Signo Tadeu Dos Reis

Iron Redox Equilibrium, Structure and Properties of Zinc Iron Phosphate Glasses

Abstract Iron redox equilibrium, structure and properties were investigated for 40Fe2O3–60P2O5 (mol%) glasses melted at different temperatures. The Fe2+/(Fe2++Fe3+) ratio increased from 17% to 50% as the melting temperature changed from 1150°C to 1400°C. The equilibrium constant, K, for the reaction of Fe3+ being reduced to Fe2+ varied with temperature as lnK=9.40–1.58×104/T. The Raman and infrared spectra indicated that the basic iron pyrophosphate structure of the 40Fe2O3–60P2O5 (mol%) glasses did not change as the Fe2+/(Fe2++Fe3+) ratio changed. All of the properties did not change to any major degree with increasing the melting temperature. The molar volume decreased while the density increased with increasing Fe2+/(Fe2++Fe3+) ratio. It was found by DTA and XRD that two phases, Fe3(P2O7)2 and Fe4(P2O7)3, crystallized from the glass when the glass was heated in nitrogen. The crystallization behavior suggested that the amount of the crystal, Fe3(P2O7)2, may increase with increasing Fe2+/(Fe2++Fe3+) ratio, which supported the opinion that there are some structural similarities between the iron phosphate glass and the crystalline Fe3(P2O7)2 in terms of the iron coordination number and bonding of the phosphate groups. The decrease in dc resistivity and increase in dielectric constant and dielectric loss tangent, which occurred with increasing the Fe2+/(Fe2++Fe3+) ratio, were attributed to the increase of the electronic hopping from Fe2+ ions to Fe3+ ions.

Chemical Durability and Structure of Zinc-iron Phosphate Glasses

Abstract The chemical durability of zinc–iron phosphate glasses with the general composition (40−x)ZnO–xFe2O3–60P2O5 has been measured. The chemical durability and density of these glasses increase with increasing Fe2O3 content. Glasses containing more than 30 mol% Fe2O3 had an excellent chemical durability. The dissolution rate (DR), calculated from the weight loss in distilled water at 90 °C for up to 32 days, was ∼ 10 −9 g / cm 2 / min which is 100 times lower than that of window glass and 300 times lower than that of a barium ferro, aluminoborate glass. The structure and valence states of the iron ions in these glasses were investigated using Mossbauer spectroscopy, X-ray diffraction, infrared spectroscopy and differential thermal analysis. X-ray diffraction indicates that the local structure of the zinc–iron phosphate is related to the short range structures of crystalline Zn2P2O7, Fe3(P2O7)2 and Fe(PO3)3. Both Fe(II) and Fe(III) ions are present in all of these glasses. The presence of an Fe–O–P related band in the infrared (IR) spectra of the glasses containing more than 30 mol% Fe2O3 is consistent with their excellent chemical durability.

Structural features and properties of lead–iron–phosphate nuclear wasteforms

The structure and properties of vitreous and crystalline lead–iron–phosphate glasses containing up to 21 wt% of a simulated high level waste have been investigated using Fe-57 Mossbauer, X-ray diffraction and Raman spectroscopies. The Mossbauer spectra indicated that both Fe(II) and Fe(III) ions were present in all the samples. The Raman spectra for the glasses contained two dominant bands, which were characteristic of pyrophosphate groups, (P–O) stretching mode of P–O nonbridging oxygen at 1074 cm−1 and sym stretching mode of bridging oxygen at 760 cm−1, respectively. The chemical durability of glassy and crystallized samples was investigated by measuring their weight loss in distilled water at 90 °C for up to 32 days. The weight loss of the lead–iron–pyrophosphate wasteforms was up to 100 times less than that for window glass. X-ray diffraction patterns showed that FeSiO3 and SiP2O7 phases are present in samples containing more than 14 wt% of the simulated nuclear waste.

Direct femtosecond laser waveguide writing inside zinc phosphate glass

We report the relationship between the initial glass composition and the resulting microstructural changes after direct femtosecond laser waveguide writing with a 1 kHz repetition rate Ti:sapphire laser system. A zinc polyphosphate glass composition with an oxygen to phosphorus ratio of 3.25 has demonstrated positive refractive index changes induced inside the focal volume of a focusing microscope objective for laser pulse energies that can achieve intensities above the modification threshold. The permanent photo-induced changes can be used for direct fabrication of optical waveguides using single scan writing techniques. Changes to the localized glass network structure that produce positive changes in the refractive index of zinc phosphate glasses upon femtosecond laser irradiation have been studied using scanning confocal micro-Raman and fluorescence spectroscopy.

