Electrospinning of fibrous tissue engineering scaffolds has been traditionally conducted using positive voltages. In the current study, positive voltage (PV) electrospinning and negative voltage (NV) electrospinning were investigated for forming fibrous membranes of poly(hydroxybutyrate-co- hydroxyvalerate) (PHBV). In both PV-electrospinning and NV-electrospinning, the fiber diameter generally increased with increasing needle inner diameter and PHBV concentration but decreased with increasing working distance. The use of a conductivity-enhancing surfactant, benzyl triethylammonium chloride (BTEAC), significantly reduced PHBV fiber diameters from the micron scale to the sub-micron scale. Interestingly, with increasing applied voltage, the fiber diameter increased for PV-electrospinning but decreased for NV-electrospinning. The PV-electrospun fibrous membranes from solutions without BTEAC (PVEfm) and with BTEAC (PVEfm-B) and NV-electrospun membranes from solutions without BTEAC (NVEfm) and with BTEAC (NVEfm-B) were characterized in terms of their structure, wettability, thermal properties and tensile properties. Both PVEfm and NVEfm exhibited similar water contact angles (～104°) but the contact angle of PVEfm-B or NVEfm-B was not measurable. The elongation at break of PVEfm-B or NVEfm-B was significantly higher than that of PVEfm or NVEfm. Using NV-electrospinning or a combination of NV- and PV-electrospinning may be very useful for developing suitable scaffolds for tissue engineering applications.
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