The Influence of Sb2O3 Addition on the Properties of Low-melting ZnO–P2O5 Glasses

The influence of 0–16 mol% Sb₂O₃ substitution for P₂O₅ on the properties of ZnO–P₂O₅ glasses has been investigated. It was shown that Sb₂O₃ could participate in the glass network and thermal stability of the glasses decreased with increasing Sb₂O₃ content. Glass transition temperature T _g, softening temperature T _s, and water durability all decreased firstly (up to 6 mol% Sb₂O₃ added) and then increased. Substitution of 12 mol% Sb₂O₃ led to a 16°C decrease in T _g and 30°C decrease in T _s, and weight loss of the glass was only 0.42 mg/cm², which is ∼11 times lower than that of the glass without Sb₂O₃ after immersion in deionized water at 90°C for 1 day. The glass containing 12 mol% Sb₂O₃ might be a substitute for Pb-based glasses in some applications.     

Prominent Nanocrystallization of 25K2O·25Nb2O5·50GeO2 Glass

Some K₂O-Nb₂O₅-GeO₂ glasses are prepared, and their crystallization behaviors are examined. 25K₂O·25Nb₂O₅·50GeO₂ glass with the glass transition temperature T _g= 622°3C and crystallization onset temperature T _x= 668°3C shows a prominent nanocrystallization. The crystalline phase is K_3,8Nb₅Ge₃O_20,4 with an orthorhombic structure. The sizes of crystals in the crystallized glasses heat-treated at 630° and 720°3C for 1 h are °10 and 20–30 nm, respectively, and the crystallized glasses obtained by heat treatments at 620°-850°3C for 1 h maintain good transparency. The density of crystallized glasses increases gradually with increasing heat-treatment temperature, and the volume fraction of crystals in the sample heat-treated at 630°3C for 1 h is estimated to be ∼35%. The usual Vickers hardness and Martens hardness (estimated by nanoindentation) of 25K₂O·25Nb₂O₅·50GeO₂ glass change steeply by heat treatment at T _g, i.e., at around 35% volume fraction of nanocrystals. The present study demonstrates that the composite of nanocrystals and the glassy phase has a strong resistance against deformation during Vickers indenter loading in crystallized glasses.     

Crystallization of ZBLAN Glass

The glass transition, onset crystallization, solidus, and liquidus temperatures of a ZBLAN glass have been measured by differential thermal analysis in a sealed Pt ampoule. The onset crystallization was observed at 335°C for a powdered glass, while for a monolithic glass, prepared by in situ quenching in the Pt capsule, the onset crystallization was observed at 395°C, 135°C higher than T _g. Surface-induced heterogeneous nucleation is therefore proposed to be important for the crystallization of ZBLAN glasses. The solidus temperature was observed at 452°C, about 10°C lower than reported for the subsystem ZrF₄–BaF₂–NaF.     

Viscosity and Surface Tension of Oxynitride Glass Melts

The viscosities and surface tensions of three MgO-Al₂O₃-Y₂O₃-SiO₂-based oxynitride glass melts were measured. Glass transition temperature, Littleton temperature, and sink-in temperature were obtained, and by using the Vogel-Fulcher-Tammann equation the viscosities were calculated from T _g (820° to 940°C) to 1600°C. The surface tensions were measured by the drop weight and the drop geometry methods and displayed values between about 500 and 600 N.mm⁻¹. These values are about a factor of two higher than the surface tensions of oxide glass melts.     

Classical and Differential Thermal Analysis Studies of the Glass-Ceramic Transformation in a YSiAlON Glass

