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Novel multicaloric cooling utilizing the giant caloric response of Ni-Mn-based metamagnetic shape-memory alloys to different external stimuli such as magnetic field, uniaxial stress and hydrostatic pressure is a promising candidate for energy-efficient and environmentally-friendly refrigeration. However, the role of microstructure when several external fields are applied simultaneously or sequentially has been scarcely discussed in literature. Here, we synthesized ternary Ni-Mn-In alloys by suction casting and arc melting and analyzed the microstructural influence on the response to magnetic fields and uniaxial stress. By combining SEM-EBSD and stress-strain data, a significant effect of texture on the stress-induced martensitic transformation is revealed. It is shown that a <001> texture can strongly reduce the critical transformation stresses. The effect of grain size on the material failure is demonstrated and its influence on the magnetic-field-induced transformation dynamics is investigated. Temperature-stress and temperature-magnetic field phase diagrams are established and single caloric performances are characterized in terms of ${\Delta}{s_T}$ and ${\Delta}{T_{ad}}$. The cyclic ${\Delta}{T_{ad}}$ values are compared to the ones achieved in the multicaloric exploiting-hysteresis cycle. It turns out that a suction-cast microstructure and the combination of both stimuli enables outstanding caloric effects in moderate external fields which can significantly exceed the single caloric performances. In particular for Ni-Mn-In, the maximum cyclic effect in magnetic fields of 1.9 T is increased by more than 200 % to -4.1 K when a moderate sequential stress of 55 MPa is applied. Our results illustrate the crucial role of microstructure for multicaloric cooling using Ni-Mn-based metamagnetic shape-memory alloys.

The world's growing hunger for artificial cold on the one hand, and the ever more stringent climate targets on the other, pose an enormous challenge to mankind. Novel, efficient and environmentally friendly refrigeration technologies based on solid-state refrigerants can offer a way out of the problems arising from climate-damaging substances used in conventional vapor-compressors. Multicaloric materials stand out because of their large temperature changes which can be induced by the application of different external stimuli such as a magnetic, electric, or a mechanical field. Despite the high potential for applications and the interesting physics of this group of materials, only few studies focus on their investigation by direct methods. In this paper, we report on the advanced characterization of all relevant physical quantities that determine the multicaloric effect of a Ni-Mn-In Heusler compound. We have used a purpose-designed calorimeter to determine the isothermal entropy and adiabatic temperature changes resulting from the combined action of magnetic field and uniaxial stress on this metamagnetic shape-memory alloy. From these results, we can conclude that the multicaloric response of this alloy by appropriate changes of uniaxial stress and magnetic field largely outperforms the caloric response of the alloy when subjected to only a single stimulus. We anticipate that our findings can be applied to other multicaloric materials, thus inspiring the development of refrigeration devices based on the multicaloric effect., Comment: To be published in Applied Physic Reviews

There is currently great interest in replacing the harmful volatile hydrofluorocarbon fluids used in refrigeration and air-conditioning with solid materials that display magnetocaloric, electrocaloric or mechanocaloric effects. However, the field-driven thermal changes in all of these caloric materials fall short with respect to their fluid counterparts. Here we show that plastic crystals of neopentylglycol (CH3)2C(CH2OH)2 display unprecedentedly large pressure-driven thermal changes near room temperature due to molecular reconfiguration, and that these changes are comparable with those exploited commercially in hydrofluorocarbons. Our discovery of colossal barocaloric effects in a plastic crystal should bring barocaloric materials to the forefront of research and development in order to achieve safe environmentally friendly cooling without compromising performance., Comment: 4 figures, 1 table, 11 supplementary figures, 3 supplementary tables

Shape memory alloys are a class of ferroic materials which undergo a structural (martensitic) transition where the associated ferroic property is a lattice distortion (strain). The sensitiveness of the transition to the conjugated external field (stress), together with the latent heat of the transition gives rise to giant mechanocaloric effects. In non-magnetic shape memory alloys, the lattice distortion is mostly described by a pure shear and the martensitic transition in this family of alloys is strongly affected by uniaxial stress whereas it is basically insensitive to hydrostatic pressure. As a result, non-magnetic alloys exhibit giant elastocaloric effects but negligible barocaloric effects. By contrast, in a number of magnetic shape memory alloys, the lattice distortion at the martensitic transition involves a volume change in addition to the shear strain. Those alloys are affected by both uniaxial stress and hydrostatic pressure and they exhibit giant elastocaloric and barocaloric effects. The paper aims at providing a critical survey of available experimental data on elastocaloric and barocaloric effects in magnetic and non-magnetic shape memory alloys., Comment: To appear in Philosophical Transactions A

