Evolution of the phase state of paramagnetic additions at various stages of synthesis and subsequent thermal treatment of glasses of the system Al 2 O 3-K 2 O-B 2 O 3 simultaneously doped with Fe 2 O 3 and MnO is studied by means of a combination of experimental techniques: Faraday rotation ͑FR͒, electron magnetic resonance ͑EMR͒, transmission electron microscopy ͑TEM͒, Mössbauer spectroscopy, and magnetic measurements. Both FR and EMR show that magnetically ordered clusters occur already at the first stage of the glass preparation. In particular, for the ratio of the Fe and Mn oxides in the charge close to 3:2, fine magnetic nanoparticles are formed with characteristics similar to those of manganese ferrite. By computer simulating the EMR spectra at variable temperatures, a superparamagnetic nature of these nanoparticles is confirmed and their mean diameter is estimated as approximately 3.2 nm. In the thermally treated glasses larger magnetic nanoparticles are formed, giving rise to FR spectra, characteristic of magnetically ordered systems, and the EMR spectra different from those in as-prepared glasses but also showing superparamagnetic narrowing. The Mössbauer spectroscopy corroborates the manganese ferrite structure of the nanoparticles and indicates their coexistence in the ferrimagnetic and superparamagnetic states. The TEM shows the presence of polydisperse nanoparticles on the background of the glass matrix, and electron diffraction of a selected region containing larger particles indicates a crystal structure close to that of MnFe 2 O 4. Energy-dispersive atomic x-ray spectra confirm that the major part of Fe and Mn introduced to the glass composition is gathered in the particles, with the concentration ratio close to 2:1, characteristic of bulk MnFe 2 O 4. Magnetic hysteresis loops of samples subjected to an additional thermal treatment demonstrate a strong increase in the coercive force, remnant magnetization, and high-field magnetic susceptibility with temperature decrease. The consistent results obtained using various techniques demonstrate that the formation of nanoparticles with characteristics close to those of MnFe 2 O 4 confers to these glasses magnetic and magneto-optical properties typical of substances possessing magnetic order.
Magnetic susceptibility, electron paramagnetic resonance (EPR) and optical absorption have been studied in a glass system 20La 2 O 3-22Al 2 O 3-23B 2 O 3-35(SiO 2 + GeO 2) with a part of La 2 O 3 substituted by Gd 2 O 3 in different concentrations. Positive Weiss constants have been found in more heavily doped glasses and ascribed to clustering of Gd 3+ ions. Computer simulations of the EPR spectra show that the short-range ordering in the environment of the Gd 3+ ions is well preserved. The relative distribution widths of the ligand coordinates are less than 2%. In the more heavily doped glasses the EPR spectra are superpositions of signals arising from isolated ions and ferromagnetic clusters. The increase of Gd 3+ concentration is shown to change substantially the strong optical absorption edge while only small changes of f-f absorption band characteristics are observed. This difference is associated with the different effect of the Gd ion clustering on the mechanisms of the strong absorption in the ultraviolet region and the f-f absorption.
Magnetic susceptibility, electron paramagnetic resonance ͑EPR͒, and optical properties have been studied in a glass system ͕20La 2 O 3 − 22Al 2 O 3 − 23B 2 O 3 −35͑SiO 2 +GeO 2 ͖͒ with a part of La 2 O 3 substituted by Gd 2 O 3 in different concentrations. Positive Weiss constants have been found in the more heavily doped glasses and ascribed to clustering of Gd 3+ ions. Two magnetic phase transitions at 55 and 12 K were detected and ascribed, respectively, to ferromagnetic and antiferromagnetic clusters containing Gd ions. The overall shape of the EPR spectra shows the presence of clustering at the higher Gd contents. At low temperatures the cluster-related resonance signal is altered in shape, indicating an onset of magnetic anisotropy field. This signal is convincingly fitted to superparamagnetic resonance arising from ferromagnetic nanoparticles. The clustering, depending on the Gd concentration, correlates with a significant shift to lower energies of the strong optical absorption band edge, ascribed to a charge transfer transition between Gd ions. A nonmonotonous change of refractive index with the increase of the Gd content indicates changes in the glass matrix and in Gd cluster structure.
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