Nanostructural aspects, free volume and phase constitution of rapidly solidified Nd-Fe-B

A complement of experimental characterization techniques - positron annihilation spectroscopy (PAS), transmission electron microscopy, synchrotron X-ray diffraction and elevated temperature ac and dc magnetic measurements - were applied to the study of melt-quenched stoichiometric Nd2Fe14B ribbons modified by various amounts of the alloying additions Ti and C. These alloying additions are known to enhance the glass-forming ability in Nd2Fe14B melts, allowing for a wider processing window to produce homogeneous nanoscale materials with tailored magnetic properties. The experimental techniques used in this study reveal the complex multi-phase and multi-scale nature of the ribbons, a result that had escaped detection by lower-resolution techniques. The as-quenched ribbons were found to consist of at least three phases: alpha-Fe nanocrystals, poorly crystalline Nd2Fe14B and glass. The measured weight fraction of glass does not show a direct correspondence with quenching wheel speed, a result attributed to the complexity of the melt-spinning heat-transfer process. The Curie temperature of the glassy component of the ribbons varies in a non-systematic way with both Ti and C alloying addition content and wheel speed. PAS provides quantitative measurements of the S (or 'shape')-parameter which represents the size of a void or open volume in the material volume probed. The experimental results indicate that an excess of free volume in the glass is associated with increased glass stability, a counterintuitive conclusion. However, the results are consistent with the model of Sietsma and Thijsse [Phys. Rev. B 52 (5) (1995) 3248] who propose that thermal relaxation in glass causes the larger free volume regions in the amorphous structure to break up into smaller voids, which necessarily increases the total number of voids, but decreases the volume per void. This void breakup fosters the processes of cooperative diffusion and subsequent devitrification. It is concluded that the free volume concentration in the amorphous component of melt-spun Nd2Fe14B alloys produced by the highest quenching wheel speeds and Ti/C alloying addition content is thus not sufficient to allow cooperative diffusion to take place, resulting in an increased stability against devitrification. (C) 2003 Elsevier Science B.V. All rights reserved.