Fabrication of Arsenic Sulfide Optical Fiber with Low Hydrogen Impurities

Arsenic sulfide glass optical fibers typically possess extrinsic absorption bands in the infrared wavelength region associated with residual hydrogen and oxygen related impurities, despite using purified precursors. We report a purification process based on the addition of tellurium tetrachloride (TeCl₄) to the glass. During melting, the chlorine from TeCl₄ reacts with the hydrogen impurities to produce volatile products (e.g., HCl) that can be removed by subsequent dynamic distillation. The processing conditions have been modified accordingly to produce optical fibers with significantly reduced loss due to hydrogen sulfide impurity content (1.5 dB/m).     

Effects of the Weak Absorption Tail on the Transmission Loss of Ge–Sb–Se Optical Fibers

Selenide glass optical fibers were fabricated for Ge₃₀Sb₁₀Se₅₈S₂ and Ge₂₀Sb₁₀Se₇₀ glasses. Their transmission loss has been measured and compared with the theoretical attenuation loss that was calculated taking into account the electronic transition absorption, Rayleigh scattering, and multiphonon absorption. A low attenuation loss of the Ge₂₀Sb₁₀Se₇₀ glass composition in 1.2–1.7 μm range has been expected due to its high optical band gap energy compared with the Ge₃₀Sb₁₀Se₅₈S₂ glass. However, the measured attenuation loss of the Ge₃₀Sb₁₀Se₅₈S₂ glass fiber was ∼13 dB/m at 1.5 μm while Ge₂₀Sb₁₀Se₇₀ glass showed ∼82 dB/m. An enhanced weak absorption tail due to the localized states of the Ge₂₀Sb₁₀Se₇₀ glass was responsible for this behavior. Structural defects are related to the localized states and discussed for the present glass compositions.     

Thermal, Dielectric, and Optical Properties of Neodymium Borosilicate Glasses for Thick Films

Because of their thermal, dielectric, and optical properties, new glass compositions and thick-filmed transparent dielectrics containing neodymium oxide (Nd₂O₃) were studied as a source of purer images in plasma display panels. In the present study, PbO–B₂O₃–SiO₂ and PbO–B₂O₃–SiO₂–ZnO–Al₂O₃ were used as starting glass compositions, to which up to 25 wt% of Nd₂O₃ then was added. Increased amounts of Nd₂O₃ increased the glass transition temperature and dielectric constant of the bulk glasses and decreased the coefficient of thermal expansion. The fired thick films (around 30 μm) allowed selectively visible light to penetrate and showed deep absorption properties at 585 nm that were related to an extraneous gas from neon discharge.     

Physical Properties of Chalcogenide and Chalcohalide Glasses

The physical properties of glasses in the Ge₃₀As₁₀Se_{(60— x )}Te _x system with x = 25, 28, 30, and 35 at.% Te, the Ge₃₀As₁₀Se₃₀Te_{(30— y )}I _y system with y = 5, 10, 20, and 30 at.% I, the Ge₃₀As₁₀Se₃₅Te_{(25— z )}I _z system with z = 2, 6, 10, and 20 at.% I, and the [Ge₃₀As₁₀Se₃₀Te₃₀]_{(100— w )}I _w system with w = 0, 5, 10, and 20 at.% I have been investigated. The changes in the glass transition temperature, density, coefficient of thermal expansion, hardness, and viscosity are attributed to the delocalized metallic bonding character of Te in the substitution of Te for Se in the Ge-As-Se-Te glass system and the network-terminating role of iodine in the substitution of I for Te in the Ge-As-Se-Te-I glass system, respectively.     

The Red-Shift of Ultraviolet Spectra and the Relation to Optical Basicity of Ce-Doped Alkali Rare-Earth Phosphate Glasses

The ultraviolet absorption and emission spectra of Ce³⁺ doped phosphate glasses based on gadolinium and sodium phosphates are studied in the present work. Compared with the cerium-free phosphate glass matrixes, CePO₄ doping shifts the ultraviolet absorption edge of glasses into the longer wavelength because of the 4f–5d absorption transition of Ce³⁺. The emission spectra correlate such red-shift with glass compositions. Explanations are based on variation in the optical basicity of glasses, which corresponds not only to the alkali content but also to the O/P ratio. The latter is proportional to the number of nonbridging oxygen in the oxyanion unit (PO₄), and most likely plays an overwhelming role in the overall optical basicity of glasses.     

