Surfactant-assisted production of TbCu2 nanoparticles

The production of surfactant-assisted metallic nanoparticles of TbCu2 has been achieved by the combination of high-energy ball milling in tungsten carbide containers and the use of oleic acid (C18H34O2) and heptane (C7H16). The alloys were first produced in bulk pellets by arc melting and subsequently milled for only 2 and 5 h in oleic acid (15 and 30% mass weight). The powders consist of an ensemble of nanoparticles with a TbCu2 lattice cell volume of ≈215 Å3, an average particle diameter between 9 and 12 nm and inhomogeneous lattice strain of 0.2–0.4%, as deduced from X-ray diffraction data. The nanometric sizes of the crystals with defined lattice planes are close to those obtained by transmission electron microscopy. Raman spectroscopy shows the existence of inelastic peaks between 1000 and 1650 cm−1, a characteristic of C18H34O2. The magnetisation shows a peak at the antiferromagnetic-paramagnetic transition with Néel temperatures around 48 K (below that of bulk alloy) and a distinctive metamagnetic transition at 5 K up to 40 K. The Curie-Weiss behaviour above the transition reveals effective Bohr magneton numbers (≈9.1–9.9 μB) which are close to what is expected for the free Tb3+ ion using Hund’s rules. The metamagnetic transition is slightly augmented with respect to the bulk value, reaching H = 24.5 kOe by the combined effect of the size reduction and the lattice strain increase and the increase of magnetic disorder. At low temperatures, there is irreversibility as a result of the existing magnetic disorder. The moment relaxation follows an Arrhenius model with uncompensated Tb moments, with activation energies between 295 and 326 K and pre-exponential factors between 10−11 and 10−13 s. The results are interpreted as a consequence of the existence of a diamagnetic surfactant which drastically decreases the magnetic coupling between interparticle moments.