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Fibres with a diameter in the nanometer range were electrospun from aqueous poly(vinyl alcohol) (PVOH). In order to improve the mass deposition rate and decrease the final fibre diameter salts (NaCl, LiCl, LiBr and LiF) were added to the solution. The aim was to increase the charge density and hence increase the electrostatic forces on the fluid. It was found that with increasing salt concentration the charge density did increase. However the mass deposition rate was found to decrease and the final fibre diameter was found to increase. The decrease in mass deposition rate is explained by considering the concept of a virtual orifice. The increase in the final fibre diameter is explained by considering the charge distribution in the jet when it behaves like a conductor compared to when it behaves like an insulator. Both mechanisms result from the increase in conductivity of the PVOH solution without significantly modifying other solution properties when salt is added. [ABSTRACT FROM AUTHOR]