Tellurite Glasses for Broadband Amplifiers and Integrated Optics

The present investigation discusses the advantage of using RE-ion-doped (Nd³⁺, Tm³⁺, and Er³⁺) TeO₂ glasses for developing fiber and planar broadband amplifiers and lasers. The spectroscopy of RE-ion-doped fibers and glasses is discussed along with the thermal properties of glass hosts. The results of emission from the ³H₄ level in single-mode Tm³⁺-doped tellurite fiber show that the emission band overlaps with Er³⁺ emission from the ⁴I_13/2 level and Nd³⁺ emission from the ⁴F_3/2 level in silicate and tellurite glasses, thereby enabling the development of amplifiers and lasers between 1350 and 1650 nm. Recent results using Z-scan measurements of nonlinear refractive index and absorption demonstrate that the third-order nonlinearity in undoped TeO₂ glasses is of the order of 2 × 10⁻¹⁵ to 3 × 10⁻¹⁵ cm²·W⁻¹ between 1300 and 1550 nm. These results are briefly discussed in view of an amplifier operation combined with ultrafast all-optical switching.     

Absorption and Scattering Losses in Glasses and Fibers for Light Guidance

Fiber optics for telecommunications applications require very high purity glass. Light loss in glass results primarily from absorption and scattering. Transition metal ions and OH ions cause most of the absorption, whereas scattering is caused by microheterogeneity. Scattering losses vary from 1 to 4 dB/km at 850 nm; absorption losses are high near 630 nm, because of Cr³⁺ and Ni²⁺ impurities, but are lower near 850 nm, making this a preferred wavelength region. Flint glass with a total loss of 50 dB/km at 850 nm, prepared using pure material and special techniques, was used as the core of thin-clad optical fibers 70 μm in diameter; these fibers had an internal loss at 850 nm of ∼450 dB/km.     

Equilibrium Amorphous Silicon–Calcium–Oxygen Films at Interfaces in Copper–Alumina Composites Prepared by Melt Infiltration

The microstructure of copper–alumina (Cu-Al₂O₃) composites that have been prepared via the melt infiltration of liquid copper into porous alumina preforms was studied in detail, using various transmission electron microscopy (TEM) techniques. Two different samples—with open pore diameters of 0.2 and 0.8 μm—were investigated. For both specimens, a single crystalline copper network that extended throughout the open porosity of the alumina preform was observed. An amorphous glass phase that contained silicon and calcium was observed at the Al₂O₃/Cu/Al₂O₃ triple junctions. The diameters of these amorphous pockets, which were strongly faceted along the Al₂O₃ grains, were up to 20 and 100 nm for the initial pore sizes of 0.2 and 0.8 μm, respectively. A glass phase that contained silicon and calcium also was present at the Cu/Al₂O₃ interfaces, whereas the Al₂O₃ boundaries remained dry. Detailed high-resolution transmission electron microscopy investigations have shown that the interfacial glass phase at the Cu/Al₂O₃ interfaces exhibited a uniform equilibrium film thickness along the interface region. However, the interfacial film thickness was dependent on the orientation of the Al₂O₃ grain, and its value varied from 0.4 nm for Al₂O₃ rhombohedral-plane termination ((1¯012)) up to 1 nm for Al₂O₃ basal-plane termination ((0001)).     

Infrared Absorption Due to H2O and D2O in a Fluorozirconate Glass

A comparative study of infrared absorption due to H₂O and D₂O impurities in a fluorozirconate glass (53ZrF₄·20BaF₂·4LaF₃·3AlF₃·20NaF) was carried out. The H₂O and D₂O were introduced into the glass by reaction of the surface at 260°C with H₂O and D₂O vapor entrained in a stream of N₂. Reaction with H₂O produced IR absorption bands at 2.9 μm (O–H stretch) and 6.1 μm (H₂O bend). Reaction with D₂O produced bands at 3.9 μm (O–D stretch) and 8.3 μm (D₂O bend). The ratios of the corresponding D₂O/H₂O peak frequencies are 0.74 for both the stretching and bending vibrations, in good agreement with the value of 0.727 predicted from the difference in the OH and OD reduced masses.     

Solid-State Preparation of BaTiO3-Based Dielectrics, Using Ultrafine Raw Materials

BaTiO₃ and Ba(Ti,Zr)O₃ dielectric powders have been prepared from submicrometer BaCO₃, TiO₂, and ZrO₂. By use of submicrometer BaCO₃ the intermediate formation of Ba₂TiO₄ second phase can be widely suppressed. Monophase perovskites of BaTiO₃ were already formed at 900°C and Ba(Ti,Zr)O₃ at 1050°C. Aggregates of very small subgrains could be easily disintegrated to particle sizes <0.5 μm.     

