Magnetocalorics

Introduction

Temperature control systems are responsible for approximately one half of the energy consumption expenditure. Hence, refrigeration based on the magnetocaloric effect (MCE), seen as a promising technology to replace traditional refrigerators, has become overwhelmingly important. There is an obvious economic interest, not only in the field of near-room-temperature refrigeration. The threat of a global helium shortage has become a recurring story since the high demand for helium-3 for the detection of nuclear weapons. In the last decade, we have seen a significant increase in the number of companies that market cryogenic refrigerators based on MCE.

Achievements

The development of new materials with a high MCE for application in magnetic refrigeration in household appliances (i.e., close to room temperature) or at low temperatures (e.g., to liquefy hydrogen, natural gas or helium) is one of our main strengths. The design of new cooling systems is another distinguishing feature. Part of our recent activity, in collaboration with the industrial sector, has consisted in the simulation and development of prototypes of adiabatic demagnetization refrigerators (ADR's) for room temperature. In the field of low temperatures, we have found extraordinary values ​​of MCE thanks to various material design strategies: ferromagnetism, frustration and polarization of rare earths by transition metals, among others. Additionally, groundbreaking results from us and other leading groups have shown that molecular materials are a special class of cryogenic magnetic refrigerants. The high modularity at a chemical level allows their properties to be changed in a controlled way. Our contributions in molecular refrigerants include, among others, the first observation of (a) a MCE higher than that of commercially used refrigerants, (b) magnetic refrigeration to temperatures close to absolute zero, (c) the feasibility of small-scale refrigeration, in nanometric deposits and layers.

New magnetic refrigerant

In spite of a remarkably large magnetocaloric effect at temperatures below ca. 10 K, molecular coolers are yet to become excellent magnetic refrigerants. Their main limitation....

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New molecules for cheaper coolers

Rare-earths are expensive and, therefore, our idea is to replace them with other materials, which are a hundred times cheaper and which would make some medical techniques cheaper, such as magnetic resonance imaging.

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Con la refrigeración mediante imanes, los frigoríficos del futuro ahorrarán un 30% de energía

El especial de I+D+i publicado el día 27 de Noviembre de 2017 por el diario ABC se hace eco de la labor efectuada por miembros del grupo en la refrigeración magnética.

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Revolucionan las técnicas de enfriamiento

Un equipo internacional de investigadores con científicos del Instituto de Ciencia de Materiales de Aragón logra por primera vez enfriar por debajo de -272,15 grados Celsius utilizando moléculas magnéticas.

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Moléculas que enfrían

Nuevos materiales magnéticos de base molecular prometen avances en las aplicaciones criogénicas.

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Present and Future

We address the experimental challenges that lie ahead to bring magnetocaloric materials closer to magnetic refrigeration applications. We look at magnetic refrigerants from two perspectives: as bulk for more conventional ADR's and as thin films anchored to a silicon surface for on-chip micro-coolers. For the former, we focus on topics that are of current interest and particularly promising, such as MCE in anisotropic magnets and MCE in frustrated quantum magnets. In parallel, we are advancing in the development of experimental tools, such as nano-calorimetry and direct measurements of MCE from room to very low temperature, which have already made valuable contributions in this field of research. One goal is to reduce the size of refrigerators to the smallest scale, progressing towards innovative niche applications. In this field, we manufacture sensors based on a silicon membrane, where we anchor molecules and metal-organic framework materials with high MCE, either growing in-situ or depositing pre-formed particles. These devices can be used as cooling platforms for all kinds of experiments that require temperatures close to absolute zero, for example, for detecting gamma and X rays in astronomy and materials science, for quantum computing or safety instrumentation.

Our multidisciplinary approach, encompassing cryogenics, quantum magnetism, surface science, and MEMS technologies, along with well-defined goals, leads us to face challenges at the frontiers of scientific and technological knowledge. The European Science Foundation (ESF), through the Expert Committee on Materials Science and Engineering, identifies magnetic refrigeration as a milestone of the Social Challenge on Clean, Safe and Efficient Energy. Advanced functional materials, such as magnetic refrigerants, offer the possibility of building compact and energy efficient magnetic cooling systems, based on the magnetocaloric effect. Furthermore, in the field of cryogenics, such refrigerators represent a means of eliminating dependence on helium (the two natural isotopes), which the EU has recently categorized as a critical raw material, due to its limited supply.

 
 

Projects

Estudio del efecto magnetocalórico y fototérmico de nuevos materiales

MAT2017-86019-R MINECO (2018 – 2020)


Elementos para un sistema de refrigeración magnética en el rango de temperatura de frigoríficos

BSH (Giengen, Zaragoza) OTRI (2013 – 2018)


Strongly correlated electron systems as advanced magnetocaloric materials

IRN-CNRS (2021 – 2025)


Molecules for information and refrigeration technologies

MAT2015-68204-R MINECO (2016 – 2018)


Moléculas para refrigeración magnética

CSIC (PIE-201960E002) (2019)


Explorando mecanismos ferroeléctricos impropios para óxidos funcionales basados en perovskita

RTI2018-098537-B-C22 Ministerio de Ciencia, Innovación y Universidades (2019 – 2021)


Refrigeradores moleculares

RTI2018-094909-J-I00 (ReMo) Ministerio de Ciencia, Innovación y Universidades (2019 – 2020)


Randomly Selected Publications

A decanuclear [(Dy6Zn4II)-Zn-III] cluster: a {Zn-4(II)} rectangle surrounding an octahedral {Dy-6(III)}.

