Magnetocaloric effect and evidence of superparamagnetism in GdAlsub(2) nanocrystallites: A magnetic structural correlation

Abstract

The correlation between structural and magnetic properties of GdA⁢l2, focusing on the role played by the disorder in magnetic ordering and how it influences the magnetocaloric effect (MCE) are discussed. Micrometric-sized particles, consisting of nanocrystallites embedded in an amorphous matrix, were prepared by a mechanical milling technique and characterized by means of x-ray diffraction, scanning and high-resolution transmission electron microscopy as well as magnetic measurements as a function of an applied external magnetic field and temperature. The results show that the average particle size is just slightly diminished (≈7%) with the milling time (between 3 and 13 h), whereas the average crystallite size undergoes an expressive reduction (≈43%). For long milling times, structural disorders mostly associated with crystallite size singularly affect the magnetic properties, leading to a large tablelike MCE in the temperature range between 30 and 165 K. Below 30 K, nanocrystallites with dimensions below a given critical size cause an enhancement in the magnetic entropy change related to superparamagnetic behavior. In contrast, for low milling times, relative cooling power values are improved. These striking features along with the small magnetic hysteresis observed make the milled GdA⁢l2 a promising material for application in the magnetic refrigeration technology. Finally, a discussion in an attempt to elucidate the origin of the spin-glass states previously reported in the literature for mechanically milled GdA⁢l2 samples for very long times (400 and 1000 h) is presented.