Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO2) nano-photocatalysts, with different phases, prepared using a modified sol-gel process were employed in the degradation of rhodamine at 10 mg L-1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450 degrees C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K-app) of 0.023 min(-1). The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024 min(-1) for 450, 500, 550 and 600 degrees C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017 min(-1), which is similar to that of the commercial titania.

Low-thermal-budget solution processing of thin films of zinc ferrite and other complex oxides

Further miniaturization of magnetic and electronic devices demands thin films of advanced nanomaterials with unique properties. Spinel ferrites have been studied extensively owing to their interesting magnetic and electrical properties coupled with stability against oxidation. Being an important ferrospinel, zinc ferrite has wide applications in the biological (MRI) and electronics (RF-CMOS) arenas. The performance of an oxide like ZnFe2O4 depends on stoichiometry (defect structure), and technological applications require thin films of high density, low porosity and controlled microstructure, which depend on the preparation process. While there are many methods for the synthesis of polycrystalline ZnFe2O4 powder, few methods exist for the deposition of its thin films, where prolonged processing at elevated temperature is not required. We report a novel, microwave-assisted, low temperature (<100°C) deposition process that is conducted in the liquid medium, developed for obtaining high quality, polycrystalline ZnFe2O4 thin films on technologically important substrates like Si(100). An environment-friendly solvent (ethanol) and non-hazardous oxide precursors (β-diketonates of Zn and Fe in 1:2 molar ratio), forming a solution together, is subjected to irradiation in a domestic microwave oven (2.45 GHz) for a few minutes, leading to reactions which result in the deposition of ZnFe2O4 films on Si (100) substrates suspended in the solution. Selected surfactants added to the reactant solution in optimum concentration can be used to control film microstructure. The nominal temperature of the irradiated solution, i.e., film deposition temperature, seldom exceeds 100°C, thus sharply lowering the thermal budget. Surface roughness and uniformity of large area depositions (50x50 mm2) are controlled by tweaking the concentration of the mother solution. Thickness of the films thus grown on Si (100) within 5 min of microwave irradiation can be as high as several microns. The present process, not requiring a vacuum system, carries a very low thermal budget and, together with a proper choice of solvents, is compatible with CMOS integration. This novel solution-based process for depositing highly resistive, adherent, smooth ferrimagnetic films on Si (100) is promising to RF engineers for the fabrication of passive circuit components. It is readily extended to a wide variety of functional oxide films.

Ethylenediamine assisted synthesis of wurtzite zinc sulphide nanosheets and porous zinc oxide nanostructures: near white light photoluminescence emission and photocatalytic activity under visible light irradiation

Porous fungus-like ZnO nanostructures have been synthesized by simple thermal annealing of the hydrothermally synthesized sheet-like ZnS(en)(0.5) complex precursor in air at 600 degrees C. Structural and morphological changes occurring during ZnS(en)(0.5) -> ZnS -> ZnO transformations have been observed closely by annealing the as-synthesized precursor at 100-600 degrees C. Wurtzite ZnS nanosheets and ZnS-ZnO composites are obtained at temperatures of 400 degrees C and 500 degrees C, respectively. Thermal decomposition and oxidation of the ZnS(en) 0.5 nanosheets have been confirmed by differential scanning calorimetry and thermo-gravimetric analysis. The visible light driven photocatalytic degradation of methylene blue dye has been demonstrated in the synthesized samples. ZnS-ZnO composite shows the highest dye degradation efficiency of 74% due to the formation of surface complex as well as higher visible light absorption as a result of band-gap narrowing effect. The porous ZnO nanostructures show efficient visible photoluminescence (PL) emission with a colour coordinate of (0.29, 0.35), which is close to that of white light (0.33, 0.33). The efficient visible PL emission as well as visible light driven photocatalytic activity of the materials synthesized in the present work might be very attractive for their applications in future optoelectronic devices, including in white light emitting devices.

