Single step production of nanoporous electrospun poly(ε-caprolactone) fibres

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

Porous electrospun polycaprolactone fibres: Effect of process parameters

The effect of electrospinning process parameters (solution flow rate, applied voltage, spinning distance) on the size and surface morphology of porous electrospun poly(ε-caprolactone) was investigated in this study. Response surface methodology was implemented for the design and conduction of electrospinning experiments. The feed solution was a 12.5% w/v poly(ε-caprolactone) (PCL) solution in a binary solvent mixture of 90%v/v chloroform/ dimethyl sulfoxide. Spinning distance of 10-25 cm, applied voltage of 10-25 kV and feed flow rate of 0.5-5 ml/h were the range of limiting values of the independent variables used for the development of a central composite design. Second order polynomial equations, correlating electrospinning process parameters to relative pore coverage and fibre average diameter were developed and validated. An increase in any of the electrospinning process parameters favoured pore formation and fibre diameter increase. Under the experimental conditions investigated, the relative pore surface coverage was 15.8-31.9% and the average fibre diameter was in the range of 1.6-3.3 μm. Applied voltage was proven to be the parameter with the strongest impact on both, fibre diameter and surface morphology

Assessing the increase in specific surface area for electrospun fibrous network due to pore induction

The effect of pore induction on increasing electrospun fibrous network specific surface area was investigated in this study. Theoretical models based on the available surface area of the fibrous network and exclusion of the surface area lost due to fibre-to-fibre contacts, were developed. The models for calculation of the excluded area are based on Hertzian, Derjaguin-Muller-Toporov (DMT) and Johnson-Kendall-Roberts (JKR) contact models. Overall, the theoretical models correlated the network specific surface area to the material properties including density, surface tension, Young’s modulus, Poisson’s ratio as well as network physical properties such as density and geometrical characteristics including fibre radius, fibre aspect ratio and network thickness. Pore induction proved to increase the network specific surface area up to 52%, compared to the maximum surface area that could be achieved by non-porous fibre network with the same physical properties and geometrical characteristics. The model based on Johnson-Kendall-Roberts contact model describes accurately the fibre-to-fibre contact area under the experimental conditions used for pore generation. The experimental results and the theoretical model based on Johnson-Kendall-Roberts contact model show that the increase in network surface area due to pore induction can reach to up to 58%

Porous electrospun PCL fibres in a single step by phase separation

Porous polycaprolactone (PCL) nanofibers were produced by phase separation during electrospinning in a single step process using binary solvent systems with a broad range of properties which consisted of a mixture of a good solvent for PCL such as chloroform (CF), dichloromethane (DCM), tetrahydrofuran (THF) and formic acid (FA), and a poor solvent such as dimethyl sulfoxide (DMSO). Phase separation was induced when the good solvent evaporated leaving a solution of PCL rich in poor solvent resulting in saturation of the solution and phase separation. The effect of the solution properties and of the ratio of good/poor solvent to the morphology of the fibres and pore formation mechanism were studied. The production of porous, bead free fibres was achieved in CF/DMSO solution with good/poor solvent ratios varying from 75-90% v/v. The ternary mixture compositions that lead to the formation of porous fibres were mapped on a ternary graph. The pore formation was favoured at high good/poor solvent ratios, whereas, the production of fibres with ribbon cross sections or fibres with beads was more pronounced at low good/poor solvent ratios. The effect of the process parameters (flow rate, voltage, distance) on the pore covered area were also studied and voltage was found to exert the strongest effect on fibre morphology while increasing the process parameters led to increased pore coverage