The experimental phase diagram study of the binary polyols system erythritol-xylitol

•Erythritol-xylitol is a partially isomorphous system with a eutectic.•Previously erythritol-xylitol was proposed as a non-isomorphous system.•The eutectic is at 25-30 mol% Erythritol and 77 °C in contrast to earlier results.•Previous studies proposed the eutectic at 25, 36 mol% Erythritol and 82 °C.•System's T-history, Tammann plot, HTXRD and FESEM presented for the 1st time.

A comprehensive phase diagram for the binary polyols system erythritol-xylitol has been mapped with a transparent characterization approach. Here, the phase equilibrium of the system has been studied experimentally using a combination of methods: Temperature-history (T-history), X-Ray Diffraction (XRD), and Field-Emission Scanning Electron Microscopy (FESEM), and linked to Tammann plots. Existing literature has previously shown the system to be a non-isomorphous type forming a simple eutectic, by combining experimental data with theoretical modelling. The present investigation shows that the system's phase diagram is a partially isomorphous type forming a eutectic, but not a non-isomorphous type forming a simple eutectic. Here, the eutectic was found within 25-30 mol% erythritol and at 77 °C, which differs from the previous studies identifying the eutectic respectively at 25 or 36 mol% erythritol and at 82 °C. The reasons for the differences are hard to deduce since the research approach is not presented as fully transparent from the past studies. In the present study, only the temperature-composition plot of the first melting (of the two components in a physical mix, but not of a single blend) indicated the shape of a simple eutectic in a non-isomorphous system. The cycles after the first melting in contrast started from the real blend, and displayed eutectic and solid-solid phase changes in T-history. These were verified as forming solid solutions with XRD and FESEM. This eutectic melts at a temperature suitable for low-temperature solar heating, but displayed glass transition, supercooling, and thermally activated degradation, thus affecting its practical aspects as a PCM.