Dispersion, ionic bonding and vibrational shifts in phospho-aluminosilicate glasses.

Understanding the relationships between structure and properties of aluminosilicate glasses is of interest in magmatic studies as well as for glass applications as mechanical or optical components. Glass properties may be tailored by the incorporation of additional elements, and here we studied the effect of phosphate incorporation on refractive index and the degree of ionic bonding in aluminosilicate glasses. The studied glasses in the system SiO2-Al2O3-Na2O-P2O5 had a metaluminous composition (Al:Na = 1) with the content of SiO2 ranging from 50 to 70 mol% and of P2O5 from 0 to 7.5 mol%. Refractive index was measured at four wavelengths from visible to near-infrared and found to decrease both with increasing P2O5 content (at the expense of NaAlO2) and with increasing SiO2 content (by substitution of SiO4 for AlO4 groups). This trend correlated with a decrease in density while, additionally, the formation of Al-O-P bonds with an SiO2-like structure may account for this change. The degree of ionic bonding, assessed via optical basicity and oxygen polarisability, decreased with increasing P2O5 and SiO2 content. Despite the complexity of the studied glasses, oxygen polarisability and optical basicity were found to follow Duffy's empirical equation for simple oxide glasses. In the high frequency infrared and Raman spectra, band shifts were observed with increasing P2O5 and SiO2 content. They indicated changing average bond strength of the glass network and showed a linear correlation with optical basicity.

Zinc borate glasses: properties, structure and modelling of the composition-dependence of borate speciation.

The short-range order of binary zinc borate glasses, xZnO-(1-x)B2O3, has been quantitatively described as a function of ZnO content over the entire glass forming range for the first time, to the best of our knowledge. Multiple spectroscopic techniques (11B NMR, Raman, infrared) reveal detailed structural information regarding borate speciation and network connectivity, and a new model for quantifying the molar fractions of short-range order units is proposed. A consistent thermal history dependence for the fraction of tetrahedral boron (N4) is well accounted for by the proposed model. The model predicts density within 0.1% of experimental values and N4 to within 1% of NMR values. The intermediate character of four-coordinated zinc in borate glasses of this series is evident by the far infrared profiles and the glass transition temperature behavior, which decreases non-monotonically with increasing ZnO content.

Pressure-Induced Structural Transformations and Electronic Transitions in TeO2 Glass by Raman Spectroscopy.

TeO2 glass has been studied by Raman spectroscopy up to the record pressure of 70 GPa. The boson peak frequency ωb exhibits a decrease of the ∂ωb/∂P slope at 5-6 GPa and saturates above 30 GPa with a practically constant value up to 70 GPa. Experiment and theory indicate that pressures up to 20 GPa induce the transformation of single Te-O-Te bridges to double Te-O2-Te bridges, leading to a more compact structure, while Raman activity developing at higher pressures around 580 cm-1 signals the increase of Te coordination from 4- to 6-fold. Natural bond orbital analysis shows that double Te-O2-Te bridges favor the s → d transition and promote the increase of Te coordination through d2sp3 hybridization. This transition leads to the formation of TeO6 octahedra, in strict difference with crystalline TeO2 at the same pressure range, and to the development of a 3D network that freezes the medium range order.

Influence of Phosphate on Network Connectivity and Glass Transition in Highly Polymerized Aluminosilicate Glasses.

Melt-derived metaluminous (Al/Na = 1) aluminosilicate glasses in the system SiO2-Al2O3-Na2O-P2O5 were prepared with P2O5 and SiO2 contents varying from 0 to 7.5 and 50 to 70 mol %, respectively. The glass structure was investigated by X-ray absorption near edge structure, far- and medium-infrared, and polarized Raman spectroscopic techniques. The results indicate the incorporation of phosphate into the aluminosilicate network not only as partially depolymerized groups but also as fully polymerized groups charge-balanced by aluminate units in Al-O-P bonds. A new analysis method based on polarized Raman spectra in the bending frequency range indicates a preference of phosphate to reorganize the smallest ring structures. Changes in the glass transition temperature with the increase in phosphate content were found to be consistent with the depolymerization of the network structure shown by spectroscopy. By contrast, increasing the silica content by substituting SiO4 for AlO4 tetrahedra, while keeping the phosphate content constant, was found to have a negligible effect on network polymerization. Still, the glass transition temperature decreased and correlated with a far-infrared sodium band shift to higher frequency. This was interpreted as local changes in bond strength caused by complex interactions between the different network formers and sodium ions.

On the Absence of Doubly Bonded Te═O Groups in TeO2 Glass.

