First-order phase transition in high-performance La(Fe,Mn,Si)13H despite negligible hysteresis

Optimizing the performance of magnetocaloric materials is facilitated by understanding the thermo-magnetic transitions they undergo, including the order of these transitions and their strength. Those ex-hibiting strong first-order phase transitions (FOPT) are accompanied by large heating and cooling responses but with relatively small cyclic responses, while materials with second-order (SOPT) character exhibit moderate heating and cooling responses. However, the lack of hysteresis could partially compensate for the lower magnitudes with a more cyclic response. One way to effectively maximize the cyclic response, combining the advantages of FOPT and SOPT, is to fine tune the transition towards the borderline of FOPT-SOPT, which can minimize hysteresis. For the well-known La(Fe,Si)13 family, it is challenging to identify and/ or evaluate the critical point where FOPT crossovers to SOPT based on conventional techniques. To address these ambiguities, in this work, we apply the field dependence exponent n criteria to a series of lowly hysteretic and high-performance La(Fe,Mn,Si)13H magnetocaloric materials with compositions close to the critical one. Even if the sample with the lowest hysteresis resembles characteristics of SOPT, it is evidently identified as undergoing FOPT from the n criteria: (1) existence of n > 2 overshoot and (2) n at the transition temperature, ntransition, is 0.37. This proximity to the critical composition (ntransition=0.4) further explains the low hysteresis observed. This FOPT character of the series is confirmed by temperature-dependent 57Fe Mossbauer spectrometry studies, fitting the hyperfine field to the Bean-Rodbell model instead of the usual Brillouin function. As it is a zero-field method, the confirmation by Mossbauer spectrometry gives further strength to the n-criterion.(c) 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http:// creativecommons.org/licenses/by/4.0/).