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Dramatic Tunability in Melting Temperature and Crystallinity of Polyethylene by Exploiting Confinement During Processing

We exploited Matrix Assited Pulsed Laser Evaporation (MAPLE) to deposit polyethylene from a quasi-vapor phase at a controlled substrate temperature, to crystallize polymers under confinement at a wide range of target crystallization temperature, Tc.  The team showed the remarkable controllability of the semi-crystalline structure of PE by MAPLE with the control of substrate temp.; see Figure A and B. In comparison to melt-crystallized PE (Fig. C), we discovered that while Tc critically determined the melting temperature, Tm, crystallinity depended not only on Tc but also on how the PE was crystallized.  We also demonstrated a greater than 20oC change in Tm of MAPLE processed PE; see Figure B. Our results, indicates that the formation of supramolecular structure of semi-crystalline phase, even with the same metastable crystallites, strongly depends on processing route; see Fig. D.