even though these compounds are most prone to such drawbacks, is the negative role of hysteresis. Since all MCE applications have a cyclic character, one of the main pre-conditions is to ensure a total (or at least partial) reversibility of the effect when either fi eld or temperature oscillations are applied. From a material point of view, this means keeping the fi eld or thermal hysteresis that could occur as small as possible. A second drawback of G-MCE materials is related to their mechanical stability. FOTs bring not only sharp magnetization jumps but also discontinuities of other physical parameters, including the unit cell. This "structural" part can have manifold aspects: symmetry breaking or cell-volume or lattice-parameter changes. The most dramatic for the stability of polycrystalline bulk samples turns out to be the cell-volume change. During thermal or magnetic fi eld cycles, the strains generated by a volume change may cause fractures or even destruction of the bulk piece, which severely hinders the applicability of these materials. Technical solutions can be used to overcome this problem, for instance by embedding the MCE material in a resin or by a porous shaping. [ 18 ] However, in such cases the MCE is "diluted", which is not satisfactory since the gap of the magnet is not effi ciently used and the thermal conductivity governing the heat transfer is decreased. Bulk G-MCE materials with a good mechanical stability should remain the preferred solution. Finally, to allow large-scale applications, a last requirement that should be borne in mind is that the MCE material must consist of elements that are available in large amounts, are not expensive, and are not classifi ed as toxic.In this context, the MnFe(P, x ) system appears to be an ideal playground. This material family is derived from the Fe 2 P compound, a prototypical example known for a long time to exhibit a sharp but weak (the latent heat L is only 0.25 kJ kg −1 ) FOT with a Curie temperature ( T C ) of 217 K. [ 19 ] In this hexagonal system, the Fe atoms occupy two inequivalent atomic positions referred to as 3f (in a tetrahedral environment of non-metallic atoms) and 3g (pyramidal). An intriguing aspect is the disappearance at T C of the magnetic moments of the iron atoms at the 3f sites, whereas there is only a limited decrease of the moments at the 3g site. This theoretical prediction has led to a cooperative description of the FOT that links the loss of longrange magnetic order at T C with the loss of the local moments at the 3f site. [ 20 ] This mechanism has recently been proposed to be the origin of the G-MCE observed in MnFe(P,Si). The disappearance of the magnetic moments is ascribed to a conversion from non-bonding d electrons to a distribution with pronounced hybridization with the surrounding Si/P atoms. [ 11 ] A practical consequence is that the FOT mechanism can be expected to be highly sensitive to substitutions at the nonmetallic site. In the present work, precisely this approach has been used to solve three problems of ...

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