Novel spherical hierarchical structures of GdOOH and Eu:GdOOH: rapid microwave-assisted synthesis through self-assembly, thermal conversion to oxides, and optical studies

We report a novel, rapid, and low-temperature method for the synthesis of undoped and Eu-doped GdOOH spherical hierarchical structures, without using any structure-directing agents, through the microwave irradiation route. The as-prepared product consists of nearly monodisperse microspheres measuring about 1.3 mu m in diameter. Electron microscopy reveals that each microsphere is an assembly of two-dimensional nanoflakes (about 30 nm thin) which, in turn, result from the assembly of crystallites measuring about 9 nm in diameter. Thus, a three-level hierarchy can be seen in the formation of the GdOOH microspheres: from nanoparticles to 2D nanoflakes to 3D spherical structures. When doped with Eu3+ ions, the GdOOH microspheres show a strong red emission, making them promising candidates as phosphors. Finally, thermal conversion at modest temperatures leads to the formation of corresponding oxide structures with enhanced luminescence, while retaining the spherical morphology of their oxyhydroxide precursor.

Effect of thermal annealing on dual photoluminescence emission characteristics of chemically synthesized uncapped Mn2+ doped ZnS quantum dots

Dual photoluminescence (PL) emission characteristics of Mn2+ doped ZnS (ZnS:Mn) quantum dots (QDs) have drawn a lot of attention recently. However, here we report the effect of thermal annealing on the PL emission characteristics of uncapped ZnS:Mn QDs of average sizes similar to 2-3 nm, synthesized by simple chemical precipitation method by using de-ionized (DI) water at room temperature. As-synthesized samples show dual PL emissions, having one UV PL band centred at similar to 400 nm and the other in the visible region similar to 610 nm. But when the samples are isochronally annealed for 2 h at 100-600 degrees C temperature range in air, similar to 90% quenching of Mn2+ related visible PL emission intensity takes place at the annealing temperature of 600 degrees C. X-ray diffraction data show that the as-synthesized cubic ZnS has been converted to wurtzite ZnO at 600 degrees C annealing temperature. The nanostructural properties of the samples are also determined by transmission electron micrograph, electron probe micro-analyser and UV-vis spectrophotometry. The photocatalytic property of the annealed ZnS:Mn sample has been demonstrated and photo-degradation efficiency of the as-synthesized and 600 degrees C annealed ZnS:Mn sample has been found out to be similar to 35% and similar to 61%, respectively, for the degradation of methylene blue dye under visible light irradiation. The synthesized QDs may find significant applications in future optoelectronic devices. (C) 2014 Elsevier B.V. All rights reserved.

Sunlight-Induced Covalent Marriage of Two Triply Interlocked Pd-6 Cages and Their Facile Thermal Separation

A template-free triply interlocked Pd-6 cage (2) was synthesized by two-component self-assembly of cis-blocked 90 degrees acceptor cis-(tmen)Pd(NO3)(2) (M) and 1,3,5-tris((E)-2-(pyridin-3-yl)vinyl)benzene (L). Assembly 2 was characterized by H-1 NMR and ESI-MS, and the structure was confirmed by X-ray crystallography, which revealed a parallel conformation of the olefin double bonds belonging to the adjacent cages in the solid state at a distance of 3.656 angstrom, thereby indicating the feasibility of 2+2] photochemical reaction. Two adjacent interlocked cages were covalently married together by intermolecular 2+2] cycloaddition in a single crystal-to-single crystal fashion upon exposure to sunlight/UV irradiation. Most surprisingly, the covalently married pair was easily separated thermally in aqueous medium under mild reaction conditions.

Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 degrees C), decomposition temperature (202 degrees C) as that with zinc acetylacetonate (136 degrees C, 220 degrees C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process. (c) 2015 Elsevier B.V. All rights reserved.

