Glass Formation and Properties of Chalcogenides in a GeSe2–As2Se3–PbSe System

The glass-forming region in a GeSe₂–As₂Se₃–PbSe system was determined, and the dependence of properties on the composition as a formula of 20 GeSe₂–(80− x )As₂Se₃− x PbSe ( x =0–30) was investigated. Measurements include density, differential scanning calorimetry, X-ray diffraction, Vis-NIR, and IR transmission spectra. A fairly large glass-forming region was obtained where the higher lead content could be introduced into the system in the As₂Se₃-rich region than in the GeSe₂-rich region. With the introduction of PbSe, the density of glass increased and the calculated molar volume decreased while the crystallization tendency increased, which was indicated by the decreasing Δ T ( T _x− T _g). The activation energy of crystallization and the Avrami exponents were also obtained using the modified Ozawa equation. Under proper annealing conditions, suitable IR transmittance glass–ceramics were obtained.     

Formation and Properties of Chalcogenide Glasses in the GeSe2–As2Se3–CdSe System

The glass-forming region in a GeSe₂–As₂Se₃–CdSe system and the dependence of properties on glass compositions as a formula of 70GeSe₂–(30− x )As₂Se₃– x CdSe ( x =0–25) were investigated. Measurements included density, micro-hardness, differential scanning calorimetry (DSC), X-ray diffraction, and IR transmission spectra. A large glass-forming region was shown while addition of Cd increases the crystallization trend of the system. Besides, the Cd content accommodated by the system to form glass is found to be lower in the As₂Se₃-rich region than in the GeSe₂-rich region. With the introduction of CdSe, density, micro-hardness, and T _g of glasses increase whereas an exothermal peak in the DSC curve appears and thermal stability (Δ T ) decreases. The activation energy of crystallization and the Avrami exponent were also obtained using the modified Ozawa equation.     

Formation and Properties of GeSe2–Ga2Se3–PbI2 Novel Chalcohalide Glasses

The glass-forming region of the GeSe₂–Ga₂Se₃–PbI₂ system was determined and homogeneous glasses were prepared. The maximum dissolvable PbI₂ can be up to 50 mol%. The structures of glasses were characterized by Raman spectroscopy. The thermal, optical, and some basic physical properties of the glasses were investigated. The results show that GeSe₂–Ga₂Se₃–PbI₂ glasses have a wide region of transmission window (0.7–16 μm) and high refractive index (∼2.5) with the addition of PbI₂. The glasses have good glass-forming ability and high glass transition temperatures. Consequently, these novel glasses may be promising candidate materials for infrared optics and nonlinear optical field.     

Phase Separation Inducing Controlled Crystallization of GeSe2–Ga2Se3–CsI Glasses for Fabricating Infrared Transmitting Glass–Ceramics

Infrared transmitting glass–ceramics based on the selected glass of 65GeSe₂–25Ga₂Se₃–10CsI were obtained by a two-stage heat-treatment method. Results of X-ray diffraction and scanning electronic microscopy indicated that droplet-like nanoparticles containing cubic Ga_2−δGe_δSe₃ crystals are homogeneously generated in the glass–ceramics and that the whole glass–ceramic process is composed of phase separation, nucleation, and crystal growth. Evolutions of the optical and mechanical properties of glass–ceramics versus annealing time at the first-stage heat treatment were also investigated. Compared with the parent glass, the fabricated glass–ceramics show considerably enhanced fracture toughness, practicable infrared transparence, and microhardness, which confer them with considerable competitive advantages over currently used infrared materials.     

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.     

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.     

Controlled Crystallization of GeSe2–Ga2Se3–CsI Chalcohalide Glasses During Molding

This is an attempt to produce molded 8–14 μm transmitting glass–ceramics by a one-step molding technique. Controlled crystallization is expected to be carried out during application of an appropriate molding process to pure glasses. GeSe₂–Ga₂Se₃–CsI chalcohalide glass was used for the attempt, and well-designed molding parameters were applied to the glass. The results indicate that large quantities of submicrometer crystalline particles are formed and regularly distributed inside the glass matrix during the molding, leading to improved toughness without influencing the 8–14 μm transmittance. This phenomenon implies that it is possible and convenient to produce molded glass–ceramics by a one-step molding technique.     

Effect of Sb2O3 on Thermal Properties of Glasses in Bi2O3–B2O3–SiO2 System

Glasses with compositions 50Bi₂O₃– x Sb₂O₃–10B₂O₃–(40– x ) SiO₂ ( x =0, 1, 3, 5, 8, 10) have been prepared by conventional melt quench technique. Substitution of Sb₂O₃ for SiO₂ exerted an obvious effect on properties of glasses, especially, increased glass transition temperature ( T _g) and crystalline temperature ( T _c) greatly. Results of infrared transmission spectra attributed the effect to the formation of new bridging bonds of Sb–O–B and Sb–O–Si in glass network.     