Designing sealing glasses for solid oxide fuel cells

Thermal and chemical properties of “invert” glasses and glass-ceramics developed for hermetic seals for solid oxide fuel cells are described. The glasses crystallize to form thermally stable pyro- and orthosilicate phases with the requisite thermal expansion match to the Y-stabilized ZrO2 (YSZ) electrolyte. In addition, the glasses bond to Cr-steel substrates at 800–850 °C without forming extensive interfacial reaction products. The thermal expansion characteristics of the glass-ceramics remain essentially unchanged after 28 days at 750 °C. Compositions with lower (≤2 mol%) B2O3 contents exhibit the lowest volatilization rates when exposed to wet forming gas at 750 °C.

Femtosecond laser writing of waveguides in zinc phosphate glasses [Invited]

We have studied the relationship between the initial glass composition and the structural changes associated with laser-induced refractive index modification in a series of Er-Yb doped and undoped zinc phosphate glasses. White light microscopy and waveguide experiments are used together with Raman and fluorescence spectroscopy to characterize the structural changes. The correlation between Raman peak shifts and fluorescence from phosphorus–oxygen hole center (POHC) defects indicates that fs-laser writing results in a depolymerization of the phosphate glass network. The results also show that the exact glass composition should be taken into account when fabricating waveguide devices in phosphate glasses, in order to both expand the fs-laser processing conditions and maximize favorable morphological changes for 3-D photonic devices.

Effects of rare-earth doping on femtosecond laser waveguide writing in zinc polyphosphate glass

We have investigated waveguide writing in Er-Yb doped zinc polyphosphate glass using a femtosecond laser with a repetition rate of 1 KHz. We find that fabrication of good waveguides requires a glass composition with an O/P ratio of 3.25. The dependence on laser writing parameters including laser fluence, focusing conditions, and scan speed is reported. Waveguide properties together with absorption and emission data indicate that these glasses can be used for the fabrication of compact, high gain amplifying devices.

Properties and structural features of iron doped BABAL glasses

The chemical durability, density and structure of the BABAL glasses with batch compositions (100-x)(0.30BaO·0.50B2O3·0.20Al2O3)·xFe 2O3 (1 < x < 10 mol%), were investigated using Mossbauer spectroscopy, electron paramagnetic resonance (EPR), X-ray diffraction, Raman and differential thermal analysis (DTA). The chemical durability for the glass of composition 27BaO·45B2O3·18Al 2O3·10Fe2O3 (mol%) at 90 °C in distilled water was 700 times lower than that of iron phosphate glass 40Fe2O3·60P2O 5 (mol%). The Mossbauer spectra indicate the presence of iron (II) and iron (III) in tetrahedral or octahedral coordination. The results obtained from the gef = 4.3 EPR line are typical of the occurrence of iron (III) occupying substitutional sites and the line gef = 2.0 is related to the association of two or more Fe ions found in the interstices (or holes occupied by the glass modifier cations) of the glass network. The paths of X-ray diffraction are typical for glasses based in borate glasses. The Raman spectra showed that the boroxol ring disappears with the increase of iron content, concomitant with the appearance of BO4 and tetraborate structural units. At these conditions, an increase of dissolution rate and clustering of iron ions is observed.

Structural modification in Er-Yb doped zinc phosphate glasses with megahertz repetition rate femtosecond pulses

Focused femtosecond laser pulses from a 1 MHz fiber laser were used to create modifications in Er- Yb doped zinc phosphate glass. Two glasses with similar phosphate glass networks but different network modifiers were investigated. To understand the resulting changes caused by the femtosecond laser pulses various characterization techniques were employed: glass structural changes were investigated with confocal Raman spectroscopy, defect generation as well as local Er and Yb environment were investigated with confocal fluorescence spectroscopy, and elemental segregation resulting from heat accumulation effects was ascertained by scanning electron microscopy.

Electrical properties of phosphate glasses

Investigation of the electrical properties of phosphate glasses where transition metal oxide such as iron oxide is the network former and network modifier is presented. Phosphate glasses containing iron are electronically conducting glasses where the polaronic conduction is due to the electron hopping from low to high iron valence state. The identification of structural defects caused by ion/polaron migration, the analysis of dipolar states and electrical conductivity in iron phosphate glasses containing various alkali and mixed alkali ions was performed on the basis of the impedance spectroscopy (IS). The changes in electrical conductivity from as-quenched phosphate glass to fully crystallized glass (glass-ceramics) by IS are analyzed. A change in the characteristic features of IS follows the changes in glass and crystallized glass network. Using IS, the contribution of glass matrix, crystallized grains and grain boundary to the total electrical conductivity for iron phosphate glasses was analyzed. It was shown that decrease in conductivity is caused by discontinuities in the conduction pathways as a result of the disruption of crystalline network where two or more crystalline phases are formed. Also, phosphate-based glasses offer a unique range of biomaterials, as they form direct chemical bonding with hard/soft tissue. The surface charges of bioactive glasses are recognized to be the most important factors in determining biological responses. The improved bioactivity of the bioactive glasses as a result of the effects of the surface charges generated by electrical polarization is discussed.