Kauzmann paradox suggests existence of a supercooled liquidous state of lower entropy than corresponding solids- the entropy catastrophe. This entropy catastrophe has remained unresolved for nine decades. This paradox, often presented in 2D space can be resolved by considering an ordered/speciated phase alongside the amorphous supercooled state necessitating a violation of the Onsager-Casimir reciprocal relations, L_ij ≠ L_ji. This vector field asymmetry implies that solidification of deeply supercooled materials must occur far-from-equilibrium where associated dynamics and asymmetry in the surface stress tensor cannot be ignored. Applying chaos-based thermodynamics speed limits, we demonstrate that solidification of deeply undercooled core-shell particles can be explained from a four-state model resulting in a three-dimensional entropy phase diagram allowing us to avert the entropy catastrophe. Under conventional fugacity and equilibrium-based models, even in consideration of thermodynamic speed limits, the entropy catastrophe predicted by Kauzmann cannot be avoided. The new four-state model, therefore, offers a new approach through which complex (ordered and disordered) materials systems avoid the Kauzmann paradox.

Bio:

Martin M. Thuo is a Professor in the Department of Materials Science & Engineering at North Carolina State University and the deputy director, NSF-STC Center for Complex Particle Systems (COMPASS). He is a fellow of the National Academy of inventors (FNAI). Previously, he was the Schafer 2050 associate professor at Iowa State University in the department of Materials Science & Engineering and in Electrical and Computer engineering. He was a Mary-Fieser (2009-2011) and NSEC (2011-2013) postdoctoral Fellow at Harvard University under Prof. George M. Whitesides. He is the recipient of several awards like the ACS nano rising star, the Schafer 2050 professorship, Akinc excellence in research award, Lynn-Anderson research excellence award, Black & Veatch faculty fellowship, among others. He is a co-host of the ICAN-X talks and serves on the boards of various journals and professional societies. His research interests encompass the general theme of frugal innovation through simplicity and surface thermodynamics.