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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Melting Hanford LAW into Iron-Phosphate Glass in a CCIM

A vitrification test has been conducted using the cold crucible induction melter (CCIM) test system at the Idaho National Laboratory. The test was conducted to demonstrate the vitrification of a Hanford low activity waste (LAW) that contains relatively large amounts of sulfate and sodium, compared to other radioactive Hanford waste streams. The high sulfate content limits the potential loading of this waste stream in conventional borosilicate glass, so this test demonstrated how this waste stream could be vitrified in an iron-phosphate glass that can tolerate higher levels of sulfate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Iron Phosphate Glass for Vitrifying Hanford AZ102 LAW in Joule Heated and Cold Crucible Induction Melters - 12240

An iron phosphate composition for vitrifying a high sulfate (∼17 wt%) and high alkali (∼80 wt%) Hanford low activity waste (LAW), known as AZ-102 LAW, has been developed for processing in a Joule Heated Melter (JHM) or a Cold Crucible Induction Melter (CCIM). This composition produced a glass waste form, designated as MS26AZ102F-2, with a waste loading of 26 wt% of the AZ-102 which corresponded to a total alkali and sulfate (represented as SO{sub 3}) content of 21 and 4.4 wt%, respectively. A slurry (7 M Na{sup +}) of MS26AZ102F-2 simulant was melted continuously at temperatures between 1030 and 1090 deg. C for 10 days in a small JHM at PNNL and for 70 hours in a CCIM at INL. The as-cast glasses produced in both melters and in trial laboratory experiments along with their canister centerline cooled (CCC) counterparts met the requirements for the Product Consistency Test (PCT) and the Vapor Hydration Test (VHT) responses in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Contract. These glass waste forms retained up to 77 % of the SO{sub 3} (3.3 wt%), 100% of the Cesium, and 33 to 44% of the rhenium (used as a surrogate for Tc) all of which either exceeded or were comparable to the retention limit for these species in borosilicate glass nuclear waste form. Analyses of commercial K-3 refractory lining and the Inconel 693 metal electrodes used in JHM indicated only minimum corrosion of these components by the iron phosphate glass. This is the first time that an iron phosphate composition was melted continuously in a slurry fed JHM and in the US, thereby, demonstrating that iron phosphate glasses can be used as alternative hosts for vitrifying nuclear waste. The following conclusions are drawn from the results of the present work. (1) An iron phosphate composition, designated as MS26AZ102F-2, containing 26 wt% of the simulated high sulfate (17 wt%), high alkali (80 wt%) Hanford AZ-102 LAW meets all the criteria for processing in a JHM and CCIM. This composition produces a homogeneous glass with a density of 2.80 ± 0.04 g/cm{sup 3} after melting between 1000 and 1050 deg. C for 3 to 5 h. (2) This is the first time that an iron phosphate glass was melted in the JHM continuously for 10 days achieving a specific melting rate of 1010 kg/m2/day and in the CCIM for 70 hrs with a melting rate of 664 kg/m{sup 2}/day. (3) The analyzed (ICP-AES) compositions for all the glasses prepared under several melting conditions are in excellent agreement with the target composition. The variation of melting conditions include: (i) use of small scale/short melting time to large scale/long melting time (300 g to 80 kg, 4 h to 10 days) operations including melting in the JHM and CCIM, (ii) use of dry or wet (slurry) melter feed, (iii) addition of reductant (sugar) in the batch, and (iv) bubbling the melt with air. (4) The chemical durability as measured by PCT and VHT for the quenched and CCC-treated waste forms prepared from laboratory, JHM or CCIM melting exceeds the DOE requirements for LAW. (5) Depending upon the melting time (4 h to 10 days), the average concentration of SO{sub 3} in the MS26AZ102F-2 iron phosphate glass waste form varies from about 1.78 (RSM) to 3.74 (laboratory melt) wt% which corresponds to an SO{sub 3} retention of 41 to 86% when melted between 1030 at 1050 deg. C in air. (6) The retention of SO{sub 3} in the glass was reduced when a reductant (sugar) was added to the slurry. (7) The retention of other problem components like Cesium and Rhenium/Tc-99 is also high; from 92 to 100% for Cs{sub 2}O under different melting conditions, and from 66 to 33% for Re{sub 2}O{sub 7} for melts processed from 3 to 5 hours and up to 10 days. (8) Corrosion tests on Inconel 693 and K-3 refractory at temperatures between 1000 and 1050 deg. C indicate that both materials should be suitable for melting iron phosphate glasses. (9) The viscosity and electrical conductivity of the MS26AZ102F-2 melt are within the acceptable limits for RSM and CCIM processing. (10)This work has shown that iron phosphate compositions are a potential alternative to borosilicate glasses for vitrifying problematic wastes such as Hanford AZ-102 LAW that contains high amounts sulfate and alkali oxides, and that iron phosphate melts such as MS26AZ102F-2 can be processed in the JHM or CCIM. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Enhanced 1.53 μm emission of Er{sup 3+} ions in phosphate glass via energy transfer from Cu{sup +} ions