Tellurium oxide clusters (TeO2)6 were investigated through density functional theory to gain information on the structure of TeO2 glass. Among a large number of stable conformers studied, a cyclic, nonsymmetric structure was optimized without terminal Te═O double bonds. The dimer of this structure, (TeO2)12, gives calculated Raman and infrared spectra in very good agreement with the experimental ones, with its total pair distribution function being also in agreement with results of neutron and high-energy X-ray diffraction studies. The (TeO2)12 cluster consists mainly of TeO4 units connected by asymmetric and nearly symmetric Te-O-Te bridges as in γ-TeO2 and involves also edge-sharing through double-oxygen Te-O2-Te bridges as in the ß-TeO2 polymorph. The optimized cluster structure is slightly unstable compared to the calculated global minimum structure, suggesting a kinetically stable product similar to its corresponding experimental TeO2 glass.

Anion polarizabilities in oxynitride glasses. Establishing a common optical basicity scale.

Inspired by the work of John Duffy on optical basicity of oxyfluoride glasses, we apply here the concept of optical basicity to oxynitride systems. While in the original work of Duffy and Ingram the basicity of a medium could be probed by s2 ions like Pb2+, the low energy intrinsic absorption edge of nitride-containing systems does not allow the use of such probe ions. This study uses therefore experimental data on refractive index and density of alkaline earth and rare earth containing silicate oxynitride glasses, prepared by the authors or taken from the literature. In addition, literature reports on experimental or calculated refractive index, density and polarizability data are used to compare pure nitride systems, e.g. bulk or thin film materials that are either crystalline or glassy. We compare simple and complex nitride systems with their oxygen counterparts, by calculating their optical basicity using the chemical composition as well as the established relationship between optical basicity, Λ, and electronic polarizability in oxide systems. Our results on oxynitride systems are in good agreement with Duffy's previous work on oxyfluoride glasses and indicate that the optical basicity varies for the isoelectronic anions in nitrides, oxides and fluorides (N3-:O2-:F-) of a cation Mm+ as follows: Λ(MFm) = 1/2Λ(M2Om) = 1/3Λ(M3Nm). Using this relation for CaO, for which the optical basicity was set as unity by Duffy and Ingram, one has Λ(CaF2) = 0.50, Λ(CaO) = 1.00 and Λ(Ca3N2) = 1.50. The optical basicity of complex nitrides can therefore be calculated by the same method established for oxides using the equivalent fractions and the basicity of the constituent nitrides. The relationship between nitride polarizability αN and basicity Λ(nitride) was found to be linear, with Λ(nitride) = 0.39αN- 0.14 where αN is given in Å3.

Calcium-modified clinoptilolite as a recovery medium of phosphate and potassium from anaerobically digested olive mill wastewater.

Olive mill wastewater (OMW) is characterized as a high-strength effluent due to the high organic load, low biodegradability, and presence of phytotoxic compounds. Most of the OMW treatment methods proposed, including adsorption, focus mainly on the reduction of chemical oxygen demand and recovery of polyphenols. Adsorption studies aiming at nutrient removal from OMW are very limited. In the present work, Ca(OH)2-treated zeolite (CaT-Z) in a granular form was used for simultaneous recovery of phosphate (PO43-) and potassium (K+) ions from two samples of anaerobically digested OMW. Nutrient adsorption was investigated as a function of contact time, pH and dilution of OMW with deionized water. The lower removal efficiency of phosphorus (P) by CaT-Z was observed at higher dilution ratios consisted of 3.125-6.25% OMW-1 and 5% OMW-2. The maximum P removal was 73.9% in 25% OMW-1 and 85.9% in 10% OMW-2. Potassium removal, as the predominant cation of OMW samples, increased from 17.3 to 46.1% in OMW-1 and from 15.1 to 57.7% in OMW-2 with increasing dilution. The maximum experimental adsorption capacities were 15.8 mg K and 2.14 mg P per gram of CaT-Z. Five sequential treatments of 50% OMW-2 with fresh CaT-Z at each stage ensured a cumulative removal of 87.5% for P and 74.9% for K. Adsorption kinetics were faster for K than for P. The plant-available P was found to be the predominant fraction on the loaded CaT-Z. Electron Probe Micro-analysis confirmed the enhanced content of K and P on the loaded CaT-Z, whereas X-ray mapping revealed the co-distribution of Ca and P. This study demonstrates the potential usage of CaT-Z as an immobilization medium of P and K from anaerobically treated OMW.

Structural Stability, Vibrational Properties, and Photoluminescence in CsSnI3 Perovskite upon the Addition of SnF2.

The CsSnI3 perovskite and the corresponding SnF2-containing material with nominal composition CsSnI2.95F0.05 were synthesized by solid-state reactions and structurally characterized by powder X-ray diffraction. Both materials undergo rapid phase transformation upon exposure to air from the black orthorhombic phase (B-γ-CsSnI3) to the yellow orthorhombic phase (Y-CsSnI3), followed by irreversible oxidation into Cs2SnI6 within several hours. The phase transition occurs at a significantly lower rate in the SnF2-containing material rather than in the pure perovskite. The high hole-carrier concentration of the materials prohibits the detection of Raman signals for B-γ-CsSnI3 and induces a very strong plasmonic reflectance in the far-IR. In contrast, far-IR phonon bands and a rich Raman spectrum are observed for the Y-CsSnI3 modification below 140 cm-1 with weak frequency shift gradients versus temperatures between -95 and +170 °C. Above 170 °C, the signal is lost due to B-α-CsSnI3 re-formation. The photoluminescence spectra exhibit residual blue shifts and broadening as a sign of structural transformation initiation.

