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At least 19 records

Field-assisted patterned dissolution of silver nanoparticles in phosphate glass

Phosphate glass samples doped with silver ions through a Na⁺-Ag⁺ ion-exchange process were treated in a hydrogen atmosphere at temperatures near 430°C for durations ranging from 4 to 5 h. Such treatment causes metallic silver precipitation at the surface as well as nanoclustering of silver atoms under the surface under conditions very similar to those used for silicate glasses. The presence of silver clusters resulted in a characteristic coloring of the glass and was verified by the observation of a plasmon resonance peak near 410–420 nm in the absorption spectra. Applying a DC voltage between 1.4 and 2 kV at temperatures between 120 and 130°C led to dissolution of the clusters in the area under the positive electrode, thereby bleaching the glass color. The use of a patterned doped-silicon electrode further led to the formation of a 300 nm thick surface relief on the glass surface and of a volume complex permittivity grating extending at least 4 μm under the surface. Such volume complex refractive index gratings may find applications in passive or active (laser) photonic devices in rare-earth doped phosphate glasses, where conventional bulk grating formation techniques have limited applicability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form

This study demonstrates the conversion of simulated pyroprocessing salt wastes [i.e., ER(SF) and ERV2] into chemically durable iron phosphate glass waste forms through reactions with ammonium hydrogen phosphate precursors [i.e., NH4H2PO4 and (NH4)2HPO4] and added Fe2O3. The reaction of the salt simulants with the phosphate precursors resulted in dehalogenation of the salt through the production of NH4Cl and NH4I (along with water), of which the NH4Cl can be used to produce UCl3 oxidant for use in the electrorefiner during pyroprocessing. These iron phosphate glasses contain a notably higher waste loading than the baseline glass-bonded sodalite ceramic waste form, which requires about 70 vol% sodalite to accommodate Cl from the salt, because they are dehalogenated prior to vitrification. The high waste loadings coupled with higher bulk densities (~3×103 kg/m3) than glass-bonded sodalite (~2.3×103 kg/m3) mean that these glasses have a higher storage volume, i.e., the volume required to immobilize a given mass of waste. The iron phosphate glass waste forms were characterized using a variety of techniques including physical property measurements and chemical durability testing. Following initial testing, a proof-of-concept demonstration was conducted to show that the NH4Cl generated from this process could be used to produce UCl3 using depleted uranium dendrites as a feedstock.

phosphate glass, pyroprocessing, waste forms, salt↗

Iron phosphate glasses: Bulk properties and atomic scale structure

Bulk properties such as glass transition temperature, density and thermal expansion of iron phosphate glass compositions, with replacement of Cs by Ba, are investigated as a surrogate for the transmutation of 137Cs to 137Ba, relevant to the immobilisation of Cs in glass. These studies are required to establish the appropriate incorporation rate of 137Cs in iron phosphate glass. Density and glass transition temperature increases with the addition of BaO indicating the shrinkage and reticulation of the iron phosphate glass network. The average thermal expansion coefficient reduces from 19.8 × 10-6 K-1 to 13.4 × 10-6 K-1, when 25 wt. % of Cs2O was replaced by 25 wt. % of BaO in caesium loaded iron phosphate glass. In addition to the above bulk properties, the role of Ba as a network modifier in the structure of iron phosphate glass is examined using various spectroscopic techniques. The FeII content and average coordination number of iron in the glass network was estimated using Mössbauer spectroscopy. The FeII content in the un-doped iron phosphate glass and barium doped iron phosphate glasses was 20, 21 and 22 ± 1% respectively and the average Fe coordination varied from 5.3 ± 0.2 to 5.7 ± 0.2 with increasing Ba content. The atomic scale structure was further probed by Fe K-edge X-ray absorption spectroscopy. The average coordination number provided by extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure was in good agreement with that given by the Mössbauer data.