Sintering of a Crystallizable CaO-B2O3-SiO2 Glass with Silver

Effects of Ag addition on sintering of a crystallizable CaO-B₂O₃-SiO₂ glass have been investigated at 700°–900°C in different atmospheres. With Ag content increasing in the range of 1–10 vol%, the softening point, the densification, the onset crystallization temperature, and the total amount of crystalline phase formed of the crystallizable glass are reduced when fired in air. A bloating phenomenon is observed when the crystallizable CaO-B₂O₃-SiO₂ glass doped with 1–10 vol% Ag is fired at 700°–900°C for 1–4 h. Fired in N₂ or N₂+ 1% H₂, however, the above phenomena disappear completely. It is thus believed that the diffusion of Ag into the crystallizable glass, which is caused by the oxidation of Ag in air, is the root cause for the above results observed.     

Fiber Strength Retention of Lanthanum- and Cerium Monazite-Coated Nextel™ 720

Nextel™ 720 fibers were coated with LaPO₄ and CePO₄ monazite. The coatings were applied using washed and unwashed rhabdophane sols derived from La(NO₃)₃/(NH₄)₂HPO₄ and a washed sol derived from Ce(NO₃)₃/H₃PO₄. The coatings were cured in-line at 900°–1300°C. Multiple coatings were also applied. Fiber strength was retained after coating with washed sols, but not with unwashed sols. These results are consistent with earlier work on LaPO₄ monazite fiber coatings derived from La(NO₃)₃/H₃PO₄.     

Electrical Conductivity of Silver Vanadium Tellurite Glasses

We have investigated mixed electronic-ionic conduction in 0.5[ x Ag₂O·(1 − x )V₂O₅]–0.5TeO₂ glasses, where the Ag₂O amount varies over a range of 5–40 mol%. The glass samples have been prepared by quenching the melt. The ac conductivity has been measured at frequencies from 10 Hz to 100 kHz and temperatures of 300–425 K. The data indicate that the conduction mechanism changed from being predominantly electronic to ionic for Ag₂O contents of >27.5 mol%. This transition is due to the change in glass structure, which affects both electronic- and ionic-transport properties. The electronic dc conductivity results have been analyzed in terms of a small polaron-hopping model.     

Wet-Chemical Routes Leading to Scandia Nanopowders

Two wet-chemical routes have been used to synthesize Sc₂O₃ nanopowders from nitrate solutions employing ammonia water (AW) and ammonium hydrogen carbonate (AHC) as the precipitants. The precursors and the resultant oxides are characterized by elemental analysis, X-ray diffractometry, differential thermal analysis/thermogravimetry, high-resolution scanning electron microscopy, and Brunauer-Emmett-Teller analysis. Crystalline γ-ScOOH· n H₂O ( n ≈ 0.5) is the only phase obtained by the AW method. This phase dehydrates to Sc₂O₃ at ∼400°C, yielding hard aggregated nanocrystalline Sc₂O₃ powders. Three types of precursors have been synthesized by the AHC method, depending on the AHC/Sc³⁺ molar ratio ( R ): amorphous basic carbonate [Sc(OH)CO₃·H₂O] at R ≤ 3, crystalline double carbonate [(NH₄)Sc(CO₃)₂·H₂O] at R ≥ 4, and a mixture of the two phases at 3 < R < 4. Among these precursors, only the basic carbonate shows spherical particle morphology, ultrafine particle size (∼50 nm), and weak agglomeration. Sc₂O₃ nanopowders (∼28 nm) with high surface area (∼49 m²/g) have been prepared by calcining the basic carbonate at 700°C for 2 h.     

Mechanical Properties of CoAl Materials with the Combined Additions of ZrO2(3Y) and Al2O3

Intermetallic CoAl powder has been prepared via self-propagating high-temperature synthesis (SHS). Dense CoAl materials (99.6% of theoretical) with the combined additions of ZrO₂(3Y) and Al₂O₃ have been fabricated via spark plasma sintering (SPS) for 10 min at 1300°C and 30 MPa. The microstructures are such that tetragonal ZrO₂ (0.3 μm) and Al₂O₃ (0.5 μm) particles are located at the grain boundaries of the CoAl (8.5 μm) matrix. Improved mechanical properties are obtained; especially the fracture toughness and the bending strength of the materials with ZrO₂(3Y)/Al₂O₃= 16/4 mol% are 3.87 MPa·m^1/2 and 1080 MPa, respectively, and high strength (>600 MPa) can be retained up to 1000°C.     