Structure, Thermal Behavior, Chemical Durability, and Optical Properties of the Na2O–Al2O3–TiO2–Nb2O5–P2O5 Glass System

The FTIR, Raman, UV-Vis, ³¹P MAS-NMR, DTA, and refractive index measurements have been combined to investigate a series of glasses with the general formula 20Na₂O–5Al₂O₃− x TiO₂–(45− x )Nb₂O₅–30P₂O₅, 15≤ x ≤45. The glass structure, as well as thermal, optical, and chemical durability properties, were then described as functions of the f _Nb/ f _Ti ratio. An increase of the f _Nb/ f _Ti ratio correlates with a decrease in length of the average phosphate chains linked through Nb–O–P and Ti–O–P bonds, with an increase in the glass stability and with increase in the linear refractive indices at 632.8 nm from 1.79 to 1.89. Furthermore, niobium is more effective than titanium in improving chemical durability.     

Subsolidus Phase Relations in the Ga2O3-In2O3-SnO2 System

Subsolidus phase relationships in the Ga₂O₃–In₂O₃–SnO₂ system were studied by X-ray diffraction over the temperature range 1250–1400°C. At 1250°C, several phases are stable in the ternary system, including Ga₂O₃( ss ), In₂O₃( ss ), SnO₂, Ga_{3− x} In_{5+ x} Sn₂O₁₆, and several intergrowth phases that can be expressed as Ga_{4−4 x} In_{4 x} Sn _{n −4}O_{2 n −2} where n is an integer. An In₂O₃–SnO₂ phase and Ga₄SnO₈ form at 1375°C but are not stable at 1250°C. GaInO₃ did not form over the temperature range 1000–1400°C.     

Glass-Forming Ability and Crystallization Tendency Evaluated by the DTA Method in the Na2O–B2O3–Al2O3 System

In order to evaluate the crystallization tendency of glasses, the ratio of the crystallization temperature to the liquidus temperature ( T _c/ T _L) was obtained by DTA measurement for the Na₂O–B₂O₃ and Na₂O–B₂O₃–Al₂O₃ systems. The critical cooling rate for glass formation ( Q *) was also measured. The measurements were performed in the composition range of (100 − x )Na₂O–( x )B₂O₃, ( x = 25–35 and 60–100 mol%), and (100 − y )0.5Na₂O·0.5B₂O₃−( y )Al₂O₃, ( y = 6–34 mol%). The relationship between T _c/ T _L and Q * was discussed. A linear relationship between T _c/ T _L and log Q * for these systems was found. Furthermore, the relationship between T _c/ T _L and Q * was verified by computer simulation based on the crystallization kinetics of glass or supercooled liquid.     

Subsolidus Phase Relationships in the Ga2O3–Al2O3–TiO2 System

Subsolidus phase relationships in the Ga₂O₃–Al₂O₃–TiO₂ system at 1400°C were studied using X-ray diffraction. Phases present in the pseudoternary system include TiO₂ (rutile), Ga_{2−2 x} Al_{2 x} O₃ ( x ≤0.78 β-gallia structure), Al_{2−2 y} Ga_{2 y} O₃ ( y ≤0.12 corundum structure), Ga_{2−2 x} Al_{2 x} TiO₅ (0≤ x ≤1 pseudobrookite structure), and several β-gallia rutile intergrowths that can be expressed as Ga_{4−4 x} Al_{4 x} Ti _{n −4}O_{2 n −2} ( x ≤0.3, 15≤ n ≤33). This study showed no evidence to confirm that aluminum substitution of gallium stabilizes the n =7 β-gallia–rutile intergrowth as has been mentioned in previous work.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Properties of Dy3+-Doped Ge–As–Ga–Se Chalcogenide Glasses

In the present work, properties of Dy³⁺-doped chalcogenide glasses as a stoichiometric formula of (0.9− x )GeSe₂– x AsSe_3/2–0.1GaSe_3/2 ( x =0.1, 0.2, 0.3, 0.4, 0.5, 0.6) were investigated as a comparison with the previously studied Ge–Ga–Se system. Property measurements include differential thermal analysis, density, Vis-NIR and IR transmission spectra, and fluorescent emission spectra. Judd–Ofelt analysis was performed using the calculated oscillator strengths of glasses. All properties of glasses show obvious dependence on compositions. Especially, the improved devitrification resistance and the longer fluorescence life at 1.34 μm emission were observed with the increasing As content. Noticeably, abnormal changes in some properties occurred to the glass whose average coordination number corresponds to the threshold of two-dimensional–three-dimensional topological phase transition.     