Optimizing the efficiency of Er{sup 3+} emission in the near-infrared telecommunication window in glass matrices is currently a subject of great interest in photonics research. In this work, Cu{sup +} ions are shown to be successfully stabilized at a high concentration in Er-containing phosphate glass by a single-step melt-quench method, and demonstrated to transfer energy to Er{sup 3+} thereby enhancing the near-infrared emission about 15 times. The spectroscopic data indicate an energy conversion process where Cu{sup +} ions first absorb photons broadly around 360 nm and subsequently transfer energy from the Stokes-shifted emitting states to resonant Er{sup 3+} absorption transitions in the visible. Consequently, the Er{sup 3+} electronic excited states decay and the {sup 4}I{sub 3/2} metastable state is populated, leading to the enhanced emission at 1.53 μm. Monovalent copper ions are thus recognized as sensitizers of Er{sup 3+} ions, suggesting the potential of Cu{sup +} co-doping for applications in the telecommunications, solar cells, and solid-state lasing realizable under broad band near-ultraviolet optical pumping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Effects of titanium nanoparticles on self-cleaning and structural features of zinc-magnesium-phosphate glass

Graphical abstract: Water contact angle for sample S2, S3, S4 and S5. The water contact angle increased with increased the titanium NPs content (mol%). - Highlights: • ZnO–MgO–P{sub 2}O{sub 5} embedded TiO{sub 2} NPs prepared by conventional melt-quenching method. • The amorphous nature is confirmed by X-ray diffraction spectroscopy. • The structural characteristics of glasses is investigated using FTIR and Raman. • Wettability of the glasses surface by water contact angle. - Abstract: The loss of glass transparency on surface pollutants contamination unless inhibited not only causes vision obscurity but also responsible for major aesthetic damages of cultural heritage. It is due to the sticking of fine dirt particles on wetting layers, a complex process with several possible ramifications still to be clarified. We report the influence of titanium dioxide or titania (TiO{sub 2}) nanoparticles (NPs) on the structural and self-cleaning properties of zinc–magnesium–phosphate glasses. Following melt-quenching method glass samples of optimized composition (42 − x)P{sub 2}O{sub 5}–8MgO–50ZnO–xTiO{sub 2} with x = 0, 1, 2, 3 and 4 mol% are prepared. XRD patterns verified their amorphous nature and TEM images revealed the nucleation of TiO{sub 2} NPs of average diameter ≈4.05 ± 0.01 nm. Fourier transform infrared (FTIR) spectra displayed four absorption band centred at 1618–3438 cm{sup −1}, 902– 931 cm{sup −1}, 757–762 cm{sup −1} and 531–560 cm{sup −1}. Raman spectra exhibited four peaks each accompanied by a blue-shift. Water contact angle is found to increase with the increase of titanium NPs concentration into the amorphous matrix. This knowledge can be used to set up strategies and selective treatments to preventing glass transparency loss via the modification of self-cleaning attributes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

XANES analysis of phosphate glasses melted with Tb 4 O 7 and SnO: evaluating the impact of valence states on structural, thermal, and luminescent properties

Barium phosphate glasses were prepared with 0.5 mol% Tb 4 O 7 added alongside SnO up to 5 mol% with the purpose of evaluating the resulting terbium and tin oxidation states and their impact on glass structural, thermal, and luminescent properties. In this work, following material synthesis by melt-quenching, the composition-structure–property investigation was pursued encompassing measurements by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, and photoluminescence (PL) spectroscopy. While XRD confirmed the amorphous nature of the glasses, results from XANES indicated that terbium occurs as terbium(III) with a predisposition for tin to exist as tin(IV) which decreased at high SnO content. The structural as well as the thermal properties appeared to be mostly impacted by the presence of tin(IV). Specifically, glass depolymerization was indicated to be induced by Sn 4+ ions, and their concentration was observed to correlate with glass transition and softening temperatures. On the other hand, the tin(II) remnants were observed to exert an impact on the luminescent properties shifting light emission from the green towards the blue-green (cyan). It is indicated that Tb 4 O 7 reacting to produce Tb 2 O 3 supports the oxidation of tin(II) to tin(IV) which in turn dominates the physical properties. However, this was somewhat circumvented at the highest SnO content wherein tin(IV) appeared to be lower.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Sol-gel derived silicate-phosphate glass SiO 2 –P 2 O 5 –CaO–TiO 2 : The effect of titanium isopropoxide on porosity and thermomechanical stability