Nucleation and crystallization studies were conducted on a YSiAlON glass that contained 17 equiv.% nitrogen (7.5 at.%) by using a two-stage nucleation-and-growth treatment. Classical and differential thermal analysis (DTA) techniques were both used to study the crystallization process, to ensure that the optimum heat-treatment schedule that yielded a fine microstructure and minimum residual glass was applied. The optimum nucleation and crystallization temperatures were determined from DTA traces that were recorded from isothermal heat treatments at different nucleating temperatures, ranging between T _g - 40°C and T _g+ 100°C for 1 h and crystal-growth temperatures in the range of 1170°-1310°C for 0.5 h, respectively. The activation energy for the crystallization process was determined, based on the analysis of the variation of peak temperature at five different heating rates. Specimens heat treated in a tube furnace under nitrogen gas were subjected to microscopical investigation, and results showed variations in the volume fraction of crystalline phases and crystal size with nucleation temperature. The nucleation temperature, T _g+ 40°C (1025°C), which corresponded to the maximum volume fraction of crystalline phases and minimum crystal size, was consistent with the optimum nucleation temperature, T _g+ 35°C (1020°C), as determined from DTA. The time and temperature of nucleation and crystal growth dictated the nature and size of the crystalline phases. Properties such as hardness and density were assessed and correlated to the nucleation temperature. The influence of sample specific surface on the devitrification mechanisms was estimated, and bulk nucleation was observed to be the dominant nucleation mechanism.     

Visible Transparent GeSe2–Ga2Se3–KX (X=I, Br, or Cl) Glasses for Infrared Optics

GeSe₂–Ga₂Se₃–KX (X=I, Br, or Cl) chalcohalide glasses are synthesized, and their optical properties and thermo-mechanical properties are investigated. A structural model is put forward to elucidate the interesting compositional dependences of the short-wavelength absorption edge (λ_s) and glass transition temperature ( T _g). These glasses are transparent in the red-light region in addition to the 3–5 and 8–14 μm atmospheric windows. Most of their T _g exceed 300°C, and they also present good thermal stability. These properties make them attractive materials for infrared optics.     

Volatility of Simulated High-Level Nuclear Waste Glass by Thermogravimetric Analysis

The volatilities of simulated, high-level nuclear waste glasses have been measured using thermogravimetric analysis (TGA). These volatilities were measured in the region of the glass transition temperature ( T _g) of the waste glasses, which is between 450° and 500°C. These data were obtained because the Waste Acceptance Preliminary Specifications require that no foreign materials be released into the canistered waste form upon heating of the canister to this glass transition temperature. In fact, all of the waste glass samples studied actually exhibited a net weight gain upon heating. This weight gain was shown to be due to oxygen uptake through oxidation of FeO. Powdered glass samples did show a small weight loss which was smaller in magnitude than the weight gain and was associated with water desorption. No true volatility was detected to the level of sensitivity (0.01 wt%) of the TGA instrument. This converts to a sensitivity of 330 μ g/m² of glass surface and a corresponding minimum value of 41 mg of volatiles for each Defense Waste Processing Facility conistered waste form. TGA experiments carried out at higher temperatures (800°C) revealed that organic concentrations in the waste glasses are less than 0.01 wt%. Thus, these results demonstrate that the Defense Waste Processing Facility will be able to comply with the Waste Acceptance Preliminary Specifications on the exclusion of foreign materials from the canistered waste forms, after exposure to T _g.     

Effect of Sintering Temperature on the Microstructural and Flux Pinning Characteristics of Bi1.6Pb0.5Sr1.8La0.2Ca1.1Cu2.1O8+δ Ceramics

We evaluated the microstructure, superconducting, and flux pinning properties of La-doped (Bi,Pb)-2212 bulk sample by varying its sintering temperature ( T _sinter) between 846° and 860°C. Significant variations in microstructure, self- and in-field J _Cs at 64 K and flux pinning properties have been observed for La-substituted samples with respect to T _sinter. The sample sintered at 858°C shows best self-field J _C while that sintered at 846°C shows the best in-field J _C due to the changes in microstructure. The activation energy of flux motion (pinning potential U _o) is estimated from the field dependent resistivity–temperature curves, and the flux pinning force ( F _P) from the field-dependent J _C values. It is found that the La-doped samples, sintered at 846°C show maximum F _P and U _o of 463 kN/m³ and 0.380±0.001 eV as against 93.6 k/Nm³ and 0.140±0.001 eV, respectively, for the sample sintered at 858°C. The undoped (Bi,Pb)-2212 shows a maximum F _P and U _o of 12.7 k/Nm³ and 0.074±0.001 eV, respectively. The origin of these enhanced properties is mainly from the normal-like defects introduced by optimum La-doping at the Sr-site, at an optimum sintering temperature.     

