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Keywords:

Science & Technology, Physical Sciences, Technology, Chemistry, Multidisciplinary, Crystallography, Materials Science, Multidisciplinary, Chemistry, Materials Science, THERMAL-ENERGY STORAGE, LATENT-HEAT CHARACTERISTICS, MONOUNSATURATED TRIACYLGLYCEROLS, ENTROPY, SERIES, PCM, 0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0912 Materials Engineering, Inorganic & Nuclear Chemistry, 3402 Inorganic chemistry, 3406 Physical chemistry, 4016 Materials engineering

Abstract:

This article reports on the synthesis, thermal behavior, and morphology of phase change materials based on diesters from 1,4-butanediol with palmitic (BD16), stearic (BD18), or behenic (BD22) acid. The crystalline contents and melting enthalpies of all substances exceed 90% and 180 J/g, respectively. The molecules display monotropic polymorphism. The metastable β′ form is built from outstretched molecules, whereas the denser, stable β form is composed of molecules with a kinked conformation. BD18 and BD22 crystallize into the β′ form during cooling. Only BD18 transforms into the β form during subsequent heating via a solid-solid transition. The resistance of BD22 to convert into the β form is believed to originate from the lack of mobility associated with longer aliphatic chains. In contrast, the polymorphic conversion is thought to be very efficient and to take place during cooling for the shorter BD16 molecules. The hypothesis is put forward that the original BD16 β′ nuclei are rapidly overgrown by the β phase by which crystal growth is postponed to larger supercooling where the β phase can grow from the melt. Consequently, BD16 only occurs in the β form. The melt crystallization of BD18 and BD22 into the β′ form hardly requires any supercooling. © 2013 American Chemical Society.