On the existence of thermodynamically stable rigid solids

• Published in: Proceedings of the National Academy of Sciences - PNAS 2018-05, Vol.115 (19), p.E4322-E4329
• Main Authors: Nath, Parswa, Ganguly, Saswati, Horbach, Jürgen, Sollich, Peter, Karmakar, Smarajit, Sengupta, Surajit
• Format: Article
• Language: English
• Subjects: Boundaries; Computer simulation; Crystal structure; Crystallinity; Crystals; Deformation; Elastic limit; Free energy; Kinetics; Metastable state; Monte Carlo simulation; Phase transitions; Physical Sciences; PNAS Plus; Rigidity; Solids; Strain; Strain rate; Superplasticity; Thermodynamics
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.1800837115

Customarily, crystalline solids are defined to be rigid since they resist changes of shape determined by their boundaries. However, rigid solids cannot exist in the thermodynamic limit where boundaries become irrelevant. Particles in the solid may rearrange to adjust to shape changes eliminating stress without destroying crystalline order. Rigidity is therefore valid only in the metastable state that emerges because these particle rearrangements in response to a deformation, or strain, are associated with slow collective processes. Here, we show that a thermodynamic collective variable may be used to quantify particle rearrangements that occur as a solid is deformed at zero strain rate. Advanced Monte Carlo simulation techniques are then used to obtain the equilibrium free energy as a function of this variable. Our results lead to a unique view on rigidity: While at zero strain a rigid crystal coexists with one that responds to infinitesimal strain by rearranging particles and expelling stress, at finite strain the rigid crystal is metastable, associated with a free energy barrier that decreases with increasing strain. The rigid phase becomes thermodynamically stable when an external field, which penalizes particle rearrangements, is switched on. This produces a line of first-order phase transitions in the field–strain plane that intersects the origin. Failure of a solid once strained beyond its elastic limit is associated with kinetic decay processes of the metastable rigid crystal deformed with a finite strain rate. These processes can be understood in quantitative detail using our computed phase diagram as reference.