The sign of lattice and spin entropy change in the giant magnetocaloric materials with negative lattice expansions

Abstract

Solid-state refrigeration based on the magnetocaloric effect (MCE) has garnered worldwide attention because of its superior energy conservation and its environmentally friendly impact. Many materials exhibiting magnetostructural/magnetoelastic transitions have been identified by their giant MCE as promising refrigerants. The common feature of these materials is their simultaneous magnetic and lattice transitions; some also undergo negative expansions, i.e., lattice contractions, along with a ferromagnetic (FM) to paramagnetic (PM) transition. For these materials, whether the signs of lattice and spin entropy change are the same or opposite has become a controversial issue, noting that a larger unit cell volume usually indicates softer phonons and therefore a bigger phonon entropy. On the basis of our experiments and published data, we demonstrate that the lattice and spin entropy changes retain the same sign at least for La(Fe,Si)13-based compounds and MM’X alloys with giant MCE, for which the lattice undergoes negative expansion along with a FM to PM transition on heating. The clarification of the sign of lattice entropy change in the total entropy change is of particular importance for a comprehensive understanding of new materials with giant magnetocaloric effect and their design.