Despite of several decades lasting extensive research of bioactive and bioresorbable glasses the systematic parametrization and determination of the key factors affecting porosity and thermomechanical characteristics still remains challenging. Here, we present silica-phosphate glasses, with the composition 70SiO 2 - 20P 2 O 5 - (10-x)CaO-xTiO 2 (mol%; x = 0, 2.5, 5, and 7.5), prepared by sol -gel method and reinforced by titanium dioxide via titanium isopropoxide (TTIP) incorporation which demonstrated tunable variation of porosity from micro-to macro -region and superb mechanical integrity during the calcination process. The presence of 7.5 mol% TiO 2 promotes dimensional stability up to 1000°C as investigated by thermomechanical analysis. The XRD showed the dominant presence of silicon phosphate [Si(P 2 O 7 )], titanium phosphate [Ti(P 2 O 7 )] and calcium phosphates [β-Ca(P 2 O 6 ) and γ- Ca 2 (P 2 O 7 )]. The effect of TiO 2 doping on the multiscale morphology and porosity was investigated by means of SEM, MIP, μCT, N 2 adsorption and USAXS/SAXS. Increasing TiO 2 content leads to the formation of open porosity up to 70vol% and drives the formation of a refined interconnected macroporosity of 2-30 μm. In contrast, mesoporosity with a dominance of 3-6nm pores decreases in all samples with increasing TiO 2 content. USAXS/SAXS revealed an increase in primary particle size with increasing TiO 2 content which is in good agreement with the nitrogen physisorption analysis showing that microporosity decreases with increasing TiO2 content.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Modeling pair distribution functions of rare-earth phosphate glasses using principal component analysis

The use of principal component analysis (PCA) to statistically infer features of local structure from experimental pair distribution function (PDF) data is assessed on a case study of rare-earth phosphate glasses (REPGs). Such glasses, co-doped with two rare-earth ions (R and R’) of different sizes and optical properties, are of interest to the laser industry. The determination of structure-property relationships in these materials is an important aspect of their technological development. Yet, realizing the local structure of co-doped REPGs presents significant challenges relative to their singly-doped counterparts; specifically, R and R’ are difficult to distinguish in terms of establishing relative material compositions, identifying atomic pairwise correlation profiles in a PDF that are associated with each ion, and resolving peak overlap of such profiles in PDFs. This study demonstrates that PCA can be employed to help overcome these structural complications, by statistically inferring trends in PDFs that exist for a restricted set of experimental data on REPGs, and using these as training data to predict material compositions and PDF profiles in unknown co-doped REPGs. The application of these PCA methods to resolve individual atomic pairwise correlations in t(r) signatures is also presented. The training methods developed for these structural predictions are pre-validated by testing their ability to reproduce known physical phenomena, such as the lanthanide contraction, on PDF signatures of the structurally simpler singly-doped REPGs. The intrinsic limitations of applying PCA to analyze PDFs relative to the quality control of source data, data processing, and sample definition, are also considered. Furthermore, while this case study is limited to lanthanide-doped REPGs, this type of statistical inference may easily be extended to other inorganic solid-state materials, and be exploited in large-scale data-mining efforts that probe many t(r) functions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Evaluation of Iron‐Phosphate Glass–Ceramic Waste Form for Electrorefiner Salt Waste Simulant Dechlorinated With Phosphoric Acid