36 MATERIALS SCIENCE↗

Effect of CaF{sub 2} addition on optical properties of barium phosphate glasses

Ternary barium phosphate glasses, (50−X)BaO−XCaF{sub 2}−50P{sub 2}O{sub 5} have been prepared by adding 0-10 mol% of CaF{sub 2} to binary barium phosphate glasses. The amorphous nature of the prepared glasses was confirmed by X-ray diffraction technique. The UV-Visible absorption spectra have been recorded, optical band gap energy Eopt and Urbach energy Etail were determined. Shift in Eopt and Etail with increase in concentration of CaF{sub 2} is noted. FTIR analysis was carried out to investigate the short and intermediate-range orders in glasses. Shift of (P-O-P) band to higher wave number with the substitution of BaO with CaF{sub 2} shows the shortening of the phosphate chains. Hardness and density of glass samples were measured and correlated with the composition of glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Calcium Phosphate Constraints in HLW Glasses: Phosphate Liquidus Model

About 50 million gallons of high-level mixed waste is currently stored in underground tanks at the United States Department of Energy’s (DOE’s) Hanford site in the State of Washington. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) will provide DOE’s Office of River Protection (ORP) with a means of treating this waste by vitrification for subsequent disposal. The tank waste will be separated into low- and high-activity waste fractions, which will then be vitrified respectively into Immobilized Low Activity Waste (ILAW) and Immobilized High Level Waste (IHLW) products. The ILAW product will be disposed in an engineered facility on the Hanford site while the IHLW product is designed for acceptance into a national geological disposal facility for high-level nuclear waste. The ILAW and IHLW products must meet a variety of requirements before they can be accepted for disposal. Glass property-composition models will be used to control the vitrification process at the WTP to ensure that the glass meets product quality and processability requirements. The quality and the validity ranges of the property-composition models and the supporting database will greatly influence waste treatment operations, including the waste loading that is achievable in the glass for each waste composition. The current baseline models for operation of the WTP were developed under the Bechtel National, Inc. (BNI) WTP contract. These models were based on LAW and HLW glass property data over a range of compositions that was guided primarily by the WTP contract and the set of tanks specified therein. The HLW testing was directed towards waste streams from the then-planned early feed tanks for the WTP (i.e., AZ-101, AZ-102, C-106/AY-102, and C-104/AY-101). These wastes are high in iron (AZ-101, AZ-102, and C-106/AY-102) or thorium (C-104/AY-101). While the baseline models may be adequate for commissioning of the facility and processing of the specified tanks, refinements and extensions or augmentations of these models will be required to process the balance of the tank waste inventory. The overall mission of the WTP will require the immobilization of tank waste compositions that are variously dominated by mixtures of aluminum, chromium, bismuth, iron, phosphorous, zirconium, and sulfur compounds as waste-loading-limiting components. Further, the WTP contract includes minimum waste loading requirements that are generally rather modest while loadings significantly higher than those in the current baseline are likely achievable. In order to achieve these higher waste loadings and to expand the applicable composition regions, new models will be needed to support the optimized operation of the WTP. Since the development of the baseline WTP models, ORP directed a program of work at the Vitreous State Laboratory (VSL) to examine various approaches for optimization of the performance of the WTP, including increasing the waste loadings in the LAW and HLW glass products. That work involved HLW rich in Al, Al+Na, Cr, Bi, S, Zr, Sr, P and Fe, in contrast to old baseline models that were based mostly on HLW tanks that were high in Fe, with one other that was also high in Th. Glass property data collected under the ORP program were compiled and combined with data collected to develop the WTP models. The combined databases have been used to update pre-existing HLW composition models or to develop new models for properties such as Product Consistency Test (PCT) responses, spinel crystallization (one-percent crystal fraction temperature, T 1% ), melt viscosity, melt electrical conductivity, nepheline formation upon slow cooling (i.e., Canister Centerline Cooling [CCC]), and Toxicity Characteristic Leach Procedure (TCLP) Cd response. While spinel is typically the most commonly occurring phase in HLW glasses, other phases can be limiting depending on the waste and glass composition. For example, various phosphate phases can become important as the phosphorus content increases. Lithium phosphate crystallization can impact PCT releases of HLW glasses, while calcium phosphate phases forming in the cold-cap can deleteriously impact feed processing in the melter. At present, however, no models exist that relate glass composition and crystallization of phosphate phases in general and calcium phosphate in particular. The present work was therefore directed towards the initial development of such models. Future work may be directed at studying amorphous phase separation in high phosphate HLW glasses. Within the River Protection Project, feed compositions are projected using the Hanford Tank Waste Operations Simulator (HTWOS), a dynamic computer model that tracks the waste through storage, retrieval, feed staging, and treatment processes. A review of the HTWOS data shows that WTP will process 4106 batches of HLW glass for the overall mission (System Plan Rev. 6, ORP-11242), each with its own waste feed and glass composition. Some of the projected HTWOS feed batches are expected to have relatively high concentrations of phosphorous compared to typical HLW streams. In the 4106 batches of HLW for the overall WTP mission P 2 O 5 varies from 0.59 wt% to 13.00 wt%, with 95 batches containing at least 10 wt% P 2 O 5 . Occurrences of phosphate crystals have commonly been noted in glasses with high bismuth and phosphorus contents. In addition, recently collected data from a set of statistically designed HLW matrix glasses prepared and characterized to support enhancement of the HLW glass property-composition models identified apatite in a number of glass samples. However, the current HLW model for crystallization (one-percent crystal fraction temperature) is applicable only to spinel crystallization in glasses. Previous projections of waste loadings and glass volume (such as those in System Plan Rev. 6, ORP-11242) have used preliminary constraints for calcium phosphate crystallization that are based on the limited available data. Additional data and improved constraints or, preferably, models that relate glass composition to crystallization of phosphate-containing phases, are therefore needed to support HLW vitrification at the WTP. The present study focuses on the development of such a model based on data from previously characterized glasses and a set of newly fabricated glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The effects of CeO{sub 2} addition on crystallization behavior and pore size in microporous calcium titanium phosphate glass ceramics

