Mechanically Drawable Thermochromic and Mechanothermochromic Polydiacetylene Sensors

Recently, the development of directly writable techniques for depositing functional materials on solid substrates has received great attention. These pen-on-paper approaches enable generation of diverse patterned images on solid substrates in a flexible, easy handling, and inexpensive manner. Herein, the development of a directly writable conjugated polymer is described. Mechanically, drawable colorimetric polydiacetylene (PDA)-wax composites are readily fabricated by using a simple mixing-molding method. Images are mechanically drawn on a paper substrate using the PDA-wax composites, display thermochromism, and mechanothermochromism. The thermochromic transition temperature is dependent on the melting point of the wax and, as a result, can be precisely controlled by the type of wax used. Optical microscopic analysis shows that formation of the DA-wax composite involves movement of wax molecules into a single diacetylene (DA) crystal. This process results in growth of the crystal. Importantly, the PDA crystal, obtained after UV light irradiation, undergoes significant shrinkage upon heating because of the release of monomers and the embedded wax molecules from the crystal. The release of these molecules creates void in the PDA supramolecules, allowing the PDA chains to undergo C-C bond rotation and hence the blue-to-red color transition.