Low-Temperature Synthesis of Praseodymium-Doped Ceria Nanopowders

Praseodymium-doped ceria (CeO₂) nanopowders have been synthesized via a simple but effective carbonate-coprecipitation method, using nitrates as the starting salts and ammonium carbonate as the precipitant. The precursors produced in this work are ammonium rare-earth double carbonates, with a general formula of (NH₄)_0.16Ce_{1− x} Pr _x (CO₃)_1.58·H₂O (0 < x ≤ 0.20), which directly yield oxide solid solutions on thermal decomposition at a very low temperature of ∼400°C. Praseodymium doping causes a gradual contraction of the CeO₂ lattice, because of the oxidation of Pr³⁺ to smaller Pr⁴⁺, and suppresses crystallite coarsening of the oxides during calcination. Dense ceramics have been fabricated from the thus-prepared nanopowders via pressureless sintering for 4 h at a low temperature of 1200°C.     

Nonradiative Energy Losses and Radiation Trapping in Neodymium-Doped Phosphate Laser Glasses

Fluorescence radiation trapping and nonradiative energy losses from the Nd³⁺⁴F_3/2 state are reported for two widely used commercial phosphate laser glasses (LHG-8 and LG-770). The effects of hydroxyl-group, transition-metal (Cu, Fe, V, Co, Ni, Cr, Mn, and Pt), and rare-earth (Dy, Pr, Sm, and Ce) impurities on the ⁴F_3/2 nonradiative decay rate in these glasses are quantified. Nd concentration quenching effects are reported for doping levels ranging from about 0.5 × 10²⁰ to 8.0 × 10²⁰ ions/cm³. The results are analyzed using the Förster–Dexter theory for dipolar energy transfer. Quenching rates for transition-metal ions correlate with the magnitude of spectral overlap for Nd emission (donor) and the metal ion absorption (acceptor). The nonradiative decay rates due to hydroxyl groups follow Förster–Dexter theory except at low Nd-doping levels (≲2 × 10²⁰ ions/cm³) where the quenching rate becomes independent of the Nd concentration. The data suggest a possible correlation of OH sites with Nd ions in this doping region. The effects of radiation trapping on the fluorescence decay are reported as a function of sample size, shape, and doping level. The results agree well with the theory except for samples with small doping-length products; in these cases, multiple internal reflections from the sample surfaces enhance the trapping effect.     

Dissolution and Separation of Ruthenium in Borosilicate Glass

The behavior of ruthenium oxide (RuO₂) in aluminoborosilicate glass used for the stabilization of nuclear waste was investigated. It was found that 0.025 mass% RuO₂ dissolved as Ru⁴⁺ in the glass at 1400°C, which caused the glass to turn yellow. When the RuO₂ amount was 0.05 mass%, needle-shaped crystals formed in the glass during slow cooling. If the added amount exceeded 0.1 mass% and the cooling rate was slow, it separated rapidly and the glass became pale after cooling. No dissolution of ruthenium was detectable after melting at 1200°C.     

Negative Thermal Expansion in (HfMg)(WO4)3

A single-phase material (HfMg)(WO₄)₃ with an orthorhombic structure, A₂ (WO₄)₃-type tungstate, has been successfully prepared for the first time by the calcination of HfO₂, MgO, and WO₃, substituting Hf⁴⁺ and Mg²⁺ for A³⁺ cations in A₂(WO₄)₃. The new material shows a negative thermal expansion coefficient of approximately −2 ppm/°C from room temperature to 800°C. The mechanism of negative thermal expansion is assumed to be the same as that of Sc₂(WO₄)₃.     

Optical Absorption and Color Caused by Selected Cations in High-Density, Lead Silicate Glass

The effect of impurities on the color of dense flint glass was investigated by comparing the optical absorption caused by cations in Na₂O·3SiO₂·2PbO glass, in Na₂O·3SiO₂·2PbO:1 wt% Sb₂O₃ glass, and in Na₂O·3SiO₂ glass; all three are colorless when of high purity. Of 11 colorants, only vanadium colored both lead glasses less intensely than the Na₂O·3SiO₂ glass. Factors that make the lead glass more susceptible to coloration are higher oxidation states of polyvalent cations, larger absorption cross sections of polyvalent cations, and the tendency of prominent absorption bands to be closer to the wavelength at which eye sensitivity is a maximum.