretical models, based on three different contact models (Hertzian, DMT, JKR), correlating the fibrous network specific surface area to material properties (density, surface tension, Young s modulus, Poisson s ratio) and network physical properties (density) and geometrical characteristics (fibre radius, fibre aspect ratio, network thickness) were developed in order to calculate the surface area increase caused by pore induction. Experimental results proved that a specific surface area increase of up to 56% could be achieved, compared to networks composed of smooth surfaced fibres. The good solvent effect on electrospun fibre surface morphology and size was examined through experimental investigation of four different good solvent (chloroform, dichloromethane, tetrahydrofuran and formic acid) based solutions at various good/poor solvent ratios. Chloroform was proven to be the most suitable solvent for good /poor solvent ratios varying from 75-90% v/v, whereas alternative mechanisms leading to different fibre morphologies were identified, interpreted and discussed. Evaporation rate of the good solvent was identified as the key parameter of the process. Second order polynomial equations, derived from the experimental data, correlating the feed solution physical parameters (viscosity, conductivity, surface tension) to the fibre average diameter produced were developed and validated. Response surface methodology was implemented for the design and conduction of electrospinning experiments on a 12.5 % w/v Chloroform/DMSO solution 90/10 % v/v in order to determine the individual process parameters (spinning distance, applied voltage, solution flow rate) effect in fibre surface morphology and size. The increase in any of these parameters results in increase of both the fibre size and the tendency for pore generation, whereas applied voltage was the parameter with the strongest effect. Findings from this thesis expand the knowledge about both phenomena occurring during the production process and end product properties, and can be used for the production of controlled morphology and size porous poly(ε-caprolactone) (PCL) fibres.

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