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Dalton Trans ; 48(41): 15386-15396, 2019 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-31257389


Two new neodymium molecular magnets of formula {[Nd(α-fur)3(H2O)2]·DMF}n (1) and {[Nd0.065La0.935(α-fur)3(H2O)2]}n (2), α-fur = C4H3OCOO, have been synthesized. In (1) the furoate ligands, in bidentate bridging mode, consolidate zig-zag chains running along the a-direction. Compound (2) is a magnetically diluted complex of a polymeric chain along the b-axis. Heat capacity, dc magnetization and ac susceptibility measurements have been performed from 1.8 K up to room temperature. Ab initio calculations yielded the gyromagnetic factors gx* = 0.52, gy* = 1.03, gz* = 4.41 for (1) and gx* = 1.35, gy* = 1.98, gz* = 3.88 for (2), and predicted energy gaps of Δ/kB = 125.5 K (1) and Δ/kB = 58.8 K (2). Heat capacity and magnetometry measurements agree with these predictions, and confirm the non-negligible transversal anisotropy of the Kramers doublet ground state. A weak intrachain antiferromagnetic interaction J'/kB = -3.15 × 10-3 K was found for (1). No slow relaxation is observed at H = 0, attributed to the sizable transverse anisotropy component, and/or dipolar or exchange interactions enhancing the quantum tunnelling probability. Under an external applied field as small as 80 Oe, two slow relaxation processes appear: above 3 K the first relaxation mechanism is associated to a combination of Orbach process, with a sizeable activation energy U/kB = 121 K at 1.2 kOe for (1), Raman and direct processes; the second, slowest relaxation mechanism is associated to a direct process, affected by phonon-bottleneck effect. For complex (2) a smaller U/kB = 61 K at 1.2 kOe is found, together with larger g*-transversal terms, and the low-frequency process is quenched. The reported complexes represent rare polymeric Nd single-ion magnets exhibiting high activation energies among the scarce Nd(iii) family.

Sci Rep ; 6: 36212, 2016 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-27796339


Additive manufacturing allows for the production of complex parts with minimum material waste, offering an effective technique for fabricating permanent magnets which frequently involve critical rare earth elements. In this report, we demonstrate a novel method - Big Area Additive Manufacturing (BAAM) - to fabricate isotropic near-net-shape NdFeB bonded magnets with magnetic and mechanical properties comparable or better than those of traditional injection molded magnets. The starting polymer magnet composite pellets consist of 65 vol% isotropic NdFeB powder and 35 vol% polyamide (Nylon-12). The density of the final BAAM magnet product reached 4.8 g/cm3, and the room temperature magnetic properties are: intrinsic coercivity Hci = 688.4 kA/m, remanence Br = 0.51 T, and energy product (BH)max = 43.49 kJ/m3 (5.47 MGOe). In addition, tensile tests performed on four dog-bone shaped specimens yielded an average ultimate tensile strength of 6.60 MPa and an average failure strain of 4.18%. Scanning electron microscopy images of the fracture surfaces indicate that the failure is primarily related to the debonding of the magnetic particles from the polymer binder. The present method significantly simplifies manufacturing of near-net-shape bonded magnets, enables efficient use of rare earth elements thus contributing towards enriching the supply of critical materials.