Stavgianoudaki, Nikoleta; Siczek, Milosz; Lis, Tadeusz; Lorusso, Giulia; Evangelisti, Marco; Milios, Constantinos J.

An Investigation of Halogen Bonding as a Structure-Directing Interaction in Dithiadiazolyl Radicals.

Nascimento, Mitchell A.; Heyer, Elodie; Less, Robert J.; Pask, Christopher M.; Arauzo, Ana; Campo, Javier; Rawson, Jeremy M.

What is a crystal to the new chemical crystallographer, after that first, automated structure analysis?.

Falvello, Larry R.

Real-Time Intracellular Temperature Imaging Using Lanthanide Bearing Polymeric Micelles.

Pinol, Rafael; Zeler, Justyna; Brites, Carlos D. S.; Gu, Yuanyu; Tellez, Pedro; Carneiro Neto, Albano N.; da Silva, Thiago E.; Moreno-Loshuertos, Raquel; Fernandez-Silva, Patricio; Isabel Gallego, Ana; Martinez-Lostao, Luis; Martinez, Abelardo; Carlos, Luis D.; Millan, Angel

Exploring through-bond and through-space magnetic communication in 1,3,2-dithiazolyl radical complexes.

Leckie, Dominique; Stephaniuk, Nadia T.; Arauzo, Ana; Campo, Javier; Rawson, Jeremy M.

Structural Insights into the Two-Step Spin-Crossover Compound Fe(3,4-dimethyl-pyridine)(2)[Ag(CN)(2)](2).

Rodriguez-Velamazan, Jose Alberto; Kitase, Kosuke; Palacios, Elias; Castro, Miguel; Fernandez-Blanco, Angel; Burriel, Ramon; Kitazawa, Takafumi

Tetra-n-butylammonium orotate monohydrate: knowleage-based comparison of the results of accurate and lower-resolution analyses and a non-routine disorder refinement.

Ara, Irene; Basdouri, Zeineb; Falvello, Larry R.; Graia, Mohsen; Guerra, Pablo; Tomas, Milagros

Polymorphism of the dinuclear Co-III-Schiff base complex [Co-2(o-van-en)(3)]center dot 4CH(3)CN (o-van-en is a 96 salen-type ligand).

Vrablova, Anna; Cernak, Juraj; Falvello, Larry R.; Tomas, Milagros

Spin-1/2 Quantum Antiferromagnet on a Three-Dimensional Honeycomb Lattice Formed by a New Organic Biradical F4BIPBNN.

Amaya, Naoki; Ono, Toshio; Oku, Yuta; Yamaguchi, Hironori; Matsuo, Akira; Kindo, Koichi; Nojiri, Hiroyuki; Palacio, Fernando; Campo, Javier; Hosokoshi, Yuko

Stability of skyrmion textures and the role of thermal fluctuations in cubic helimagnets: A new intermediate phase at low temperature.

Laliena, Victor; Campo, Javier

Identifying early pathogenic events during vascular calcification in uremic rats.

Hortells, Luis; Sosa, Cecilia; Guillen, Natalia; Lucea, Susana; Millan, Angel; Sorribas, Victor

A symmetric, triply interlaced 3-D anionic MOF that exhibits both magnetic order and SMM behaviour.

Campo, J.; Falvello, L. R.; Forcen-Vazquez, E.; Saenz de Pipaon, C.; Palacio, F.; Tomas, M.

Rational Electrostatic Design of Easy-Axis Magnetic Anisotropy in a Zn-II-Dy-III-Zn-II Single-Molecule Magnet with a High Energy Barrier.

Oyarzabal, Itziar; Ruiz, Jose; Manuel Seco, Jose; Evangelisti, Marco; Camon, Agustin; Ruiz, Eliseo; Aravena, Daniel; Colacio, Enrique

Fluoride-Bridged {Gd-III M-3(III) (2)} ( M= Cr, Fe, Ga) Molecular Magnetic Refrigerants**.

Pedersen, Kasper S.; Lorusso, Giulia; Morales, Juan Jose; Weyhermueller, Thomas; Piligkos, Stergios; Singh, Saurabh Kumar; Larsen, Dennis; Schau-Magnussen, Magnus; Rajaraman, Gopalan; Evangelisti, Marco; Bendix, Jesper

Thermometry at the nanoscale.

