Size-dependent melting thermodynamics of nanorods in theory and experiment†
Compared with other morphological nanomaterials, nanorods have many unique properties that are closely related to their thermal stability. However, current studies on melting thermodynamic theory of nanorods are still not perfect, and the mechanism and the quantitative regularities of the effect of size of nanorods on melting thermodynamics still remain unclear. Herein, we proposed a melting model of nanorods, derived the thermodynamic relations (free of any adjustable parameters) between the melting temperature, melting enthalpy, and melting entropy, respectively, and the radius of nanorods, and discussed the mechanism of the effect of nanorods and the size dependences of melting thermodynamic properties. Experimentally, taking the melting of Se nanorods as an experimental system, Se nanorods with different diameters were prepared by a Na2SeSO3 disproportionation method, and then the melting temperature and melting thermodynamic properties were determined by differential scanning calorimetry. The effects of the diameter of Se nanorods on the melting temperature and the melting thermodynamic properties were obtained. The experimental results are consistent with the theoretical relations. Both theoretical and experimental results demonstrate that the radius and length of nanorods have significant effects on the melting temperature and the melting thermodynamic properties; for nanorods with a large aspect ratio, the main factors of influence are interfacial tension and radius. Compared with spherical nanoparticles with the same radius, the reduced values of the melting temperature and the thermodynamic properties of nanorods are just half of those corresponding to spherical nanoparticles; the melting temperature, the melting enthalpy, and the melting entropy decrease with the decrease in the radius, and when the radius exceeds 10 nm, these physical quantities are all linearly related to the reciprocal of the radius. The theory can describe the quantitative size-dependent melting thermodynamic properties of nanorods, explain and predict the melting behaviors of nanorods.