Highlights: ► We prepare a phosphate glass ceramic in the system of CaO–TiO{sub 2}–P{sub 2}O{sub 5} and add 2 to 6 mol% CeO{sub 2} to it. We determine the optimum percentage of CeO{sub 2} addition. ► We study phase separation, suitable time and temperature for crystallization in the microporous Calcium Titanium Phosphate Glass Ceramics utilizing DTA, SEM and XRD. ► We investigate on pore size utilizing BET and SEM techniques before and after CeO{sub 2} addition. ► CeO{sub 2} increases the pore size in the Calcium Titanium Phosphate Glass Ceramics. -- Abstract: In this research the effect of the addition of CeO{sub 2} to microporous Calcium Titanium Phosphate glass ceramics was studied. Different molar percentages of CeO{sub 2} were added to three samples of a base glass whose composition was P{sub 2}O{sub 5} 30, CaO 45, TiO{sub 2} 25 (mol%). The first sample had 2 mol% CeO{sub 2}, the second sample had 4 mol% CeO{sub 2}, and the third sample had 6 mol% CeO{sub 2}. The fourth sample did not contain any CeO{sub 2}. The glass samples were melted and crystallized to bulk glass ceramics by a conventional method. Differential Thermal Analysis (DTA) was utilized to determine the appropriate nucleation and crystallization temperatures. Among the samples, the DTA curve of the sample which had 2 mol% CeO{sub 2} had the sharpest crystallization peak. Therefore, this sample was chosen to prepare the glass ceramics. Using X-ray Diffraction (XRD) it was found that in all samples β-Ca{sub 3}(PO{sub 4}){sub 2} and CaTi{sub 4}(PO{sub 4}){sub 6} were the major phases. The β-Ca{sub 3}(PO{sub 4}){sub 2} phase was dissolved away by soaking the glass ceramics in HCl, leaving a porous skeleton of CaTi{sub 4}(PO{sub 4}){sub 6}. CeO{sub 2} addition increased the glass transition temperature and decreased the crystallization time and temperature. It was shown that CeO{sub 2} addition resulted in an increase in the mean pore diameter while the specific surface area decreased. The median pore diameter and specific surface area were determined as 27 nm and 14 m{sup 2}/g, respectively, for the sample containing 2 mol% CeO{sub 2}.

36 MATERIALS SCIENCE↗

The Effect of Glass Chemistry on Caesium Volatility in Iron Phosphate Glass Systems - 19344

The UK currently has a stockpile of 99,000 m{sup 3} of intermediate level waste (ILW), with this figure expected to rise to 191,000 m{sup 3} by 2125. Current immobilisation options include cementation and thermal treatment, with cementation being the preferred candidate due to the simplicity of processing. However, thermal processing such as vitrification could offer significant volume reductions, up to 75 % for some waste-streams. In comparison, cementation is generally associated with a volume increase, with a typical waste package seeing a volume increase of 200 - 400 %. For vitrification to be accepted as the preferred treatment option of ILW in the UK, the issue of volatility during the vitrification process must be addressed. Volatile components of ILW such as Cs-137 and Sr-90 account for almost 50 % of the current total radioactivity produced by the UK's ILW stockpile. Therefore, the efficient retention of these elements into the glass immobilisation medium must be considered. Various approaches can be employed when trying to increase volatile retention, however this project has focussed on the influence of glass chemistry on volatility. A series of iron phosphate glasses containing 5 mol % of B{sub 2}O{sub 3}, MnO and ZnO have been produced, where additives have been substituted in place of Fe{sub 2}O{sub 3} in a standard 40Fe{sub 2}O{sub 3}-60P{sub 2}O{sub 5} system. All glass samples were characterised using Raman spectroscopy, SEM-EDX, thermal analysis, XRD and XRF. The glasses were then doped with caesium carbonate and re-melted in the system described below. A simple off-gas system has been developed and commissioned to capture and characterise volatiles released from the glass during melting. The off-gas system has been refined several times, with the most recent design comprising of a sealed stainless steel system, connected to two gas washing bottles containing 150 ml of 50 % nitric acid. Nitrogen gas is passed through the system for the duration of the experiment at a flow rate of ∼ 0.9 L/min to ensure efficient carryover of the volatiles released from the glass melt into the solutions in the gas washing bottles. The total retention of the volatiles can be measuring by analysing the contents of the gas washing bottles using ICP-MS and XRF of the final glass product. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Bonding Environments and Radiation Stabilities of Phosphate Glasses

