Optical Active Nano-Glass-Ceramics

This paper reviews the synthesis and characterization of several transparent glass-ceramics with optical active nanocrystals. Glass-ceramics containing ferroelectric Sr_xBa_1-xNb₂O₆ nanocrystals with an ellipsoidal shape show optical phase modulations in the presence of alternative electric fields. In the glass-ceramics with Ba₂TiSi₂O₈ (BTS) nanocrystals, BTS crystalline layers with a thickness of approximately 120 nm are formed at the surface and ellipsoidal-shaped crystallites with a diameter of 100–200 nm are dispersed in the glass matrix. Some TeO₂-based and GeO₂-based glasses show a prominent nanocrystallization. RE-doped CaF₂ nanocrystals are patterned in a spatially selected region by laser irradiations. The size, morphology, and dispersion state of nanocrystals should be carefully checked in each glass system and composition. The basic concept for the design of glass system and composition is also discussed. Some data on optical active performances in transparent glass-ceramics with nanocrystals were introduced.     

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.     

Kinetics of Enthalpy Relaxation at the Glass Transition in Ternary Tellurite Glasses

The kinetics of enthalpy relaxation (recovery) at the glass transition in x K₂O·(20− x )MgO·80TeO₂ glasses has been examined from heat capacity measurements using differential scanning calorimetry to clarify the features of the structural relaxation in ternary TeO₂-based glasses. Ternary glasses such as 10K₂O·10MgO·80TeO₂ show high thermal resistance against crystallization compared with binary glasses. The degree of fragility m estimated from the activation energy for viscous flow E _η and the glass transition temperature T _g is m = 55–62, indicating a fragile character in TeO₂-based glasses. Large heat capacity changes of 43.1–48.2 J·mol⁻¹·K⁻¹ are also observed at the glass transition. The activation energy for enthalpy relaxation Δ H is evaluated from the cooling rate dependence of the limiting fictive temperature, and values of Δ H = 897–1268 kJ·mol⁻¹ are obtained. Negative deviation from additivity in Δ H is also observed. Values of the Kovacs–Aklonis–Huchinson–Ramos (KAHR) parameter θ estimated from Δ H and T _g are 0.33–0.42 K⁻¹. It has been proposed that ternary glasses have more homogeneous and constrained glass structure compared with binary glasses.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

SCR of NOx with NH3 over Cu/NaZSM-5 and Cu/HZSM-5 in the presence of decane

The selective catalytic reduction of NO_x with NH₃ in the presence of decane over Cu/ZSM-5 catalysts prepared from H⁺ and Na⁺ZSM-5 precursors were investigated. Cu/NaZSM-5 catalyst showed significantly higher NO_x conversion compared to Cu/HZSM-5. However, the presence of decane decreased the activity of both the catalysts, due to coke formation. Cu/HZSM-5 catalyst showed a larger decline in NO_x conversion with time on stream compared to Cu/NaZSM-5. The higher activity of Cu/NaZSM-5 is attributed, to the promoting effect of Na⁺ cations in the formation of active Cu⁺ and nitrite and nitrate intermediates species and retardation of coke formation.     

Scintillation from Eu2+ in Nanocrystallized Glass

A Eu²⁺-doped SiO₂–Al₂O₃–CaO–CaF₂ glass was prepared and converted into a transparent glass ceramic by heat treatment. The crystalline phase and its size were determined by X-ray diffraction and a transmission electron microscopy. The scintillation of Eu²⁺ ions in both glass and ceramic under X-ray excitation was investigated and compared with that in a single-crystal scintillator.     

晶粒尺寸对（TiB2＋TiC）/Ni3Al复合材料循环氧化性能的影响（英文）

采用放电等离子烧结法制备（TiB2＋TiC）/Ni3Al复合材料。在950°C下烧结的（TiB2＋TiC）/Ni3Al复合材料的组织比在1050°C下烧结的（TiB2＋TiC）/Ni3Al复合材料的组织更细小。对烧结温度分别为950°C和1050°C的复合材料在900°C下进行循环氧化性能测试。结果表明,在950°C下烧结的复合材料的循环氧化质量损失要小于在1050°C下烧结的复合材料的。晶粒细化有助于在氧化过程汇总的选择性氧化,使得连续的TiO2和Al2O3氧化膜得以在复合材料表面形成,从而提高复合材料的抗氧化性能。     

High Resistance of Cu–Ferrierite to Coke Formation During NH3-SCR in the Presence of n-Decane

Selective catalytic reduction of NO _x by NH₃ over Cu–FER and Cu–ZSM-5 in the presence of n-decane and SO₂ was investigated. NO _x conversion over Cu–ZSM-5 decreased in the presence of n-decane, owing to inhibition of the active sites by coke formation. In contrast, coke formation was negligible over Cu–FER, which maintained its NO _x conversion activity even in the presence of decane. Coke formation was negligible over H–ZSM-5 and H–FER supports, which suggests that Cu species were involved in coke formation. Temperature-programmed reduction by H₂ and electron spin resonance spectroscopy indicated that [Cu–O–Cu]²⁺ was probably the Cu species involved in coke formation over Cu–ZSM-5.     

Characterization of carbon nanofibers synthesized by microwave plasma-enhanced CVD at low-temperature in a CO/Ar/O2 system

The low-temperature synthesis of carbon nanofibers by microwave plasma-enhanced chemical vapor deposition using a CO/Ar/O₂ system and their characterizations were performed. At the optimum oxygen concentration of O₂/CO = 7/1000, vertically aligned CNFs can be synthesized at temperatures as low as 180 °C with growth rates of 4–6 nm/s. The diameter of bulk CNFs is about 50–100 nm and the surface of CNFs is covered by branching fibers and their nuclei with a diameter of about 5–20 nm. Not only the peaks originating from carbon chains, but also oxygen containing groups, such as CO and COC, are observed in the FTIR spectra. The CNFs growth rate is almost independent from the substrate temperature and it is concluded that an elementary process not on the substrates, but in the gas phase, is the rate-determining step in the present CO/Ar/O₂ microwave-plasma-enhanced CVD system.     

The effect of the hydrothermal treatment with aqueous NaOH solution on the photocatalytic and photoelectrochemical properties of visible light-responsive TiO2 thin films

The effect of the hydrothermal treatment with aqueous NaOH solution on the photoelectrochemical and photocatalytic properties of visible light-responsive TiO₂ thin films prepared on Ti foil substrate (Vis-TiO₂/Ti) by a radio-frequency magnetron sputtering (RF-MS) deposition method has been investigated. The hydrothermally treated Vis-TiO₂/Ti electrodes exhibited a significant increase in their photocurrent under UV and visible light irradiation as compared to untreated Vis-TiO₂/Ti electrode. SEM investigations revealed that the surface morphology of Vis-TiO₂/Ti are drastically changed from the assembly of the TiO₂ crystallites to the stacking of nanowires with diameters of 30–50 nm with increasing hydrothermal treatment time (3–24 h), accompanying the increase in their surface area. The separate evolution of H₂ and O₂ from water under solar light irradiation was successfully achieved using the Vis-TiO₂/Ti/Pt which is hydrothermally treated for 5 h, while the H₂ evolution ratio was 15 μmol h⁻¹ in the early initial stage, corresponding to a solar energy conversion efficiency of 0.23%.