Glass Formation and Crystallization Behavior of a Novel GeS2–Sb2S3–PbS Chalcogenide Glass System

In the present work, a large glass-forming region was found in the novel GeS₂–Sb₂S₃–PbS system, in which up to 58 at.% PbS could be incorporated without deteriorating the thermal and physical properties of glasses. Infrared (IR) transmitting glass ceramics with a large amount of small-sized crystals (<100 nm) were then produced by choosing sub-stable compositions and annealing at fairly low temperatures (15°–30°C above T _g) for long durations (up to 100 h). Crystals were identified by X-ray diffraction as Pb₂GeS₄, PbGeS₃, PbS, PbSb₂S₄, etc., depending on base glass compositions. Compared with base glasses, glass ceramics showed much improved thermal shock resistance and fracture toughness, making them good candidate materials for IR optics.     

Nucleation and Crystallization of a Lithium Aluminosilicate Glass

An aluminosilicate glass of composition 61SiO₂6Al₂O₃10MgO6ZnO·12Li₂O·5TiO₂ (mol%) has been prepared by a melting process and investigated as far as crystallization is concerned. Glass-ceramic is easily obtained because glass shows a high tendency to crystallize starting from 700°C. The crystalline phases evolve with temperature, showing the aluminosilicates to be the main phase up to 1050°C, followed by metasilicates and silicates, some of which have lower melting points. The titanates of Mg and Zn develop from the phase-separated glass, soon after T _g, and grow to form nucleation centers for the other crystalline phases. The evolution from phase-separated glass to glass-ceramic has been followed by many thermal, diffractometric, spectroscopic, and microscopic techniques.     

Defect Centers in Gamma-Irradiated Single-Crystal Al2O3

The γ-irradiation-induced optical absorption spectra of annealed Al₂O₃ single crystals were analyzed. The samples were beat-treated in O₂ or vacuum from 1600° to 1800°C. Four absorption bands are reported with average peak positions at 3.4,4.8,5.5, and 6.6 eV for samples annealed in O₂ at ≥ 1750°C. Vacuum anneals up to 1800°C and O₂ anneals at < 1700°C failed to generate observable bands in the energy range studied. There is also evidence that one or more bands exist at >6.6 eV. The radiation-induced change in the absorption spectra is reported and the defect centers responsible for the measured optical absorption bands are discussed with respect to the aliovalent impurities in the host lattice. Special attention is given to the role of the Fe³⁺ impurity ion.     

Effect of PO2 on Bulk and Grain Boundary Resistance of n-Type BaTiO3 at Cryogenic Temperatures

Complex impedance analysis at cryogenic temperatures has revealed that the bulk and grain boundary properties of BaTiO₃ polycrystals are very sensitive to the oxygen partial pressure during sintering. Polycrystals sintered at P _O2 as low as 10⁻¹⁵ atm were already electrically heterogeneous. The activation energy of the bulk conductivity in the rhombohedral phase was found to be close to that of the reduced undoped single crystal (i.e., 0.093 eV). The activation energy of the grain boundary conductivity increases with the temperature of the postsinter oxidation treatment from 0.064 to 0.113 eV. Analysis of polycrystalline BaTiO₃ sintered in reducing atmosphere and then annealed at P _O2= 0.2 atm has shown that the onset of the PTCR effect occurs at much higher temperatures than expected in the framework of the oxygen chemisorption model. The EPR intensity of barium and titanium vacancies increases after oxidation at T > 1000°C. A substantial PTCR effect is achieved only after prolonged annealing of the ceramic in air at temperatures as high as 1200–1250°C. This result suggests that the PTCR effect in polycrystalline BaTiO₃ is associated with interfacial segregation of cation vacancies during oxidation of the grain boundaries.     