This report is a summary of some key take-aways presented during the Phosphate Round Table Workshop held in 2020, which was led by PNNL and ANL and funded by DOE-NE. Phosphate glasses have a wide range of commercial and industrial uses due to their unique optical, chemical, and physical properties. They are a candidate material for use as an advanced waste form matrix for immobilizing radioactive waste due to their unique ability to immobilize high fractions of alkali- and sulfur-rich streams in chemically durable glasses. This literature review provides an overview of the structure of phosphate glasses, waste-form related properties of interest (e.g., chemical durability and radiation stability), a summary of how specific composition ratios affect chemical durability (e.g., [Fe]/[P] ratio, [O]/[P] ratio, Fe 2+ /Fe 3+ ratio), as well different ways that phosphate glasses can be affected by radiation. All of these are of interest to the waste form community as phosphate glasses, primarily Fe-P-O glasses, are investigated for usage in immobilizing various types of nuclear waste including U.S. legacy wastes as well as a method for treating salt-based high-level wastes from molten salt reactors and pyroprocessing of used nuclear fuels.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Higher Fe{sup 2+}/total Fe ratio in iron doped phosphate glass melted by microwave heating

Highlights: • Iron doped phosphate glasses prepared using microwave heating and conventional heating under air and reducing atmosphere. • Presence of iron predominantly in the ferrous oxidation state in all the glasses. • Significant concentrations of iron in the ferrous oxidation state on both octahedral and tetrahedral sites in all the glasses. • Ratio of Fe{sup 2+} with total iron is found higher in microwave prepared glasses in comparison to conventional prepared glasses. - Abstract: Iron doped phosphate glasses containing P{sub 2}O{sub 5}–MgO–ZnO–B{sub 2}O{sub 3}–Al{sub 2}O{sub 3} were melted using conventional resistance heating and microwave heating in air and under reducing atmosphere. All the glasses were characterised by UV–Vis–NIR spectroscopy, Mössbauer spectroscopy, thermogravimetric analysis and wet colorimetry analysis. Mössbauer spectroscopy revealed presence of iron predominantly in the ferrous oxidation state on two different sites in all the glasses. The intensity of the ferrous absorption peaks in UV–Vis–NIR spectrum was found to be more in glasses prepared using microwave radiation compared to the glasses prepared in a resistance heating furnace. Thermogravimetric analysis showed increasing weight gain on heating under oxygen atmosphere for glass corroborating higher ratio of FeO/(FeO + Fe{sub 2}O{sub 3}) in glass melted by direct microwave heating. Wet chemical analysis also substantiated the finding of higher ratio Fe{sup +2}/ΣFe in microwave melted glasses. It was found that iron redox ratio was highest in the glasses prepared in a microwave furnace under reducing atmosphere.

36 MATERIALS SCIENCE↗

Insights on the structure and properties of sodium iron phosphate glasses from molecular dynamics simulations

