Rare earths in fluoride glasses: The LnF3AlF3ThF4BaF2 systems and related glasses

Glass compositions have been investigated in the BaF₂AlF₃ThF₄LnF₃ systems (Ln = rare earths or Y). Glasses have been obtained for the compositions 0.2 BaF₂, 0.3 AlF₃, 0.2 ThF₄, 0.3 LnF₃ and 0.3 BaF₂, 0.3 AlF₃, 0.2 ThF₄, 0.2 LnF₃ for the rare earths heavier than samarium. The glassy transition occurs near 450°C and fusion near 750°C; the density is between 5 and 6 and refractive index between 1.48 and 1.50. Large amounts of alkali fluorides (LiF, NaF, KF) may be included in the glass composition. The glassy area has been drawn in the pseudo-ternary system NaF(Al_0.5Y_0.5)F₃(Ba_0.5Th_0.5)F₃. Alkali incorporation leads to a decrease of the characteristic temperatures. Numerous new glassy compositions are given deriving from the basic ternary or quaternary systems with the addition of alkali fluoride, MgF₂ and CaF₂.     

Raman spectroscopic studies of aluminium fluoroberyllate glasses

Aluminium fluoroberyllate glasses obtained in the vitreous domain from the quaternary system BaF₂CaF₂AlF₃BeF₂ have been studied by Raman spectroscopy. The observed bands have been assigned by comparison with those of cryolite molten aluminofluorides, and of various fluoroberyllates in the crystalline and molten state. The following species have been identified: (AlF₄)^? tetrahedral groups, (AlF₆)^?3 octahedral groups polymerized in chains, and a few polymerized species of beryllium fluoride and probably Be₂F₇^?3 dimers.     

Vibrational spectra and structure of chloro-fluorozirconate glasses

A series of barium chloro-fluorozirconate glasses have been prepared. Their IR absorption, IR reflectivity and Raman spectra have been measured down to 33 cm^?1. The glass transition and crystallization temperatures have also been measured. The high frequency IR absorption and Raman modes of the chloro-fluorozirconate glasses have been assigned as in fluorozirconate glasses. The IR reflection spectra of chloride-containing glasses differed from the fluorozirconates in that one band was clearly related to Cl atom motions. The structure of the glasses probably consists of zig-zag chains of ZrCl₂F₄ mixed halide octahedra plus a pure fluoride matrix whose structure is similar to that of a ZrF₄BaF₂ glass with the same composition.     

Fluoride glasses in the ZrF4BaF2YF3AlF3 quaternary system

The quaternary system ZrF₄BaF₂YF₃AlF₃ has been investigated in order to determine the nature of the vitreous domain. Addition of aluminium fluoride to the basic ZrF₄BaF₂YF₃ ternary system results in an increase in the size of the vitreous area and a lowering of the crystallization rate.The change of density, refractive index and T_G with respect to composition has been studied. It has been shown that the substitution of Zr⁴⁺/Al³⁺ involves a change in the cationic distribution rather than in the anionic packing.     

An X-ray diffraction study of the structure of barium fluorozirconate and fluorohafnate glasses

Two binary glasses have been prepared in the ZrF₄BaF₂ and HfF₄BaF₂ systems, containing 64 mol.% ZrF₄ and 66 mol.% HfF₄, respectively. The two plate-like glass samples were studied by X-ray diffraction, and the resulting data were subjected to a Fourier analysis. The pair correlation functions thus obtained yield a ZrF (or HfF) nearest neighbor coordination number of ～ 7.6 for both glasses. The second peak in the correlation functions has been assigned to a combination of FF and BaF interactions, while the third peak is probably due in part to ZrZr (Hf-Hf) interactions. The diffraction data have been compared with the predictions of structural models for barium fluorozirconate and fluorohafnate glasses.     

Mössbauer study of europium in fluorozirconate glass

¹⁵¹Eu Mössbauer spectra of fluorozirconate glasses of nominal composition 0.61 ZrF₄ · (0.32 ? x) BaF₂ · x EuF₂ · 0.07 ThF₄ with x = 0.10 and 0.20 show that Eu²⁺ is present in sites with isomer shifts in the range ?15.5 to ?12.9 mm/s, corresponding to EuF bond lengths of 2.3–2.8 Å and a coordination number ranging from 8 to 12. The glasses contain a minor amount (～10%) of Eu³⁺ in well-defined sites. Effective Debye temperatures deduced from the recoilless fractions for the two ions are θ_D²⁺ = 145 K and θ_D³⁺ = 261 K. The differences in coordination and bonding indicate that trivalent eurpoium is a network former, whereas the divalent ions are network modifiers.     

