Investigations of Reversible Thermochromism in Three-Component Systems
Thermochromic materials undergo temperature-dependent colour changes. Although there are several origins of thermochromism, two distinct types of thermochromism are common in thermochromic mixtures. Melt-lightened thermochromism occurs when the colour density of a mixture decreases with increasing temperature, and is usually associated with colour loss upon mixture melting. Melt-darkened thermochromism occurs when the colour density of a mixture increases with increasing temperature, and is usually associated conversion from a decoloured solid state to a coloured melt. Three-component thermochromic systems generally consist of a leuco dye (minor component), a phenolic colour developer (intermediate component), and a high melting-point organic solvent (dominant component). In these systems, the colouring behaviour is controlled by competing binary interactions, with the dye:developer interaction responsible for colour formation and the developer:solvent interaction responsible for colour erasure. In the present study, three-component mixtures composed of CVL (dye), long-chain alkyl gallates (phenolic developer), and long-chain alkyl alcohols (long-chain solvent) were examined. The thermochromic behaviour (i.e., melt-lightened vs. melt-darkened thermochromism) of these mixtures was examined as a function of the matching of the alkyl chain length of the gallate developer and alcohol solvent. When the alkyl chain lengths were well matched, the developer:solvent interaction dominated in the solid state and melt-darkened thermochromism was observed. When the alkyl chain lengths were poorly matched, the dye:developer interaction dominated in the solid state, and melt-lightened thermochromism was observed. The colour density of the molten state was determined by the developer:dye molar ratio, with high molar ratios yielding coloured melts and low molar ratios yielding decoloured melts. Additional studies employing chemically dissimilar developers and solvents (e.g., bisphenol A with 1-hexadecanol) yielded mixtures that displayed optimal melt-lightened thermochromism. The high solid-state colour density due to weak developer:solvent interactions provides further evidence that competing binary interactions are responsible for the colouring behaviour observed for three-component thermochromic systems. Ternary thermochromic phase diagrams were used to define compositional regions of optimal thermochromic behaviour (i.e., high colour contrast), providing a useful experimental tool for the rapid identification of ideal sample compositions. Additionally, an examination of the properties of thermally erasable ink-jet printer inks was carried out during the present study.