We report on calorimetry under applied hydrostatic pressure and magnetic field at the antiferromagnetic (AFM)-ferromagnetic (FM) transition of Fe$_{49}$Rh$_{51}$. Results demonstrate the existence of a giant barocaloric effect in this alloy, a new functional property that adds to the magnetocaloric and elastocaloric effects previously reported for this alloy. All caloric effects originate from the AFM/FM transition which encompasses changes in volume, magnetization and entropy. The strong sensitivity of the transition temperatures to both hydrostatic pressure and magnetic field confers to this alloy outstanding values for the barocaloric and magnetocaloric strengths ($|\Delta S|$/$\Delta p$ $\sim$ 12 J kg$^{-1}$ K $^{-1}$ kbar$^{-1}$ and $|\Delta S|$/$\mu_0\Delta H$ $\sim$ 12 J kg$^{-1}$ K$^{-1}$ T$^{-1}$). Both barocaloric and magnetocaloric effects have been found to be reproducible upon pressure and magnetic field cycling. Such a good reproducibility and the large caloric strengths make Fe-Rh alloys particularly appealing for solid-state cooling technologies at weak external stimuli., Comment: To apperar in Phys. Rev. B

Recent progress on caloric effects are reviewed. The application of external stimuli such as magnetic field, hydrostatic pressure, uniaxial stress and electric field give rise respectively to magnetocaloric, barocaloric, elastocaloric and electrocaloric effects. The values of the relevant quantities such as isothermal entropy and adiabatic temperature-changes are compiled for selected materials. Large values for these quantities are found when the material is in the vicinity of a phase transition. Quite often there is coupling between different degrees of freedom, and the material can exhibit cross-response to different external fields. In this case, the material can exhibit either conventional or inverse caloric effects when a field is applied. The values reported for the many caloric effects at moderate fields are large enough to envisage future application of these materials in efficient and environmental friendly refrigeration., Comment: Featured Article

Neutron scattering and ultrasonic methods have been used to study the lattice dynamics of two single crystals of Ni-Mn-In Heusler alloys close to Ni$_{50}$Mn$_{34}$In$_{16}$ magnetic superelastic composition. The paper reports the experimental determination of the low-lying phonon dispersion curves and the elastic constants for this alloy system. We found that the frequencies of the TA$_{2}$ branch are relatively low and it exhibits a small dip anomaly at a wave number $\xi_{0} \approx 1/3$, which softens with decreasing temperature. Associated with the softening of this phonon, we also observed the softening of the shear elastic constant $C'=(C_{11}-C_{12})/2$. Both temperature softenings are typical for bcc based solids which undergo martensitic transformations and reflect the dynamical instability of the cubic lattice against shearing of $\{110\}$ planes along $<1\bar{1}0>$ directions. Additionally, we measured low-lying phonon dispersion branches and elastic constants in applied magnetic fields aimed to characterize the magnetoelastic coupling., Comment: 8 pages, 7 figures. Accepted for publication in the Physical Review B

We have studied the effect of Fe addition on the structural and magnetic transitions in the magnetic shape memory alloy Ni-Mn-Ga by substituting systematically each atomic species by Fe. Calorimetric and AC susceptibility measurements have been carried out in order to study the magnetic and structural transformation properties. We find that the addition of Fe modifies the structural and magnetic transformation temperatures. Magnetic transition temperatures are displaced to higher values when Fe is substituted into Ni-Mn-Ga, while martensitic and premartensitic transformation temperatures shift to lower values. Moreover, it has been found that the electron per atom concentration essentially governs the phase stability in the quaternary system. However, the observed scaling of transition temperatures with $e/a$ differs from that reported in the related ternary system Ni-Mn-Ga., Comment: 8 pages, 8 figures. Accepted for publication in the Physical Review B

The elastocaloric effect in the vicinity of the martensitic transition of a Cu-Zn-Al has been studied by inducing the transition by strain or stress measurements. While transition trajectories show significant differences, the entropy change associated with the whole transformation (\DeltaSt) is coincident in both kind of experiments since entropy production is small compared to \DeltaSt. The values agree with estimations based on the Clausius- Clapeyron equation. The possibility of using these materials for mechanical refrigeration is also discussed., Comment: 4 pages, 4 figures

We report magnetization and differential thermal analysis measurements as a function of pressure accross the martensitic transition in magnetically superelastic Ni-Mn-In alloys. It is found that the properties of the martensitic transformation are significantly affected by the application of pressure. All transition temperatures shift to higher values with increasing pressure. The largest rate of temperature shift with pressure has been found for Ni$_{50}$Mn$_{34}$In$_{16}$ as a consequence of its small entropy change at the transition. Such a strong pressure dependence of the transition temperature opens up the possibility of inducing the martensitic transition by applying relatively low hydrostatic pressures., Comment: 3 pages, 3 figures. Accepted for publication in Applied Physics Letters