Radiation effects in ZrF4 based glasses: I. Electron spin resonance

Binary ZrF₄BaF₂, HfF₄BaF₂, and multicomponent ZrF₄ based glasses have been studied by electron spin resonance spectroscopy after liquid-nitrogen-temperature X-irradiations and room-temperature γ-ray irradiations. Polycrystalline BaF₂, ZrF₄ and HfF₄ were investigated in the same manner for comparison purposes. Isochronal anneal experiments have distinguished several resonances in the glasses which are characterized as due to F₂^? molecular ions, F⁰ interstitial atoms and Zr³⁺ and Hf³⁺ ions. Two more signals are tentatively assigned as due to a hole trapped on several fluorine ions and a hole trapped on an oxygen impurity. In lead-containing glasses the formation of Zr³⁺ is strongly inhibited, presumably due to the competitive formation of Pb⁺ ions. However, the radiation production of Pb³⁺ ions was independently observed, thus suggesting that the Pb²⁺ ions may serve as traps for charge carriers of either sign. No defects were detected which could be explicitly associated with other cationic constituents, such as La³⁺, Al³⁺, or Li⁺.     

Optical properties of new low-phonon SnF2–PbF2–ZnF2 glasses

New fluoride glasses were developed in the SnF₂–PbF₂–ZnF₂ system. Additions of 5 mol% of CsCl or 6–15 mol% of AlF₃ were found to stabilize the glass formation. The IR absorption of the glasses and the optical properties of the europium ions doped in the glasses were compared with those of a fluorozirconate glass as a representative fluoride glass. The IR spectra showed that the new glasses have the peak of the phonon energy at 400 cm⁻¹, which is about 100 cm⁻¹ lower than that of the fluorozirconate glass. The results of the fluorescence measurement of the europium ions revealed that the multi-phonon relaxation rate in these glasses is smaller than that in the fluorozirconate glass.     

Lanthanum fluorozirconate glasses

Investigations in the ZrF₄-BaF₂-LaF₃ ternary system show the existence of a vitreous area in the range: ZrF₄: 56–67%, BaF₂:25–36%, LaF₃:3–13%. For a standard glass of molar composition 0.62 ZrF₄, 0.30 BaF₂, 0.08 LaF₃, the refractive index is 1.5248 with the glassy transition occuring at 310°C and fusion occuring at 545°C.Quaternary glasses have been obtained by including a MF fluoride (M = Na or Li) with the previous ternary glass according to the formula: (0.62 – 0.4x)ZrF₄(0.30 –0.5x)BaF₂(0.088 – 0.1x)LaF₃xMF. Evolution of glassy transition, refractive index, density and molar refractivity is discussed in relation to the structural role of the Na⁺ and Li⁺ ions. In these zirconium fluoride glasses, lithium could act as a network former at low concentration and as a network modifier at higher concentration.     

New fluoride glasses based on 4f and 5f elements

New fluoride glasses have been isolated in the ternary systems ThF₄-LnF₃-BaF₂ with Ln = the lanthanides Yb, Y, Tm. The melt must be quenched to reduce crystallization. They are simply prepared from oxides by an appropriate NH₄F, HF treatment. The IR transmission is remarkable, the optical window lying in the 0.25-10 μm region.     

Crystallization kinetics of fluoride nanocrystals in oxyfluoride glasses

Oxyfluoride glasses containing different alkaline earth fluoride (CaF₂, SrF₂, and BaF₂) were prepared and their crystallization behavior was analyzed using non-isothermal kinetics based upon differential scanning calorimetry (DSC) scan results. The glass containing CaF₂ showed the fastest kinetics for CaF₂ crystallization, while that containing BaF₂ showed the slowest kinetics for BaF₂ crystallization. On the other hand, all the oxyfluoride glasses showed very similar behavior in the crystallization of glass matrices. The difference in the crystallization behavior of the oxyfluoride glasses was discussed based upon the difference in the size of alkaline earth ions and the difference in the dissociation energy of alkaline earth-fluorine bonds.     