The importance of glass and glass–ceramic nuclear waste forms has been reaffirmed in recent years by the growing interest in nuclear power as a reliable energy source. Determination of processing methods for the disposal of halide-containing wastes will be essential for the advancement of nuclear technologies such as non-aqueous fuel reprocessing. Phosphate-based dechlorination and subsequent vitrification of radioactive salt waste into an iron-phosphate waste form have been identified as a potential processing scheme for electrochemical processing waste. The impact of H 3 PO 4 -based dechlorination of complex salt mixtures on the vitrification process and structure of the final iron-phosphate waste form has not yet been investigated. In this work, iron-phosphate glass–ceramics were made from simulant salt waste (48LiCl–33KCl–19NaCl mol%) dechlorinated with the H3PO4-based method. The glass-forming region was compared to that of traditionally prepared Na 2 O–Fe 2 O 3 –P 2 O 5 systems. For a candidate glass-forming composition, the processing scheme presented here was determined to favor Fe 3+ species. The O/P molar ratio was consistent for the candidate composition when dechlorinated at 400°C and 600°C in air and argon environments, indicating glass network connectivity was maintained despite variations in processing parameters. The results presented here validate processing schemes requiring iron-phosphate waste form synthesis following H 3 PO 4 -based dechlorination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Emission characteristics of holmium ions in fluoro-phosphate glasses for photonic applications

Optical properties of Ho{sup 3+} doped different fluorophosphate (FP) glasses have been synthesized and discussed. Thermal properties have been studied through differential scanning calorimetry (DSC).The Judd-Ofelt (J-O) intensity parameters Ω{sub λ} (λ= 2, 4, 6) from absorption spectra have been evaluated. Various radiative parameters have been obtained for the different excited states using J-O theory. From the emission spectra, different laser properties have been studied and discussed. The nature of decay curve analysis was performed for the {sup 5}F{sub 4}({sup 5}S{sub 2}) level. These glasses are expected to give interesting application in the field of photonic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Structure and transport investigations on lithium-iron-phosphate glasses

Cathode materials for Lithium Ion Batteries (LIB’s) are being constantly studied and reviewed especially in the past few decades. LiFePO{sub 4} (LFP) is one of the most potential candidates in the pedigree of cathode materials and has been under extensive study ever since. In this work, we report the synthesis of amorphous analogs of crystallite LFP by conventional melt quenching method. Thermal study by using differential scanning calorimetry (DSC) was used to determine the glass transition T{sub g} and crystallization T{sub c} temperatures on the obtained glass sample Fourier transform infrared (FTIR) absorption spectroscopy is being used to investigate the structural properties of the glass sample. The intrinsic electrical conductivity measurements were done using broad-band impedance spectroscopy with wide different temperature ranges. The conduction mechanism is described by non-adiabatic small polaron hopping between nearest neighbors. Based on the obtained results, we suggest that the glassy LFP is more suitable cathode material as compared to its crystalline counterpart.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Study of a wide-aperture combined deformable mirror for high-power pulsed phosphate glass lasers

A deformable mirror with the size of 410 × 468 mm controlled by bimorph piezoceramic plates and multilayer piezo stacks is developed. The response functions of individual actuators and the measurements of the flatness of the deformable mirror surface are presented. The study of mirrors with an interferometer and a wavefront sensor has shown that it is possible to improve the surface flatness down to a residual roughness of 0.033 μm (RMS). The possibility of correction of beam aberrations in an ultra-high-power laser using the created bimorph mirror is demonstrated. (letters)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Glass transition temperature studies of planetary ball milled glasses: Accessing the rapidly cooled glassy state in Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 7, Oxy-thio phosphate glasses

This paper details the very first in-depth study of the glass transition temperature (T g ) for planetary balled milled (PBM) Na 4 P 2 S 7-x O x (NaPSO), where 0 ≤ x ≤ 7, glasses. For 0 ≤ x ≤ 5, fully amorphous, homogeneous, and chemically reacted compositions can be prepared. For samples with 5 < x ≤ 7, partially amorphous but fully chemically reacted glass-ceramics can be produced. The reproducible, thermally cyclable onset T g and the onset crystallization temperature, T c , were investigated as a function of the composition and of the short-range order (SRO) structures of the glasses. Additionally, we examined the extreme sub-T g exothermic relaxations present due to the high energy milling processing and correspondingly high effective quenching rate. Using a differential scanning calorimeter (DSC) and scanning from well below the onset T g , the glasses are observed to relax exothermally below T g . The integrated relaxation enthalpy, ΔH rel , is ~ 0 for the x = 2 glass, but is significantly exothermic for lower and higher values of x. Once the high fictive state of these glasses has been erased by scanning to above the T g , but below the T c of the glass, the DSC scans of the glasses recover normal behavior for a normally cooled glass without any relaxation exotherm. The T g s of these glasses remain relatively constant for 0 ≤ x ≤ 3, but for glasses with 3 < x ≤ 5, T g increases sharply following the combined effects of the phosphate chain length increasing caused by the formation of bridging oxygens and the increasing concentration of more charge dense non-bridging oxygens (NBOs). For x > 5, both T g and Tc decrease sharply, becoming nearly identical at x = 7 where glass formation essentially ceases. For smaller values of x, T c increases with both chain length and the structural complexity of the composition but decreases sharply for glass-ceramics of x > 5.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Corrosion Tests with Developmental Iron Phosphate Glass Waste Forms

