Combining fast scanning chip calorimetry and nanoindentation: Young's modulus and hardness of poly (L-lactic acid) containing α′- and α-crystals

Fast scanning chip calorimetry (FSC) allows subjecting polymer melts to well-defined vitrification, crystal nucleation, and crystal growth pathways and, therefore, precise control of morphologies, from fully amorphous glassy states to semicrystalline structures containing perfect crystals. Due to the required use of nanogram-sized samples, needed to achieve high cooling rates, their mechanical properties, in order to establish structureproperty relations, are difficult to assess. In this work, indentation modulus and indentation hardness of FSC samples are successfully determined on example of semicrystalline poly (L-lactic acid) (PLLA) containing spherulitically grown disorder alpha '- or rather perfect alpha-crystals, with the correctness of the applied preparation and analyses routes confirmed by nanoindentation measurements on milligram-sized samples prepared through hotstage microscopy, and by applying both static single-step and quasi-continuous stiffness measurements. Modulus and hardness data are consistent with prior analyses of bulk samples, confirming that semicrystalline PLLA containing alpha-crystals exhibits around 10-20 % higher values of these properties compared to PLLA containing alpha '-crystals, related to the different molecular-chain packing in the crystal lattice. This work demonstrates that combination of FSC and nanoindentation techniques is an effective tool for determining mechanical properties of samples solidified at specific thermal pathways which otherwise cannot be realized.