Ni$_{50}$Mn$_{34}$In$_{16}$ undergoes a martensitic transformation around 250 K and exhibits a field induced reverse martensitic transformation and substantial magnetocaloric effects. We substitute small amounts Ga for In, which are isoelectronic, to carry these technically important properties to close to room temperature by shifting the martensitic transformation temperature., Comment: 3 pages, 5 figures. Accepted for publication in Applied Physics Letters

We study the temperature dependence of strain under constant magnetic-fields in Ni-Mn based ferromagnetic Heusler alloys in the form Ni-Mn-$X$ ($X$: Ga, In, Sn, Sb) which undergo a martensitic transformation. We discuss the influence of the applied magnetic-field on the nucleation of ferromagnetic martensite and extract information on the easy-axis of magnetization in the martensitic state., Comment: 3 pages, 3 figures. Accepted for publication in Applied Physics Letters

At certain compositions Ni-Mn-$X$ Heusler alloys ($X$: group IIIA-VA elements) undergo martensitic transformations, and many of them exhibit inverse magnetocaloric effects. In alloys where $X$ is Sn, the isothermal entropy change is largest among the Heusler alloys, particularly in Ni$_{50}$Mn$_{37}$Sn$_{13}$ where it reaches a value of 20 Jkg$^{-1}$K$^{-1}$ for a field of 5T. We substitute Ni with Fe and Co in this alloy, each in amounts of 1 at% and 3 at% to perturb the electronic concentration and examine the resulting changes in the magnetocaloric properties. Increasing both Fe and Co concentrations causes the martensitic transition temperature to decrease, whereby the substitution by Co at both compositions or substituting 1 at% Fe leads to a decrease in the magnetocaloric effect. On the other hand, the magnetocaloric effect in the alloy with 3 at% Fe leads to an increase in the value of the entropy change to about 30 Jkg$^{-1}$K$^{-1}$ at 5T., Comment: 5 pages, 7 figures. Accepted for publication in the Journal of Applied Physics

We report on measurements of the adiabatic temperature change in the inverse magnetocaloric Ni$_{50}$Mn$_{34}$In$_{16}$ alloy. It is shown that this alloy heats up with the application of a magnetic field around the Curie point due to the conventional magnetocaloric effect. In contrast, the inverse magnetocaloric effect associated with the martensitic transition results in the unusual decrease of temperature by adiabatic magnetization. We also provide magnetization and specific heat data which enable to compare the measured temperature changes to the values indirectly computed from thermodynamic relationships. Good agreement is obtained for the conventional effect at the second-order paramagnetic-ferromagnetic phase transition. However, at the first order structural transition the measured values at high fields are lower than the computed ones. Irreversible thermodynamics arguments are given to show that such a discrepancy is due to the irreversibility of the first-order martensitic transition., Comment: 5 pages, 4 figures. Accepted for publication in the Physical Review B

Applying a magnetic field to a ferromagnetic Ni$_{50}$Mn$_{34}$In$_{16}$ alloy in the martensitic state induces a structural phase transition to the austenitic state. This is accompanied by a strain which recovers on removing the magnetic field giving the system a magnetically superelastic character. A further property of this alloy is that it also shows the inverse magnetocaloric effect. The magnetic superelasticity and the inverse magnetocaloric effect in Ni-Mn-In and their association with the first order structural transition is studied by magnetization, strain, and neutron diffraction studies under magnetic field., Comment: 6 pages, 8 figures. Published in the Physical Review B

We report on experiments aimed at comparing the hysteretic response of a Cu-Zn-Al single crystal undergoing a martensitic transition under strain-driven and stress-driven conditions. Strain-driven experiments were performed using a conventional tensile machine while a special device was designed to perform stress-driven experiments. Significant differences in the hysteresis loops were found. The strain-driven curves show re-entrant behaviour (yield point) which is not observed in the stress-driven case. The dissipated energy in the stress-driven curves is larger than in the strain-driven ones. Results from recently proposed models qualitatively agree with experiments., Comment: 5 pages, 5 figures

We report on measurements of the adiabatic second order elastic constants of the off-stoichiometric Ni$_{54}$Mn$_{23}$Al$_{23}$ single crystalline Heusler alloy. The variation in the temperature dependence of the elastic constants has been investigated across the magnetic transition and over a broad temperature range. Anomalies in the temperature behaviour of the elastic constants have been found in the vicinity of the magnetic phase transition. Measurements under applied magnetic field, both isothermal and variable temperature, show that the value of the elastic constants depends on magnetic order, thus giving evidence for magnetoelastic coupling in this alloy system., Comment: 7 pages, 5 figures. Accepted for publication in Physical the Review B