Structure and properties of orthoborate glasses in the Eu2O3-(Sr,Eu)O-B2O3 quaternary.

The structure and properties of melt-quenched glasses and partially crystallized samples from the borate series (1-2x)Eu2O3-x((Eu,Sr)O-B2O3) were investigated in the supermodified regime of x < 0.5, using Raman, infrared (IR), electron spin resonance (ESR), and UV-vis absorption and fluorescence spectroscopic techniques. ESR and optical spectroscopy showed that, despite the strongly reducing synthesis conditions, the Eu(2+)/Eu(3+) equilibrium remained shifted to the side of trivalent Eu(3+). Stable and transparent overmodified borate glasses were produced for compositions with x ≥ 0.36. Higher europium oxide concentrations resulted in precipitation of crystalline Eu2Sr3(BO3)4 and EuBO3 phases, as traced by X-ray diffraction. Raman and IR spectroscopy showed that the metaborate configuration which is present at x = 0.46 transforms gradually, with increasing Eu2O3 levels, into orthoborate [BO3](3-) triangular units. At higher europium oxide content (x ≤ 0.36), the presence of Eu(3+) supports the formation of orthoborate [BØ2O2](3-) tetrahedral species. These units organize into [B3O9](9-) rings, which exist in equilibrium with [BO3](3-) triangles. As a consequence, distinct variations can be observed also in the macroscopic properties such as density, glass transition temperature, refractive index, optical basicity, and oxygen polarizability. This observation confirms previous findings on manganese-strontium borates with high modification levels.

Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses.

Ionic sulfophosphate liquids of the type ZnO-Na2O-Na2SO4-P2O5 exhibit surprising glass forming ability, even at slow or moderate cooling rate. As a concept, they also provide high solubility of transition metal ions which could act as cross-linking sites between the sulfate and phosphate entities. It is therefore investigated how the replacement of ZnO by MnO and/or FeO affects the glass structure and the glass properties. Increasing manganese levels are found to result in a monotonic increase of the transition temperature Tg and most of the mechanical properties. This trend is attributed to the change of metal-ion coordination from four-fold around Zn(2+) to six-fold around Mn(2+) ions. The higher coordination facilitates cross-linking of the ionic structural entities and subsequently increases Tg. Raman and infrared spectroscopy show that the structure of these glasses involves only SO4(2-) and PO4 (3-) monomers as well as P2O7(4-) dimers. Replacement of ZnO by MnO is found to favour PO4(3-) over P2O7(4-) species, a trend which is enhanced by co-doping with FeO. Both transition metal ions show, like Zn(2+), a preference to selectively coordinate to phosphate anionic species, as opposed to sodium ions which coordinate mainly to sulfate anions. EPR spectroscopy finally shows that divalent Mn(2+) ions are present primarily in MnO6-clusters, which, in the studied sulfophosphate glasses, convert upon increasing MnO content from corner-sharing to edge-sharing entities.

Composition and temperature dependence of cesium-borate glasses by molecular dynamics.

The structural aspects of xCs2O-(1-x)B2O3 glasses have been investigated by molecular dynamics as functions of Cs2O content (x=0.2, 0.3, and 0.4) and temperature (T=300 and 1250 K). The tetrahedral (BØ4-) and triangular (BØ3,BØ2O-, and BØO2 (2-)) short-range order borate units were found to be the structure-building entities of the simulated glasses [Ø=bridging oxygen (BO) and O-=nonbridging oxygen (NBO) atom]. The increase of Cs2O content results in the progressive increase of the NBO-containing triangle population at the expense of the BO4- tetrahedral units. The same effect is caused by temperature increase at a fixed Cs2O content, and this was associated with the "fragile" characteristics of alkali borate glasses. A comparison of simulated Cs and Li borates showed very similar structures at x=0.2, but dissimilar ones when the alkali content exceeds this composition. In particular, for x>0.2 Cs borates exhibit a preference for NBO formation relative to Li borates. Differences in the microstructure of sites hosting Cs ions were found, and this permits their classification into bridging (b type) and nonbridging type (nb type) of sites. b-type sites consist exclusively of BO atoms, while both BO and NBO atoms participate in nb-type sites. These differences in Cs-site local bonding characteristics were found to be reflected on the Cs-O(site) vibration frequencies. Also, the computed Cs-O vibrational responses for simulated Cs borates were found to compare well with experimental far-infrared spectra.