Vibrational characteristics of aluminum-phosphate compounds by an experimental and theoretical approach.

Aluminum phosphates are materials with relatively wide potential applications in many industries. The vibrational features of selected compounds were established on Raman and infrared spectroscopy. The experimentally determined spectra are compared to those calculated by ab initio methods. This gives a unique possibility of a proper assignment of the experimental spectral features to specific modes of vibration. In the results, it was evidenced that the spectra are characterized by two specific intense bands in the mid- and high-frequency range due to the P-O-P and P-O bonds in [PO4] tetrahedron vibrations. The position of the high-frequency band is related to the number of bridging oxygen atoms connecting [PO4] tetrahedrons in the unit cell. Additionally, the differences in the spectra were evidenced as a result of different polymorphic forms of the selected compounds. Therefore, the results may be useful in determining the phase composition of polyphase materials or structural features of aluminum-phosphate glasses and glass-ceramic materials.

A new iron-phosphate compound (Fe7P11O38) obtained by pyrophosphate stoichiometric glass devitrification.

Iron phosphates are a wide group of compounds that possess versatile applications. Their properties are strongly dependent on the role and position of iron in their structure. Iron, because of its chemical character, is able to easily change its redox state and accommodate different chemical surroundings. Thus, iron-phosphate crystallography is relatively complex. In addition, the compounds possess intriguing magnetic and electric properties. In this paper, we present crystal structure properties of a newly developed iron-phosphate compound that was obtained by devitrification from iron-phosphate glass of pyrophosphate stoichiometry. Based on X-ray diffraction (XRD) studies, the new compound (Fe7P11O38) was shown to adopt the hexagonal space group P63 (No. 173) in which iron is present as Fe3+ in two inequivalent octahedral and one tetrahedral positions. The results were confirmed by Raman and Mössbauer spectroscopies, and appropriate band positions, as well as hyperfine interaction parameters, are assigned and discussed. The magnetic and electric properties of the compound were predicted by ab initio simulations. It was observed that iron magnetic moments are coupled antiferromagnetically and that the total magnetic moment of the unit cell has an integer value of 2 µB. Electronic band structure calculations showed that the material has half-metallic properties.

Development of a New Sr-O Parameterization to Describe the Influence of SrO on Iron-Phosphate Glass Structural Properties Using Molecular Dynamics Simulations.

Iron-phosphate glasses, due to their properties, have many potential applications. One of the most promising seems to be nuclear waste immobilization. Radioactive 90Sr isotope is the main short-lived product of fission and, due to its high solubility, it can enter groundwater and pose a threat to the environment. On the other hand, Sr is an important element in hard tissue metabolic processes, and phosphate glasses containing Sr are considered bioactive. This study investigated the effect of SrO addition on a glass structure of nominal 30Fe2O3-70P2O5 chemical composition using classical molecular dynamics simulations. To describe the interaction between Sr-O ion pairs, new interatomic potential parameters of the Buckingham-type were developed and tested for crystalline compounds. The short-range structure of the simulated glasses is presented and is in agreement with previous experimental and theoretical studies. The simulations showed that an increase in SrO content in the glass led to phosphate network depolymerization. Analysis demonstrated that the non-network oxygen did not take part in the phosphate network depolymerization. Furthermore, strontium aggregation in the glass structure was observed to lead to the non-homogeneity of the glass network. It was demonstrated that Sr ions prefer to locate near to Fe(II), which may induce crystallization of strontium phosphates with divalent iron.

An Insight into the Correlation between Chemical Composition Changes of Aluminum-Iron-Polyphosphate Glasses and Thermal Properties.

The present study aimed to investigate the influence of the gradual substitution of Fe2O3 by Al2O3 on the thermal properties of polyphosphate glasses. The conducted considerations based on differential scanning calorimetry (DSC) and heating microscopy thermal analysis provided much essential information about the correlation between glass chemical composition and its characteristic parameters, such as transformation temperature, specific heat, crystallization temperature, crystallization enthalpy, the activation energy of crystal growth, melting temperature, and Angell glass thermal stability. The obtained estimation of viscosity changes as a function of temperature could be very helpful for researchers to correctly plan the vitrification process and thus radioactive waste immobilization. A precise analysis of DSC curves and X-ray diffraction patterns revealed the possibility of crystallization process design in order to create materials with different levels of crystallinity and phase composition. The drawn conclusions allow choosing the glass with the optimal concentration of Al2O3 and Fe2O3, which ensures the relatively low melting temperature, viscosity, and glass crystallization ability, with application potential in nuclear waste immobilization.

Thermoluminescence Enhancement of LiMgPO4 Crystal Host by Tb3+ and Tm3+ Trivalent Rare-Earth Ions Co-doping.

We investigated the influence of terbium and thulium trivalent rare-earth (RE) ions co-doping on the luminescent properties enhancement of LiMgPO4 (LMP) crystal host. The studied crystals were grown from the melt by micro-pulling-down (MPD) technique. Luminescent properties of the obtained crystals were investigated by thermoluminescence (TL) method. The most favorable properties and the highest luminescence enhancement were measured for Tb and Tm double doped crystals. A similar luminescence level can be also obtained for Tm, B co-doped samples. In this case, however, the low-temperature TL components have a significant contribution. The measured luminescent spectra showed a typical emission of Tb3+ and Tm3+ ions of an opposite trapping nature, namely the holes and electron-trapping sites, respectively. The most prominent transitions of 5D4 → 7F3 (550 nm for Tb3+) and 1D2 → 3F4 (450 nm for Tm3+) were observed. It was also found that Tb3+ and Tm3+ emissions show temperature dependence in the case of double doped LMP crystal sample, which was not visible in the case of the samples doped with a single RE dopant. At a low temperature range (up to around 290 °C) Tm3+ emission was dominant. At higher temperatures, the electrons occupying Tm3+ sites started to be released giving rise to emissions from Tb-related recombination centers, and emissions from Tm3+ centers simultaneously decreased. At the highest temperatures, emission took place from Tb3+ recombination centers, but only from deeper 5D4 level-related traps which had not been emptied at a lower temperature range.