Unveiling the dependence of glass transitions on mixing thermodynamics in miscible systems

The dependence of the glass transition in mixtures on mixing thermodynamics is examined by focusing on enthalpy of mixing, ΔH_mix with the change in sign (positive vs. negative) and magnitude (small vs. large). The effects of positive and negative ΔH_mix are demonstrated based on two isomeric systems of o- vs. m-methoxymethylbenzene (MMB) and o- vs. m-dibromobenzene (DBB) with comparably small absolute ΔH_mix. Two opposite composition dependences of the glass transition temperature, T_g, are observed with the MMB mixtures showing a distinct negative deviation from the ideal mixing rule and the DBB mixtures having a marginally positive deviation. The system of 1, 2-propanediamine (12PDA) vs. propylene glycol (PG) with large and negative ΔH_mix is compared with the systems of small ΔH_mix, and a considerably positive T_g shift is seen. Models involving the properties of pure components such as T_g, glass transition heat capacity increment, ΔC_p, and density, ρ, do not interpret the observed T_g shifts in the systems. In contrast, a linear correlation is revealed between ΔH_mix and maximum T_g shifts.