Corrosion tests are in progress to assess the dissolution behavior of developmental iron phosphate waste forms for salt waste from electrochemical separation operations. Specimens cut from materials made at PNNL to represent a range of waste salt loadings in prototype composition DPF-5 and a range of iron oxide loadings in prototype composition DPF-3 were subjected to modified ASTM C1308 tests to assess the compositional effects on the relative durabilities and retention of immobilized salt cations. The materials were composed of different amounts of glass and crystalline phases. The test results show both the intrinsic durability of the material and the salt cation retention decrease as the total amount of salt cations added to the material is increased. The results of ASTM C1220 and ASTM C1285 tests conducted with materials DPF5-280 and DPF5-336, which contained about 28% and 34% salt cations (on a mass oxide basis) and bounded the durabilities of the other materials, show that solution feedback does not attenuate the dissolution rate. This suggests the degradation of iron phosphate waste forms can be modelled by using a constant rate that probably depends on the composition and volume fraction of the glass phase. A reference composition should be formulated and used in tests to determine those dependencies. The ASTM C1220 and ASTM C1285 tests with DPF5-280 and DPF5-336 remain in progress to corrode the specimens enough to distinguish the relative extents of glass and crystalline phase corrosion by microscopic examinations. Those results are expected to provide insights regarding the relative dissolution rates of crystalline and glass phases and impact on durability to inform the formulation of the reference composition.

Ebert, W. L.↗
DOE OSTI2014

Spectroscopic and dielectric response of zinc bismuth phosphate glasses as a function of chromium content

Graphical abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. The optical absorption spectra of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. - Highlights: • ZnF{sub 2}–Bi{sub 2}O{sub 3}–P{sub 2}O{sub 5}:Cr{sub 2}O{sub 3} glasses were prepared by melt quenching and annealing. • Spectroscopic and dielectric properties of chromium ions were investigated. • ESR and optical absorption spectra indicate the co-existence of Cr{sup 6+} ions with Cr{sup 5+} ions and Cr{sup 3+} ions. • Cr{sup 3+} ions act as modifiers and influence the semiconducting nature of the glass system. - Abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. Amorphous nature of these samples is confirmed by X-ray diffraction (XRD) analysis. FTIR study reveals bands due to CrO{sub 6}(o{sub d}) and CrO{sub 4}{sup 2−}(T{sub d}) units along with conventional phosphate groups. The optical absorption and ESR studies of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. The highest concentration of Cr{sup 3+} ions (in octahedral sites, with network modifying positions) is found in the sample with 2.0 mol% of Cr{sub 2}O{sub 3}. The analysis of dielectric properties indicates a gradual increase in semiconducting character with increase in the concentration of Cr{sub 2}O{sub 3} from 0.2 to 2.0 mol%. The studies on dielectric breakdown strength identify the highest insulating strength for lowest mol% of Cr{sub 2}O{sub 3} in the present samples.

36 MATERIALS SCIENCE↗
DOE OSTI2013

EPR and magnetic susceptibility investigation of iron-zinc-phosphate glass ceramics

(Fe{sub 2}O{sub 3}){sub x}⋅(P{sub 2}O{sub 5}){sub 40}⋅(ZnO){sub 60−x} glass ceramics containing different concentrations of Fe{sub 2}O{sub 3} ranging from 1 to 20 mol% were obtained by heat treatment of glass samples at 650 °C for 2 h. The structural and magnetic properties of these glass ceramics were investigated by means of electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The EPR spectra of the studied samples revealed absorptions centered at g ≈ 2.0 and 4.3. The compositional variations of the intensity and line width of these absorption lines was interpreted in terms of the variation in Fe{sup 3+} and Fe{sup 2+} ions concentration in the glass ceramics as well as the interaction between the iron ions. The magnetic susceptibility data evidenced the presence of both Fe{sup 3+} and Fe{sup 2+} ions, with their relative content depending on the Fe{sub 2}O{sub 3} concentration. Dipolar and superexchange interactions involving iron ions were revealed depending on the iron content of the sample.

36 MATERIALS SCIENCE↗