A Rapidly Responding Sensor for Methanol Based on Electrospun In2O3–SnO2 Nanofibers

In this paper, we presented a simple and effective electrospinning technique for the preparation of In₂O₃–SnO₂ composite nanofibers. The morphology and chemical structure of the as-prepared samples were analyzed by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The results showed that large quantities of In₂O₃–SnO₂ composite nanofibers with diameters from 60 to 100 nm were obtained. The In₂O₃–SnO₂ composite nanofibers exhibited excellent gas sensing properties to methanol, such as fast response/recovery properties, high sensitivity, and good selectivity.     

Energetics of La2O3–HfO2–SiO2 Glasses

A series of La₂O₃–HfO₂–SiO₂ glasses, approximately along the join 0.73SiO₂–0.27( x HfO₂–(1− x )La₂O₃), 0< x <0.3), was prepared using containerless processing techniques (aerodynamic levitation combined with laser heating in oxygen). The enthalpy of formation and enthalpy of vitrification at 25°C were obtained from drop solution calorimetry of these glasses and appropriate crystalline compounds in a molten lead borate (2PbO–B₂O₃) solvent at 702°C. The enthalpy of formation from crystalline oxides was exothermic and became less exothermic with increasing HfO₂ content. Heat contents were measured by transposed temperature drop calorimetry and depended linearly on the HfO₂ content. Differential scanning calorimetry showed that both the onset glass transition and the onset crystallization temperature of these glasses increased with increasing HfO₂ content. Upon slow cooling in air, the glasses crystallized to a mixture of baddeleyite, cristobalite, lanthanum disilicate, and hafnon.     

Structure and Properties of Low Phonon Antimony Glasses in the K2O–B2O3–Sb2O3–ZnO System

The monolithic glass-forming region of the low phonon and low softening point antimony glasses containing high Sb₂O₃ (40–75 mol%) in the novel quaternary K₂O–B₂O₃–Sb₂O₃–ZnO system has been found with the help of X-ray diffraction (XRD) analysis. The structure of a series of glasses with the general composition of (mol%) 15K₂O–15B₂O₃–(70− x )Sb₂O₃– x ZnO (where x =5–25) has been evaluated by infrared reflection spectral (FT-IRRS) analyses. All the glasses are found to possess a low phonon energy of around 600 cm⁻¹, as revealed by FT-IRRS. Their softening point ( T _s), glass transition temperature ( T _g), and coefficient of thermal expansion (CTE) have been found to vary in the ranges of 351°–379°C, 252°–273°C, and 195–218 × 10⁻⁷ K⁻¹, respectively. These properties are found to be controlled by their fundamental property, like the covalent character of the glasses, which is found to increase with an increase in Sb₂O₃ content. In addition, the devitrified glasses have been characterized by XRD and field emission scanning electron microscopy, which manifests the presence of nanozinc antimony oxide crystals with sizes of 21–43 nm. The exhibited properties have revealed that they are a new class of versatile materials.     

Preparation and Aging Behavior of Chemical-Solution-Deposited (Pb(Mg1/3Nb2/3)O3)1-x–(PbTiO3)x Thin Films without Seeding Layers

The aging behavior of the solid-solution series (Pb(Mg_1/3Nb_2/3)O₃)_{1− x} –(PbTiO₃) _x (PMN_{1− x} −PT _x ) prepared by chemical-solution deposition without seeding layers was investigated. A strong influence of the rapid thermal annealing step on the film density was determined. The best nucleation and density of the thin films occurred when each deposited layer was separately pyrolyzed and crystallized. The thin-film microstructure was investigated using scanning electron microscopy. Conventional capacitance-voltage and hysteresis measurements were performed. For the first time, investigations on the fatigue performance and the leakage current for alternating-current and direct-current voltage were executed, which are important for the reliability in device applications.     

Pyrochlore Phases in the System ZnO–Bi2O3–Sb2O5: I. Stoichiometries and Phase Equilibria

Two cubic pyrochlore phases exist in the system ZnO–Bi₂O₃–Sb₂O₅. Neither has the supposed "ideal" stoichiometry, Zn₂Bi₃Sb₃O₁₄. One, P ₁, is a solid solution phase, Zn_{2+ x} Bi_{2.96−( x − y )}Sb_{3.04− y} O_14.04+δ where 0< x <0.13(1), 0< y <0.017(2) and a =10.4285(9)−10.451(1) Å. The other, P ₂, is a line phase, Zn₂Bi_3.08Sb_2.92O_13.92 with a =10.462(2) Å. Subsolidus phase relations at 950°C involving phases P ₁ and P ₂ in the ZnO–Bi₂O₃–Sb₂O₅ phase diagram have been determined.     

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.