Crystallization in fluoride glasses: I. Devitrification on reheating

The devitrification of glass from the BaF₂LaF₃ZrF₃AlF₃ quaternary system is studied as a function of sample size and heating rate by differential scanning calorimetry. Results are analyzed in terms of a theory of non-isothermal crystallization kinetics similar to that of Matusita and Sakka but modified to allow for diffusion controlled growth of the crystallites.     

Electrical and dielectric properties of MnF2–ZnF2–NaPO3 glasses

Direct electrical conductivity and dependencies of complex electrical modulus vs. temperature and frequency have been measured on glasses from the MnF₂–ZnF₂–NaPO₃ system. These glasses are sensitive to atmospheric humidity and as a consequence, the electrical conductivity increases up to temperature of 50 °C. A hydrated layer is created by the effect of water and leads to the significant increase of the electrical conductivity in the case of 0MnF₂–20ZnF₂–80NaPO₃ glass. This behavior is governed by Arrhenius relation where the values of activation energy are increasing and values of the electrical conductivity are decreasing with the amount of MnF₂. Dielectric measurements show that a heterogeneous phase is formed in the bulk of glasses. This may be seen when plotting complex electrical modulus in the complex plane. The records made by the light microscope confirmed the occurrence of the other phase in the bulk of glasses.     

Raman study of the structure of glasses along the join SiO2GeO2

In order to better understand the distribution of tetrahedra in multicomponent tetrahedral network structures of melts and glasses, we have investigated the Raman spectra of binary SiO₂GeO₂ glasses. We compare the Raman spectral features of the end-member glasses and discuss their vibrational origins. The mixing of GeO₂ and SiO₂ melts results in a continuous random network structure of TO₄ tetrahedra (T  Si, Ge) in the glass. Raman bands corresponding to the asymmetric stretch (v_as) of oxygen in GeOGe, SiOSi and SiOGe bonds are observed in the glasses having intermediate compositions along the SiO₂GeO₂ join. The presence of three distinct v_as (TOT) bands in the spectrum of a glass having Si/Ge one reveals that a considerable degree of SiGe disorder exists in the glass. The presence of a single symmetric oxygen stretching band in the spectra of binary SiO₂GeO₂ glasses indicates that the symmetric stretch modes (v_s) of oxygen in SiOSi, SiOGe and GeOGe bonds are strongly coupled. An observed decrease in the halfwidth of the v_s (TOT) band in the spectra of SiO₂GeO₂ glasses with increasing concentration of GeO₂ may be attributed to a decrease in the average TOT bond angle and a predominance of six-membered ring structures. Results of the present study support the assignment of the bands in the 900–1200 cm^?1 region of the alumino-silicate glasses, spectra to the v_as(AlOSi) and v_as(SiOSi) modes. In contrast to the alumino-silicate glasses, however, the SiO₂GeO₂ glasses have a much higher degree of disorder of the network-forming cations.     

Infrared spectra and structure of superionic conducting glasses in the system AgIAg2OMoO3

Thin blown films of glasses with the mole ratio Ag₂O/MoO₃ = 1 in the system AgIAg₂OMoO₃ (or the pseudobinary system AgIAg₂MoO₄) show three absorption bands in the range 4000-200 cm^?1; 875 cm^?1 (w), 780 cm^?1 (s), and 320 cm^?1 (m, b), which are characteristic of tetrahedral MoO₄^2? ions. The glasses with the ratio Ag₂O/MoO₃ < 1 have two additional bands at 600 cm^?1 (w) and 450 cm^?1 (vw), which are characteristic of condensed ions of MoO₄ tetrahedra, probably Mo₂ O₇^2? ions. These glasses are thus composed of Ag⁺, I^?, MoO₄^2?, and probably Mo₂O₇^2? ions, and classified as “ionic” glasses containing one type of cations. The presence of partial covalency in the Ag⁺… ^?OMo link and the influence of ion exchange of Ag⁺ with K⁺ on IR spectra are discussed. The molar volume of the glasses with the ratio Ag₂O/MoO₃ = 1 is primarily determined by a fairly dense packing of the constituent anions, I^? and MoO₄^2?.     

