CaF2 has been a common constituent in a wide variety of welding fluxes, including those used for submerged arc welding (SAW). The widespread use of CaF2 stems from its role in lowering the liquidus temperature as well as the viscosity of the molten slag that covers the weld pool. However, the harmful effect of fluoride evaporation from molten flux, on the environment as well as the health of the users is becoming increasingly evident over the years. This has led to increasing attention towards reducing the CaF2 concentration in the fluxes. The fluoride-free formulations face the challenging requirement to maintain the thermo-physical properties (viscosity, liquidus temperature etc) like those observed in fluoride-containing fluxes. In the present work, three fluxes with compositions in the CaO-MnO-SiO2-Al2O3 system have been identified as promising alternatives to the CaF2-rich fluxes. However, the thermo-physical properties of any such flux need to be comparable to CaF2-based commercial SAW fluxes before it can be adopted for regular use. The single hot thermocouple technique (SHTT) has been used by several researchers in the past as a tool for observing the melting and solidification characteristics of fluxes. This device has been developed in the present work and is used to characterise the melting behaviour of the fluxes. The measured solidus and liquidus temperatures from SHTT were compared with the results from differential thermal analysis (DTA) and simulations using the FactSage™ software for a comprehensive understanding. In spite of having a slight deviation in the measured values from the multiple techniques, the results obtained from these multiple methods show that the selected compositions could be potential CaF2 free alternative welding fluxes.