Inelastic and elastic neutron scattering have been used to study a single crystal of the Ni$_{54}$Mn$_{23}$Al$_{23}$ Heusler alloy over a broad temperature range. The paper reports the first experimental determination of the low-lying phonon dispersion curves for this alloy system. We find that the frequencies of the TA$_2$ modes are relatively low. This branch exhibits an anomaly (dip) at a wave number $\xi_{0} ={1/3}\approx 0.33$, which softens with decreasing temperature. Associated with this anomalous dip at $\xi_{0}$, an elastic central peak scattering is also present. We have also observed satellites due to the magnetic ordering., Comment: 6 pages, 6 figures. Accepted for publication in the Physical Review B

We report on the existence of acoustic emission during the paramagnetic-monoclinic to ferromagnetic-orthorhombic magnetostructural phase transition in the giant magnetocaloric Gd5Si2Ge2 compound. The transition kinetics have been analyzed from the detected acoustic signals. It is shown that this transition proceeds by avalanches between metastable states., Comment: 5 pages, 4 figures

The magnetocaloric effect (MCE) in paramagnetic materials has been widely used for attaining very low temperatures by applying a magnetic field isothermally and removing it adiabatically. The effect can be exploited also for room temperature refrigeration by using recently discovered giant MCE materials. In this letter, we report on an inverse situation in Ni-Mn-Sn alloys, whereby applying a magnetic field adiabatically, rather than removing it, causes the sample to cool. This has been known to occur in some intermetallic compounds, for which a moderate entropy increase can be induced when a field is applied, thus giving rise to an inverse magnetocaloric effect. However, the entropy change found for some ferromagnetic Ni-Mn-Sn alloys is just as large as that reported for giant MCE materials, but with opposite sign. The giant inverse MCE has its origin in a martensitic phase transformation that modifies the magnetic exchange interactions due to the change in the lattice parameters., Comment: 12 pages, 4 figures, to appear in Nature Materials (online published, 15 May 2005)

We have studied the driving rate and temperature dependence of the power-law exponents that characterize the avalanche distribution in first-order phase transitions. Measurements of acoustic emission in structural transitions in Cu-Zn-Al and Cu-Al-Ni are presented. We show how the observed behaviour emerges within a general framework of competing time scales of avalanche relaxation, driving rate, and thermal fluctuations. We have confirmed our findings by numerical simulations of a prototype model., Comment: 4 pages, 3 figures

Measurements of magnetic hysteresis loops in Cu-Al-Mn alloys of different Mn content at low temperatures are presented. The loops are smooth and continuous above a certain temperature, but exhibit a magnetization discontinuity below that temperature. Scaling analysis suggest that this system displays a disorder induced phase transition line. Measurements allow to determine the critical exponents $\beta=0.03\pm 0.01$ and $\beta \delta = 0.4 \pm 0.1$ in agreement with those reported recently [Berger et al., Phys. Rev. Lett. {\bf 85}, 4176 (2000)], Comment: 4 pages, 5 figures

We have studied the effect of ageing within the miscibility gap on the electric, magnetic and thermodynamic properties of a non-stoichiometric Heusler Cu-Al-Mn shape-memory alloy, which undergoes a martensitic transition from a $bcc$-based ($\beta$-phase) towards a close-packed structure ($M$-phase). Negative magnetoresistance which shows an almost linear dependence on the square of magnetization with different slopes in the $M$- and $\beta$-phases, was observed. This magnetoresistive effect has been associated with the existence of Mn-rich clusters with the Cu$_2$AlMn-structure. The effect of an applied magnetic field on the martensitic transition has also been studied. The entropy change between the $\beta$- and $M$-phases shows negligible dependence on the magnetic field but it decreases significantly with annealing time within the miscibility gap. Such a decrease is due to the increasing amount of Cu$_2$MnAl-rich domains that do not transform martensitically., Comment: 9 pages, 9 figures, accepted for publication in PRB

The significance of thermal fluctuations on nucleation in structural first-order phase transitions has been examined. The prototype case of martensitic transitions has been experimentally investigated by means of acoustic emission techniques. We propose a model based on the mean first-passage time to account for the experimental observations. Our study provides a unified framework to establish the conditions for isothermal and athermal transitions to be observed., Comment: 5 pages, 4 figures, accepted in Phys. Rev. Lett

We show that the magnetoelastic coupling between the magnetization and the amplitude of a short wavelength phonon enables the existence of a first order premartensitic transition from a bcc to a micromodulated phase in $Ni_{2}MnGa$. Such a magnetoelastic coupling has been experimentally evidenced by AC susceptibility and ultrasonic measurements under applied magnetic field. A latent heat around 9 J/mol has been measured using a highly sensitive calorimeter. This value is in very good agreement with the value predicted by a proposed model., Comment: 4 pages RevTex, 3 Postscript figures, to be published in Physical Review Letters