Iron phosphate glasses are promising nuclear waste forms while more detailed understanding of their structures and structure-property relations are still needed to better design waste glass compositions. In this work we report studies of three series of sodium iron phosphate (NFP) glasses: 60P 2 O 5 -(40-x)Fe 2 O 3 -xNa 2 O (x = 0→40), (100–2x)P 2 O 5 -xFe 2 O 3 -xNa 2 O (x = 5→17.5) and one with different iron redox ratio, to understand the composition as well as the iron redox effects on the structure and properties of these glasses using molecular dynamics simulations with effective two-body and three-body potentials. Structural analyses, including pair distribution function, bond angle distribution, Q n distribution, and polyhedral connectivity, were performed to obtain in-depth information on short-range and medium-range structural features. The P-O pair distributions showed a first peak splitting with phosphorus-bridging and non-bridging oxygen contributions. This and the average P-O and other cation-oxygen bond distances are in excellent agreement with experiments. The coordination number of P 5+ remained four while that of Fe 3+ increased from 4.30 to 4.72 with decreasing Fe/Na ratio. Polyhedral linkage analysis showed [PO 4 ] units linked with [PO 4 ] and [FeO x ] through corner-sharing while the [PO 4 ]-[FeO x ] linkages become dominant for compositions with Fe 2 O 3 larger than 15 mol%. The effect of iron redox ratio on the structure of NFP glasses was also studied and it was found that bond lengths and coordination numbers were not strongly affected, while the reduction of iron introduced higher network distortions, as evident by O-P-O bond angle and Q n distribution. The glass transition temperature (T g ) showed a monotonic increase with Fe 2 O 3 in the first series, in good agreement with experiments, while those of the second series showed a maximum at P 2 O 5 = 82 mol%. Here, calculated elastic moduli were found to increase with Fe 2 O 3 in the first glass series, which was be explained by the increase of network connectivity, while those of the second series decrease with Fe 2 O 3 due to decrease of P 2 O 5 .

36 MATERIALS SCIENCE↗

New insights on P-related paramagnetic point defects in irradiated phosphate glasses: Impact of glass network type and irradiation dose

P-related paramagnetic point defects were studied in irradiated Yb-doped phosphate glasses by electron paramagnetic resonance spectroscopy (X and Q-bands). A strong impact of the glass network type on the defect nature is shown. In all glasses, r-POHC defects formation is in strong correlation with Q{sup 2} tetrahedra amount supporting the structure of r-POHC. Ultra-phosphate glasses contain the larger defect type: Peroxy radicals, P{sub 1}, P{sub 2}, and P{sub 4} defects whose formation is linked to Q{sup 3} tetrahedra presence. In meta-phosphate and poly-phosphate glasses, peroxy radicals appear with r-POHC thermal recovery. In meta-phosphate glasses, a combination of P{sub 1} and P{sub 3} defects was evidenced for the first time, whereas in poly-phosphate glasses, only P{sub 3} defects were identified. Dose effect as well as defect recovery were analyzed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An extended topological model for binary phosphate glasses

We present a topological model for binary phosphate glasses that builds on the previously introduced concepts of the modifying ion sub-network and the strength of modifier constraints. The validity of the model is confirmed by the correct prediction of T{sub g}(x) for covalent polyphosphoric acids where the model reduces to classical constraint counting. The constraints on the modifying cations are linear constraints to first neighbor non-bridging oxygens, and all angular constraints are broken as expected for ionic bonding. For small modifying cations, such as Li{sup +}, the linear constraints are almost fully intact, but for larger ions, a significant fraction is broken. By accounting for the fraction of intact modifying ion related constraints, q{sub γ}, the T{sub g}(x) of alkali phosphate glasses is predicted. By examining alkali, alkaline earth, and rare earth metaphosphate glasses, we find that the effective number of intact constraints per modifying cation is linearly related to the charge-to-distance ratio of the modifying cation to oxygen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural features of silver-doped phosphate glasses in zone of femtosecond laser-induced modification

Femtosecond (fs) laser writing of two-dimensional microstructures (waveguides) is demonstrated in bulk phosphate glasses doped with silver ions. Silver-content phosphate and silver-content niobium–phosphate glasses with high concentration of silver oxide 55 mol% were used as samples for fs laser writing. The chemical network structure of the synthesized samples is analyzed through Raman spectroscopy and was found to be strongly sensitive to Nb incorporation. It was found that the direct laser writing process enables not only reorganization of glass network, but also formation of color centers and silver nanoparticles that are revealed in appearance of luminescence signal and plasmon absorption. The process of NPs' formation is more efficient for Nb-phosphate glass, while color centers are preferably formed in phosphate glass. - Graphical abstract: Formation of silver NPs on the surface of 0.5Ag{sub 2}O–0.4P{sub 2}O{sub 5}–0,1Nb{sub 2}O{sub 5} glass induced by CW laser irradiation. - Highlights: • The structure of 0.5Ag{sub 2}O–0.1Nb{sub 2}O{sub 5}–0.4P{sub 2}O{sub 5} and 0.55Ag{sub 2}O–0.45P{sub 2}O{sub 5} glasses was investigated by Raman spectroscopy. • Fs laser writing induces formation of silver NPs in investigated glasses. • Surface plasmon resonance in the absorption spectra confirms the formation of NP. • The possibility of CW laser induced formation of silver NPs on the surface of sample with niobium is shown.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox effects on the structure and properties of Na-Mo-Fe-phosphate glasses