Brites, Carlos D. S.; Lima, Patricia P.; Silva, Nuno J. O.; Millan, Angel; Amaral, Vitor S.; Palacio, Fernando; Carlos, Luis D.

Molecular nanoclusters as magnetic refrigerants: The case of Fe-14 with very large spin ground-state.

Evangelisti, M; Candini, A; Ghirri, A; Affronte, M; Piligkos, S; Brechin, EK; McInnes, EJL

Switching of the Chiral Magnetic Domains in the Hybrid Molecular/Inorganic Multiferroic (ND4)(2)[FeCl5(D2O)].

Rodriguez-Velamazan, J. Alberto; Fabelo, Oscar; Campo, Javier; Rodriguez-Carvajal, Juan; Qureshi, Navid; Chapon, Laurent C.

Lanthanide Luminescence to Mimic Molecular Logic and Computing through Physical Inputs.

Hernandez-Rodriguez, Miguel A.; Brites, Carlos D. S.; Antorrena, Guillermo; Pinol, Rafael; Cases, Rafael; Perez-Garcia, Lluisa; Rodrigues, Mafalda; Plaza, Jose Antonio; Torras, Nuria; Diez, Isabel; Millan, Angel; Carlos, Luis D.

Design and optimization of a magnet for magnetocaloric refrigeration.

Francisco Beltran-Lopez, Jesus; Palacios, Elias; Velazquez, David; Burriel, Ramon

Dynamics of chiral solitons driven by polarized currents in monoaxial helimagnets

Laliena, Victor; Bustingorry, Sebastian; Campo Javier;

Intermediate magnetic phase of the magnetoelectric compound (Ca,Sr)BaCo4O7 described with the superspace formalism

J. Lohr, A. L. Larralde, J. Curiale, R. Sanchez, J. Campo, G. J. Cuello, D. Sheptyakov, L. Keller, M. Kenzelmann, G. Aurelio

On new solvatomorphs of the metalloligand [Ni(o-van-en)]

Anna Vráblová, Milagros Tomás, Ján Titiš, Juraj Černák and Larry R. Falvello.

Field induced slow magnetic relaxation in a zig-zag chain-like Dy(III) complex with the ligand o-phenylenedioxydiacetato

Černák, Juraj; Harčarová, Katarína; Falvello, Larry R.; Dlháň, Ľubor; Boča, Roman

Building C(sp3) Molecular Complexity on 2,2’-Bipyridine and 1,10-Phenanthroline in Rhenium Tricarbonyl Complexes

Arevalo, Rebeca; López, Ramón; Falvello, Larry R.; Riera, Lucía; Perez, Julio

A new twist on an old ligand: a [Mn16] double square wheel and a [Mn10] contorted wheel

Thomais G. Tziotzi; Marco Coletta; Mark Gray; Cameron L. Campbell; Scott J. Dalgarno; Giulia Lorusso; Marco Evangelisti; Euan K. Brechin; Constantinos J. Milios;

Efficient Brownian oscillators and nanoheaters based on gallium-doped e-Fe2O3†

Yuanyu Gu; Nuno J. O. Silva; Marie Yoshikiyo; Asuka Namai; Rafael Pinñol; Guillaume Maurin-Pasturel; Yuwen Cui; Shin-ichi Ohkoshi; Angel Millan; Abelardo Martinez

A novel method to obtain integral parameters of the orientation distribution function of textured polycrystals from wavelength-resolved neutron transmission spectra

Miguel Angel Vicente Alvarez; Victor Laliena; Florencia Malamud; Javier Campo; Javier Santisteban

Stability of Ag(III) towards Halides in Organosilver(III) Complexes

Daniel Joven-Sancho, Miguel Baya, Larry R. Falvello, Antonio Martín, Jesús Orduna and Babil Menjón*

Large magnetocaloric effect in EuGd2O4 and EuDy2O4

E.Palacios, R.Sáez-Puche, J.Romero, Y.Doi, Y.Hinatsu, M.Evangelisti

Creation of single chiral soliton states in monoaxial helimagnets

S. A. Osorio, V. Laliena, J. Campo, and S. Bustingorry

Magnonic Goos-Hänchen effect induced by one dimensional solitons

Victor Laliena, Javier Campo

New magnetic intermediate state, “B-phase,” in the cubic chiral magnet MnSi

M. Ohkuma, M. Mito, M. Pardo, Y. Kousaka, S. Iwasaki, K. Ohishi, J. Akimitsu, K. Inoue, V. Laliena, J. Campo.

Scattering of spin waves by a Bloch domain wall: Effect of the dipolar interaction.

Victor Laliena, Athanasios Athanasopoulos and Javier Campo.

Experimental Techniques

Typical experimental techniques employed frequently in these investigations

Magneto caloric effect

lore ipsum...

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Magnetometry

AC susceptibility and
Magnetization at
High magnetic fields (0<40T) and Very low temperatures (mK)

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Thermal Properties

Heat Capacity at low temperatures
DSC
etc..

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PPMS

Heat Capacity at low temperatures
DSC
etc..

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