First-order phase transitions are accompanied by a latent heat. Consequently, manipulating them by means of an external field causes a caloric effect. Although transitions from antiferromagnetic to paramagnetic states are not controlled by a magnetic field, a large barocaloric effect is expected when strong cross-correlations between the volume and magnetic order occur. Here we examine how geometric frustration in itinerant antiferromagnetic compounds can enhance the barocaloric effect. We study the thermodynamic behaviour of the frustrated antiferromagnet Mn3GaN, and report an entropy change of 22.3 J kg(-1) K(-1) that is concomitant with a hydrostatic pressure change of 139 MPa. Furthermore, the calculated value of the adiabatic temperature change reaches 5 K by depressurization of 93 MPa. The giant barocaloric effect in Mn3GaN is caused by a frustration-driven enhancement of the ratio of volume change against the pressure coefficient of the Néel temperature. This mechanism for enhancing the barocaloric effect can form the basis for a new class of materials for solid-state refrigerants.

Magnetostructural correlations in antiperovskite manganese nitrides were investigated systematically for stoichiometric and solid solution Mn3Cu1−xAxN (A = Co, Ni, Zn, Ga, Ge, Rh, Pd, Ag, In, Sn or Sb). This class of nitrides is attracting great attention because of their giant negative thermal expansion, which is achieved by doping Ge or Sn into the A site as a relaxant of the sharp volume contraction on heating (spontaneous volume magnetostriction ωs) because of the magnetovolume effects. The physical background of large ωs and mechanism of how the volume contraction becomes gradual with temperature are central concerns for the physics and applications of these nitrides. An entire dataset of thermal expansion, crystal structure and magnetization demonstrates that the cubic triangular antiferromagnetic state is crucial for large ωs. The intimate relationship between ωs and the magnetic structure is discussed in terms of geometrical frustration related to the Mn6N octahedron and magnetic stress concept. The results presented herein also show that ωs depends on the number of d electrons in the A atom, suggesting the important role of the d orbitals of the A atom. Not all the dopants in the A site, but the elements that disturb the cubic triangular antiferromagnetic state, are effective in broadening the volume change. This fact suggests that instability neighboring the phase boundary is related to the broadening. The relation between the gradual volume change and the local structure anomaly is suggested by recent microprobe studies.

Large negative thermal expansion (NTE) has been discovered during the last decade in materials of various kinds, particularly materials associated with a magnetic, ferroelectric or charge-transfer phase transition. Such NTE materials have attracted considerable attention for use as thermal-expansion compensators. Here, we report the discovery of giant NTE for reduced layered ruthenate. The total volume change related to NTE reaches 6.7% in dilatometry, a value twice as large as the largest volume change reported to date. We observed a giant negative coefficient of linear thermal expansion α=−115 × 10−6 K−1 over 200 K interval below 345 K. This dilatometric NTE is too large to be attributable to the crystallographic unit-cell volume variation with temperature. The highly anisotropic thermal expansion of the crystal grains might underlie giant bulk NTE via microstructural effects consuming open spaces in the sintered body on heating.

To meet strong demands for the control of thermal expansion necessary because of the advanced development of industrial technology, widely various giant negative thermal expansion (NTE) materials have been developed during the last decade. Discovery of large isotropic NTE in ZrW2O8 has greatly advanced research on NTE deriving from its characteristic crystal structure, which is now classified as conventional NTE. Materials classified in this category have increased rapidly. In addition to development of conventional NTE materials, remarkable progress has been made in phase-transition-type NTE materials using a phase transition accompanied by volume contraction upon heating. These giant NTE materials have brought a paradigm shift in the control of thermal expansion. This report classifies and reviews mechanisms and materials of NTE to suggest means of improving their functionality and of developing new materials. A subsequent summary presents some recent activities related to how these giant NTE materials are used as practical thermal expansion compensators, with some examples of composites containing these NTE materials.

We report a comprehensive study on the magnetic and structural properties of the spinel sulfides LiInCr 4 S 8 , LiGaCr 4 S 8 , and CuInCr 4 S 8 , where Li + /Cu + and Ga 3+ /In 3+ ions form a zinc-blende-type order. On the basis of synchrotron X-ray diffraction and magnetization data obtained using polycrystalline samples, these three sulfides are suggested to be breathing pyrochlore magnets with alternating antiferromagnetic and ferromagnetic interactions on the small and large tetrahedra, respectively. The measured magnetization processes of the three sulfides up to 72 T are significantly different. The magnetization curves of LiInCr 4 S 8 and CuInCr 4 S 8 have large hysteresis loops with different shapes, while there is no hysteresis in that of LiGaCr 4 S 8 . Geometrical frustration of the small tetrahedron is likely to give rise to a wide variety of ground states, indicating the rich physics in these antiferromagnetic-ferromagnetic breathing pyrochlore magnets. CrGa/In Li/Cu S (a) J (b) Cr J' d d'