This study focuses on the synthesis of FeRh nanoparticles via pulsed laser ablation in liquid and on controlling the oxidation of the synthesized nanoparticles. Formation of monomodal γ-FeRh nanoparticles was confirmed by transmission electron microscopy (TEM) and their composition confirmed by atom probe tomography (APT). For these particles, three major contributors to oxidation were analysed: (1) dissolved oxygen in the organic solvents, (2) the bound oxygen in the solvent and (3) oxygen in the atmosphere above the solvent. The decrease of oxidation for optimized ablation conditions was confirmed through energy-dispersive X-ray (EDX) and Mössbauer spectroscopy. Furthermore, the time dependence of oxidation was monitored for dried FeRh nanoparticles powders using ferromagnetic resonance spectroscopy (FMR). By magnetophoretic separation, B2-FeRh nanoparticles could be extracted from the solution and characteristic differences of nanostrand formation between γ-FeRh and B2-FeRh nanoparticles were observed.
The development of magnetocaloric materials represents an approach to enable efficient and environmentally friendly refrigeration. It is envisioned as a key technology to reduce CO2 emissions of air conditioning and cooling systems. Fe-Rh has been shown to be one of the best-suited materials in terms of heat exchange per material volume. However, the Fe-Rh magnetocaloric response depends on its composition. Hence, the adaptation of material processing routes that preserve the Fe-Rh magnetocaloric response in the generated structures is a fundamental step towards the industrial development of this cooling technology. To address this challenge, the temperature-dependent properties of laser synthesized Fe-Rh nanoparticles and the laser printing of Fe-Rh nanoparticle inks are studied to generate 2D magnetocaloric structures that are potentially interesting for applications such as waste heat management of compact electrical appliances or thermal diodes, switches, and printable magnetocaloric media. The magnetization and temperature dependence of the ink’s γ-FeRh to B2-FeRh magnetic transition is analyzed throughout the complete process, finding a linear increase of the magnetization M (0.8 T, 300 K) up to 96 Am2/kg with ca. 90% of the γ-FeRh being transformed permanently into the B2-phase. In 2D structures, magnetization values of M (0.8 T, 300 K) ≈ 11 Am2/kg could be reached by laser sintering, yielding partial conversion to the B2-phase equivalent to long-time heating temperature of app. 600 K, via this treatment. Thus, the proposed procedure constitutes a robust route to achieve the generation of magnetocaloric structures.
Pronounced magnetocaloric effects are typically observed in materials that often contain expensive and rare elements and are therefore costly to mass produce. However, they can rather be exploited on a small scale for miniaturized devices such as magnetic micro coolers, thermal sensors, and magnetic micropumps. Herein, a method is developed to generate magnetocaloric microstructures from an equiatomic iron–rhodium (FeRh) bulk target through a stepwise process. First, paramagnetic near‐to‐equiatomic solid‐solution FeRh nanoparticles (NPs) are generated through picosecond (ps)‐pulsed laser ablation in ethanol, which are then transformed into a printable ink and patterned using a continuous wave laser. Laser patterning not only leads to sintering of the NP ink but also triggers the phase transformation of the initial γ‐ to B2‐FeRh. At a laser fluence of 246 J cm−2, a partial (52%) phase transformation from γ‐ to B2‐FeRh is obtained, resulting in a magnetization increase of 35 Am2 kg−1 across the antiferromagnetic to ferromagnetic phase transition. This represents a ca. sixfold enhancement compared to previous furnace‐annealed FeRh ink. Finally, herein, the ability is demonstrated to create FeRh 2D structures with different geometries using laser sintering of magnetocaloric inks, which offers advantages such as micrometric spatial resolution, in situ annealing, and structure design flexibility.
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