Optical absorption of cobalt (II) in binary thallium borate glasses

The optical absorption spectra of cobalt (II) in Tl₂OB₂O₃ glasses have been studied and compared with those in binary alkali borate glasses. In thallium borate glasses cobalt (II) may be present in octahedral and/or in tetrahedral symmetry depending upon the composition of the glass. In low thallium borate glasses cobalt (II) is octahedral while the concentration of tetrahedral cobalt (II) increases with increasing Tl₂O content of the glass; the formation of tetrahedral cobalt (II) becomes noticeable when the concentration of Tl₂O reaches above the critical concentration of about 19 mol %. The ligand field parameters: 10Dq and B have been calculated from the absorption spectra of cobalt (II) in different glasses and it has been found that the Racah parameter, B, is more in Tl₂OB₂O₃ glasses than those in Na₂OB₂O₃ or K₂OB₂O₃ glasses of corresponding molar composition. This indicates that the donor capacity of the BO₄ group in thallium borate glasses is lower than that in alkali borate glasses; this is consistent with the NMR results in Tl₂OB₂O₃ glasses containing less than 20 mol % Tl₂O where three BO₄ groups have been found to form with each Tl₂O unit added.     

Structure and properties of silver phosphate glasses — Infrared and visible spectra

The infrared and visible spectra of glasses in the Ag₂OP₂O₅ glass-forming system were obtained. The infrared data were interpreted as indicating the presence of polymeric chains in these glasses. The partial covalent nature of the AgOP bond was discussed. A mixed NaPO₃AgPO₃ glass showed no unexpected bands in the infrared spectrum, again showing that silver is behaving in a manner similar to alkali metal ions in phosphate glasses. The shift in the absorption edge in the visible spectra of glasses of different Ag/P ratio was shown to arise from either an increase in the concentration of nonbridging oxygens with increasing silver content, or the presence of colloidal silver metal particles.     

NMR studies on rapidly solidified SiO2Al2O3 and SiO2Al2O3Na2O-glasses

²⁷Al and ²⁹Si MAS NMR studies were performed on roller-quenched SiO₂Al₂O₃-glasses with Al₂O₃ contents ranging from 10 to 60 mol% and on SiO₂Al₂O₃Na₂O glasses containing 10 mol% Al₂O₃ and 2.5 to 10 mol% Na₂O. Pure aluminium silicate glasses show NMR peaks at 0, 30 and 60 ppm. The frequency distribution of the different Al-sites is not affected by the glass composition. In glasses of the system SiO₂Al₂O₃Na₂O the 30 ppm peak decreases to zero as the Na₂O content increases. The 30 ppm peak is assigned to distorted triclustered AlO-tetrahedra, rather than to fivefold coordinated Al. Triclustering of tetrahedra may provide for charge neutrality in glasses with molar excess of Al₂O₃ over Na₂O. As charge balance is increasingly achieved by addition of alkali ions, the tendency of tetrahedral triclustering is reduced, reflected by the disappearance of the 30 ppm peak in glasses containing ≥ 7.5 mol% Na₂O.     

Raman spectroscopic investigation of the structure of silicate glasses (II). Soda-alkaline earth-alumina ternary and quaternary glasses

Raman spectra of some ternary and quaternary glasses in the system Na₂OCaOMgOAl₂O₃SiO₂ are presented. The spectra are interpreted in terms of the structural alteration of the glass as the composition is altered from the binary end members to more complicated glasses. Addition of CaO and MgO to soda-silica glasses act only to increase the disorder of the network slightly. Addition of Al₂O₃ greatly modifies the network. In some soda-lime-aluminosiliscate compositions an estimate can be made of the amount of aluminum in four- and six-fold coordination. It is shown that the amounts of four- and sixfold coordinated aluminum depend on the glass composition.     

Glasses and glass-ceramics from naturally occurring CaOMgOAl2O3SiO2 materials (I) glass formation and properties

Once oil is extracted from oil shales, the inorganic solid which remains is from the CaOMgOAl₂O₃SiO₂ system. The material is easily melted and forms a glass upon cooling. Its viscosity in the forming region is actually less than that of commercial soda-lime glass. Shale glasses exhibit excellent dielectric behavior, while their other properties are generally comparable to commercial glasses. These glasses appear to be promising materials for future applications.