Josep-Lluís Tamarit

Giant solid-state barocaloric effect in the Ni–Mn–In magnetic shape-memory alloy

The search for materials showing large caloric effects close to room temperature has become a challenge in modern materials physics and it is expected that such a class of materials will provide a way to renew present cooling devices that are based on the vapour compression of hazardous gases. Up to now, the most promising materials are giant magnetocaloric materials. The discovery of materials showing a giant magnetocaloric effect at temperatures close to ambient has opened up the possibility of using them for refrigeration. As caloric effects refer to the isothermal entropy change achieved by application of an external field, several caloric effects can take place on tuning different external parameters such as pressure and electric field. Indeed the occurrence of large electrocaloric and elastocaloric effects has recently been reported. Here we show that the application of a moderate hydrostatic pressure to a magnetic shape-memory alloy gives rise to a caloric effect with a magnitude that is comparable to the giant magnetocaloric effect reported in this class of materials. We anticipate that similar barocaloric effects will occur in many giant-magnetocaloric materials undergoing magnetostructural transitions involving a volume change.

Inverse barocaloric effect in the giant magnetocaloric La-Fe-Si-Co compound.

Application of hydrostatic pressure under adiabatic conditions causes a change in temperature in any substance. This effect is known as the barocaloric effect and the vast majority of materials heat up when adiabatically squeezed, and they cool down when pressure is released (conventional barocaloric effect). There are, however, materials exhibiting an inverse barocaloric effect: they cool when pressure is applied, and they warm when it is released. Materials exhibiting the inverse barocaloric effect are rather uncommon. Here we report an inverse barocaloric effect in the intermetallic compound La-Fe-Co-Si, which is one of the most promising candidates for magnetic refrigeration through its giant magnetocaloric effect. We have found that application of a pressure of only 1 kbar causes a temperature change of about 1.5 K. This value is larger than the magnetocaloric effect in this compound for magnetic fields that are available with permanent magnets.

Barocaloric effect in the magnetocaloric prototype Gd5Si2Ge2

We report on calorimetric measurements under hydrostatic pressure that enabled us to determine the barocaloric effect in Gd5Si2Ge2. The values for the entropy change for moderate pressures compare favourably to those corresponding to the magnetocaloric effect in this compound. Entropy data are complemented with direct measurements of the adiabatic pressure-induced temperature change.

Barocaloric and magnetocaloric effects in Fe49Rh51

We report on calorimetry under applied hydrostatic pressure and magnetic field at the antiferromagnetic-ferromagnetic (AFM/FM) transition of Fe49Rh51. Results demonstrate the existence of a giant barocaloric effect in this alloy, a 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 (|?S|/?p ~ 12 J kg-1K-1kbar-1 and |?S|/µ0?H~ 12 J kg-1K-1T-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.

Anisotropy of Intermolecular Interactions from the Study of the Thermal-Expansion Tensor

The anisotropy of the intermolecular interactions in the low-temperature ordered phases of three chemically and structurally related compounds [neopentylglycol, (CH3)2C(CH2OH)2, pivalic acid, (CH3)3C(COOH), and neopentylalcohol, (CH3)3C(CH2OH)], all of which display an orientationally disordered high-temperature phase, has been shown by means of the isobaric thermal-expansion tensor. The variation of the directions of the principal components of the thermal-expansion tensor as a function of temperature, as well as the variation of its principal coefficients, is evidence of the large differences in the intermolecular interactions for each compound; or, more precisely, between the strong intermolecular hydrogen bonds and the weak van der Waals interactions. In addition, the differences in the hydrogen-bonding schemes expected a priori from the molecular structures of the studied compounds have been enhanced. Finally, the volume expansivity as well as the packing coefficient have been analysed in the orientationally disordered high-temperature phase of each of the three compounds.Part of this work was presented at the EPDIC 1997 meeting (5th European Powder Diffraction Conference).

Reversible adiabatic temperature changes at the magnetocaloric and barocaloric effects in Fe49Rh51

We report on the adiabatic temperature changes (ΔT) associated with the magnetocaloric and barocaloric effects in a Fe49Rh51 alloy. For the magnetocaloric effect, data derived from entropy curves are compared to direct thermometry measurements. The agreement between the two sets of data provides support to the estimation of ΔT for the barocaloric effect, which are indirectly determined from entropy curves. Large ΔT values are obtained at relatively low values of magnetic field (2 T) and hydrostatic pressure (2.5 kbar). It is also shown that both magnetocaloric and barocaloric effects exhibit good reproducibility upon magnetic field and hydrostatic pressure cycling, over a considerable temperature range.

Benzocaine polymorphism: Pressure-temperature phase diagram involving forms II and III

Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases.

Dimorphism of the prodrug l‐tyrosine ethyl ester: Pressure–temperature state diagram and crystal structure of phase II

Polymorphism is important in the field of solid-state behavior of drug molecules because of the continuous drive for complete control over drug properties. By comparing different structures of a series of L-tyrosine alkyl esters, it became apparent that the ethyl ester possesses dimorphism. Its structure was determined by powder diffraction and verified by density functional theory calculations; it is orthorhombic, P2(1) 2(1) 2(1) with a = 12.8679(8) Å, b = 14.7345(7) Å, c = 5.8333 (4) Å, V = 1106.01(11) Å, and Z = 4. The density of phase II is in line with other tyrosine alkyl esters and its conformation is similar to that of l-tyrosine methyl ester. The hydrogen bonds exhibit similar geometries for phase I and phase II, but the H-bonds in phase I are stronger. The solid II-solid I transition temperature is heating-rate dependent; it levels off at heating rates below 0.5 K min(-1), leading to a transition temperature of 306 ± 4 K. Application of the Clapeyron equation in combination with calorimetric and X-ray data has led to a topological diagram providing the relative stabilities of the two solid phases as a function of pressure and temperature; phase II is stable under ambient conditions.

Overall stability for the ibuprofen racemate: experimental and topological results leading to the pressure-temperature phase relationships between its racemate and conglomerate.

Enantiomer resolution is much sought after for pharmaceutical applications, because many optically active drug molecules have only one pharmaceutically active enantiomer. Although it is always possible to force separation, it will come at a cost. The present method, based on thermodynamics, provides a relatively easy approach to investigate whether separation can be thermodynamically spontaneous. A topological phase diagram of the binary enantiomer system at 0.5 mol-fraction is constructed as a function of temperature and pressure after analysis of pressure and heat related quantities. It is demonstrated that for ibuprofen, an optically active analgesic, the racemate is the only stable solid form; the phase relationship between the racemate and the conglomerate is analogous to dimorphism with overall monotropy in pure chemical compounds.

Molecular mixed crystals of neopentane derivatives. A comparative analysis of three binary systems showing crossed isodimorphism

Abstract A thermodynamic analysis is presented for three binary systems out of the four neopentane derivatives: neopentylglycol (NPG), pentaglycerin (PG), pentaerythritol (PE) and tris(hydroxymethyl) aminomethane (TRIS). These substances give rise to a plastic crystalline state, which is bcc for TRIS and fcc for NPG, PG and PE. In each of the three systems considered TRIS is one of the components: they are examples of crossed isodimorphism and the estimation of metastable melting points is an essential part of the analysis. Unlike the plastic-crystalline state, miscibility in the ordered solid state is poor, with the exception of the PE side in the system PE/TRIS. In the analysis, the liquid mixtures were taken as ideal and for the plastic crystalline solutions the excess Gibbs energy was expressed in terms of the (A,B,⊖) model.