ZnFe 2 O 4 ferrite nanoparticles are arousing a great interest in the biomedical field, thanks to their superparamagnetic behavior at room temperature. Functional properties depend on composition, size, nanoparticle architecture and, in turn, on the synthesis methods. Bulk ZnFe 2 O 4 has the normal spinel structure (all Zn 2+ ions in tetrahedral and all Fe 3+ ions in octahedral positions), but at the nanometric size inversion takes place with a cationic mixing on divalent and trivalent sites. The sensitivity of the Raman probe to cation disorder favored the appearance of several works on a rich variety of nanosized zinc ferrites. An overview on these results is reported and discussed at variance with synthesis methods, grain dimensions, and dopants. We add to this landscape our results from new nanosized powder samples made by microwave-assisted combustion, with different dopants (Ca, Sr on Zn site and Al, Gd on Fe site). A detailed analysis of A 1g , E g , 3F 2g Raman modes has been performed and Raman band parameters have been derived from bestfitting procedures and carefully compared to literature data. The vibrational results are discussed taking into account the characterization from X-ray powder diffraction raction, SEM-EDS probe, EPR spectroscopy and, of course, the magnetic responses.
Black phosphorus (BP) is a two-dimensional material potentially of great interest for applications in the fields of energy, sensing, and microelectronics. One of the most interesting methods to obtain BP is the conversion from red phosphorus (RP) by means of high-energy mechanochemical synthesis. To date, however, this synthesis process was not well characterized. In this work, starting from the mathematical model of energy transfer during the ball milling process, we investigate the effects on RP → BP conversion of three experimental parameters, the rotation speed, the milling time, and the weight ratio between the spheres and the milled material (BtPw ratio). The efficiency of the conversion process was verified by solid-state NMR, Raman spectroscopy, and X-ray diffraction. Whereas the first two parameters have a minor importance, the BtPw ratio plays a primary role in the RP → BP conversion. Yields approaching 100% can be obtained also with short milling times (15 min) and adequate rotation speed (e.g., 500 r.p.m.), provided that the BtPw ratio >40:1 is used. These results confirm the energy sustainability of the mechanochemical synthesis approach.
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