Real-Time Nucleation and Crystallization Studies of a Fluorapatite Glass–Ceramics Using Small-Angle Neutron Scattering and Neutron Diffraction

Real-time small-angle neutron scattering (SANS) and neutron diffraction (ND) studies have been performed on a calcium fluorapatite (Ca₅(PO₄)₃F) (FAP) glass–ceramic composition. The cast glass exhibited scattering at low q and a peak in I ( q ) at higher q . The scattering at low q is thought to arise from a larger-scale nucleated structure, while the peak in I ( q ) is thought to arise from a finer spinodally decomposed structure. High temperature viscoelastic measurements show two reductions in the storage modulus ( E ') and two peaks in the damping factor (tan δ) consistent with a glass that has undergone amorphous phase separation (APS) during the casting process. On heating to 780°C, the scattering at low q increased in intensity, while the peak in I ( q ) increased in intensity and moved to lower q , consistent with the coarsening of the finer scale phase separated structure. During isothermal experiments, the scattering at low q increased in intensity and the peak in I ( q ) moved to lower q , corresponding to a final spacing of about 35 nm. After about 30 min at 740°C, and 12 min at 750°C the coarsening process effectively stopped and is inhibited by the glass transition temperature ( T _g) of the second glass phase. ND showed the glass to crystallize on heating to FAP and then mullite (2SiO₂·3Al₂O₃). At high temperatures, both the FAP and mullite crystal phases partially re-dissolved, but were found to re-crystallize rapidly on subsequent cooling. The results indicate that the proposed crystal growth hold is actually a crystal dissolution hold, with re-crystallization occurring rapidly on cooling. The results indicate that it is important to control not only the heat-treatment cycle but also the cooling cycle.     

Stable and Metastable Phase Relationships in the System ZrO2–ErO1.5

Stable and metastable phase relationships in the system ZrO₂–ErO_1.5 were investigated using homogeneous samples prepared by rapid quenching of melts and by arc melting. The rapidly quenched samples were annealed in air for 48 h at 1690°C or for 8 months at 1315°C. Two tetragonal phases ( t - and t '-phases) were observed after quenching samples heated at 1690°C to a room temperature, whereas one t -phase and cubic ( c -) phase were found in those treated at 1315°C. Since the t '-phase is obtained through a diffusionless transformation during cooling from a high-temperature c -phase, t - and c -phases can coexist at high temperature. The t - and c -phases field spans from 4 to 10 mol% ErO_1.5 at 1690°C and from 3 to 15 mol% ErO_1.5 at 1315°C. The equilibrium temperature T ^t-m ₀ between the t - and monoclinic ( m -) phases estimated from A_s and M_s temperatures decreased with increasing ErO_1.5 contents.     

Synthesis and Electrical Properties of Dense Ce0.9Gd0.1O1.95 Ceramics

Uniform spherical powders of Ce_0.9Gd_0.1O_1.95 with an average diameter of 250 nm were obtained at 700°C from a sol-gel process of mixing nitrates and ethylene glycol. Broadening of the X-ray peaks of the fluorite structure reveals a small crystallite size within the powders. Sintering in air of pressed pellets of the powders at 1585°C gives ceramics of 99% theoretical density with grain sizes 1-10 µm and a cubic unit cell a = 5.422 ± 0.034 Å. The electrical conductivity σ=σ_o+σ_e has two components. In air or argon, the electronic component σ_e is negligible and the oxide-ion conductivity σ_o is not described by a classical Arrhenius equation; a pronounced curvature at T similar/congruent T * has been observed in the Arrhenius plot of the bulk conductivity. The system could be modeled by a condensation of mobile oxygen vacancies into ordered clusters below a temperature T * similar/congruent 583 ± 45°C and a motional enthalpy Δ H _m= 0.63 ± 0.01 eV for the vacancies. A measured trapping energy Δ H _t(1 - T/T *) has Δ H _t= 0.19 ± 0.01 eV = 2.57 kT *. In a reducing atmosphere, σ_e exhibits a small-polaron motional enthalpy Δ H _p= 0.40 ± 0.08 eV for transfer of a 4 f electron from a Ce³⁺ to a Ce⁴⁺ ion and a Δ H _p+Δ H _pt= 0.51 ± 0.04 eV at T < T *.     

