To confirm the findings from fibre diameter studies DSC was used to explore the thermal properties of nanofibers fabricated under different atmospheric conditions. DSC was used to measure the energy required (mW/mg) to heat each nanofiber sample over a temperature range from 25°C to 260°C for 9 samples corresponding to each of the controlled parameter conditions. Melt enthalpy values were determined by taking the integral of the melting temperature curve from the thermograms. As the fibre diameter decreased so did the melt enthalpy which was expressed by a broad low endothermic peak. The atmospheric conditions that yielded the largest fibres (17.5°C, 70%RH: 385nm) yielded the largest melt enthalpy of 12.07J/g, this is in comparison to the 4.47J/g yielded by the finest fibres (32.5°C, 20%RH: 276nm). These observations suggest decreased crystallinity and a less ordered molecular structure with decreasing fibre diameter. Lee et al, (2004) demonstrated a similar effect by using DSC to show higher molecular weight PVA shifted the Tm from 224.7°C to 232.7°C due to the effectively increased crystalline structure [35].