Na-Mo-Fe-phosphate glasses were prepared with reducing and oxidizing raw materials and the effects of the different Fe 2+ /Fe 3+ and Mo 5+ /Mo 6+ ratios on glass structure and properties were determined. Mssbauer spectroscopy confirms significantly greater concentrations of Fe 2+ ions in the reduced glasses and distorted Fe 3+ O 4 sites preferred over the Fe 3+ O 6 sites in the oxidized glasses. Raman spectroscopy reveals the presence of isolated Mo 6+ O 6 sites in the oxidized glasses, and highly distorted Mo 5+ O 5 sites in reduced Mo-rich glasses. The presence of specific Fe- and Mo-polyhedra is correlated with the average phosphate anion length, as characterized by high-pressure liquid chromatography. Generally, for the similar compositions, oxidized glasses have greater molar volumes than the reduced glasses, associated with the formation of isolated Mo 6+ O 6 octahedra and the absence of highly crosslinked Mo 5+ OPO 4 units. Tg increases with increasing Fe 3+ fractions in the Fe-rich glasses, whereas for the Mo-rich glasses, T g increases with greater Mo 5+ fractions.

36 MATERIALS SCIENCE↗

Spectroscopic and laser properties of Er{sup 3+} doped fluoro-phosphate glasses as promising candidates for broadband optical fiber lasers and amplifiers

Highlights: • Erbium doped different fluoro-phosphate glasses are prepared and characterized. • Spectroscopic properties have been determined using Judd–Ofelt and Mc-Cumber theory. • Prominent laser transition Er{sup 3+}:{sup 4}I{sub 13/2} → {sup 4}I{sub 15/2} is observed at 1.53 μm. - Abstract: Different fluoro-phosphate glasses doped with 0.5 mol% Er{sup 3+} doped are prepared by melt quenching method. Both structural and spectroscopic properties have been characterized in order to evaluate their potential as both laser source and amplifier materials. Optical absorption measurements are carried out and analyzed through Judd–Ofelt and Mc-Cumber theories where spectroscopic parameters such as intensity parameters Ω{sub l} (λ = 2,4,6), transition probabilities, radiative lifetimes, stimulated absorption cross-sections and emission cross-sections at 1.5 μm have been evaluated for Er{sup 3+} doped different fluorophosphate glasses. The various luminescence and gain properties are explained from photoluminescence studies. The decay curve analysis have been done for obtaining the decay time constants of Er{sup 3+} excited level {sup 4}I{sub 13/2} in all the fluoro-phosphate glasses. The obtained results of each glass matrix are compared with the equivalent parameters for several other host glasses. These fluoro-phosphate glasses are found to be suitable candidates for laser and amplifier applications.

36 MATERIALS SCIENCE↗

Ferric oxide quantum dots in stable phosphate glass system and their magneto-optical study

Graphical abstract: We report synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles (NCs) content on the optical and magneto-optical properties of the glasses. Faraday rotation of the glass nanocomposites was measured and showed variation in Verdet constant with concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and there is a threefold enhancement in the Verdet constant of ferric oxide quantum dot-glass nanocomposite. Highlights: ► We synthesize ferric oxide embedded low melting stable phosphate glass nanocomposite. ► Glasses doped with 0.25 and 2% ferric oxide show particle size in the range of 4–12 nm. ► The host phosphate glass itself shows fairly good Verdet constant (11.5°/T cm). ► Glasses doped with 0.25% ferric oxide show high Verdet constant (30.525°/T cm). ► The as synthesis glasses may have potential application in magneto optical devices. -- Abstract: Herein, we report the synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles content on the optical and magneto-optical properties of the glasses. The optical study clearly showed red shift in optical cut off with increasing ferric oxide concentration. The band gap of the host glass was observed to be 3.48 eV and it shifted to 3.14 eV after doping with ferric oxide. The glasses doped with 0.25 and 2% ferric oxide showed particle size of 4–6 nm and 8–12 nm, respectively. Faraday rotation of the glass nanocomposites was measured and showed variation in the Verdet constant as per increasing concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and threefold enhancement was observed in the Verdet constant of ferric oxide quantum dot-glass nanocomposite.

36 MATERIALS SCIENCE↗