Red Color GeSe2-Based Chalcohalide Glasses for Infrared Optics

GeSe₂–Ga₂Se₃–CsI chalcohalide glasses are synthesized, and their optical properties and thermo-mechanical properties are studied. A typical characteristic of the glasses is their excellent transparency in the red-light region in addition to the 8–14 μm atmospheric window, which is of vital importance to the quality control of infrared systems. The short-wavelength absorption edge λ_s of the glass system has a distinct blue shift with increasing CsI content, and the physicochemical interpretations are suggested and formulated. These glasses present a glass transition temperature ( T _g) around 300°C and good thermal stability. Consequently, they can be promising candidate materials for infrared optics, although their hardness is relatively weak.     

Structural Variation of the BaTi4O9 Thin Films Grown by RF Magnetron Sputtering

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using rf magnetron sputtering and the structure of the thin films were then investigated. For the films grown at low temperature (≤350°C), an amorphous phase was formed during the deposition, which then changed to the BaTi₅O₁₁ phase when the annealing was conducted below 950°C. However, when the annealing temperature was higher than 950°C, a BaTi₄O₉ phase was formed. On the contrary, for the films grown at high temperature (>450°C), small BaTi₄O₉ grains were formed during the deposition, which grew during the annealing. The homogeneous BaTi₄O₉ thin films were successfully grown on Pt/Ti/SiO₂/Si substrate when they were deposited at 550°C and subsequently rapid thermal annealed at 900°C for 3 min.     

Temperature-Dependent Iron Solubility in Mullite

Sample disks prepared from Al₂O₃ (61 wt%), SiO₂ (28 wt%), and Fe₂O₃(II wt%) powders were sintered at 1270° and 1440°C and then annealed between 1300° and 1670°C. The annealed samples consisted of mullite as the main compound with minor amounts of glass and sometimes magnetite. The iron content of the mullites decreases strongly from ∼ 10.5 wt% Fe₂O₃ at 1300°C to ∼ 2.5 wt% Fe₂O₃ at 1670°C. A complex temperature-controlled exsolution mechanism of iron from mullite is considered.     

Preparation of Superconducting Bi(Pb)-Sr-Ca-Cu-O Thick Films on Magnesia Substrate

Superconducting Bi(Pb)-Sr-Ca-Cu-O powders were prepared by the emulsion-drying method The powders consisting of the low- T _c phase (Bi(Pb)₂Sr₂Ca₁Cu₂O_y) and small amount of Ca₂PbO₄ were prepared by calcining under low oxygen partial pressure at 750°, 800°C. These calcined powders were used to prepare thick films on single-crystal MgO(100) substrates using a screen-printing technique to study the effect of the calcinations temperature and annealing procedure on the high-T_c phase (Bi(Pb)₂Sr₂Ca₂Cu₃O_y)formation. The formation of high-T_c phase was observed to be dependent on the calcinations conditions. The high- T_c phase formed very quickly (sintering at 840°C for 4 h), and the best films showed a sharp superconducting transition at about 105 K.     

Elastic Properties and Molar Volume of Rare-Earth Aluminosilicate Glasses

The elastic properties, molar volume, and glass transition temperature ( T _g) of rare-earth-containing aluminosilicate glasses were investigated in the compositions of SiO₂–LnAlO₃ and SiO₂–Ln_3/4Al_5/4O₃, where Ln is Y, La, Nd, Eu, or Yb. The molar volume decreased with decreased ionic size of the Ln³⁺ ion, and T _g and elastic moduli increased in the same order. The Yb-containing glasses showed the highest Young's modulus among all the oxide glasses, even higher than the highest value ever known for glass containing Y₂O₃, as expected from the smaller ionic radius of Yb³⁺ than that of Y³⁺. The bulk modulus was found to be almost proportional to the inverse four-thirds power of the molar volume of glasses in each composition, indicating that Ln³⁺ ions can substitute for each other without changing the glass structure except for the size of the local structure around themselves. From the comparison of these properties, the structural role of rare-earth ions in these glasses is discussed.