Porous materials for thermal management under extreme conditions

A brief analysis is presented of how heat transfer takes place in porous materials of various types. The emphasis is on materials able to withstand extremes of temperature, gas pressure, irradiation, etc., i.e. metals and ceramics, rather than polymers. A primary aim is commonly to maximize either the thermal resistance (i.e. provide insulation) or the rate of thermal equilibration between the material and a fluid passing through it (i.e. to facilitate heat exchange). The main structural characteristics concern porosity (void content), anisotropy, pore connectivity and scale. The effect of scale is complex, since the permeability decreases as the structure is refined, but the interfacial area for fluid-solid heat exchange is, thereby, raised. The durability of the pore structure may also be an issue, with a possible disadvantage of finer scale structures being poor microstructural stability under service conditions. Finally, good mechanical properties may be required, since the development of thermal gradients, high fluid fluxes, etc. can generate substantial levels of stress. There are, thus, some complex interplays between service conditions, pore architecture/scale, fluid permeation characteristics, convective heat flow, thermal conduction and radiative heat transfer. Such interplays are illustrated with reference to three examples: (i) a thermal barrier coating in a gas turbine engine; (ii) a Space Shuttle tile; and (iii) a Stirling engine heat exchanger. Highly porous, permeable materials are often made by bonding fibres together into a network structure and much of the analysis presented here is oriented towards such materials. © 2005 The Royal Society.

Ablation and ultrafast dynamics of zinc selenide under femtosecond laser irradiation

The ablation in zinc selenide (ZnSe) crystal is studied by using 150-fs, 800-nm laser system. The images of the ablation pit measured by scanning electronic microscope (SEM) show no thermal stress and melting dynamics. The threshold fluence is measured to be 0.7 J/cm2. The ultrafast ablation dynamics is studied by using pump and probe method. The result suggests that optical breakdown and ultrafast melting take place in ZnSe irradiated under femtosecond laser pulses.

Precipitation of nanocrystals in glasses by electron irradiation: An alternative path to form glass ceramics?

This letter demonstrates an alternative method to form gallium silicate glass ceramics using high-energy electron irradiation. Compared with glass ceramics obtained from the conventional thermal treatment method, the distribution and crystal sizes of the precipitated Ga2O3 nanoparticles are the same. An advantage of this method is that the spatial distribution of the precipitated nanoparticles can be easily controlled. However, optically active dopants Ni2+ ions do not participate in the precipitation during electron irradiation. (c) 2007 American Institute of Physics.

Valence state change and refractive index change induced by femtosecond laser irradiation in Sm3+ doped fluoroaluminate glass

We report femtosecond laser induced valence state and refractive index change in transparent Sin(3+)-doped fluoroaluminate glass. The effect of annealing on the induced changes was studied and the thermal stability of these changes was discussed. The results show that the femtosecond laser induced valence state change is more stable than the induced refractive index change. The observed phenomenon could be applied to design the thermally erasable or stable storage medium. (c) 2007 Elsevier B.V. All rights reserved.

Study of thermal behaviors in CO2 laser irradiated glass

To understand mechanisms underlying laser-induced damage of BK7 and fused silica, we calculate the temperature field of the substrates with CO2 laser irradiating at a given laser power and beam radius. We find that the two glasses show different thermal behaviors. A model is developed for estimating the time t to heat the surface of the substrates up to a particular temperature T with cw CO2 laser irradiation. We calculate theoretically the duration t that the samples are irradiated, from the beginning to visual catastrophic damage, with the assumption of damage threshold determined by the critical temperature. The duration t that the samples are irradiated, from the beginning to visual catastrophic damage, is investigated experimentally as well. Here we take the melting point or softening point as the critical temperature, given the thermomechanical coupling properties, which is enough to cause damage for BK7. Damage features are characterized by the sound of visual cracks. Finally, we calculate stresses induced by laser heating. The analysis of stress indicates that the damage of BK7 is due to the stresses induced by laser heating. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Study of thermal behaviors in CO2 laser irradiated glass

To understand mechanisms underlying laser-induced damage of BK7 and fused silica, we calculate the temperature field of the substrates with CO2 laser irradiating at a given laser power and beam radius. We find that the two glasses show different thermal behaviors. A model is developed for estimating the time t to heat the surface of the substrates up to a particular temperature T with cw CO2 laser irradiation. We calculate theoretically the duration t that the samples are irradiated, from the beginning to visual catastrophic damage, with the assumption of damage threshold determined by the critical temperature. The duration t that the samples are irradiated, from the beginning to visual catastrophic damage, is investigated experimentally as well. Here we take the melting point or softening point as the critical temperature, given the thermomechanical coupling properties, which is enough to cause damage for BK7. Damage features are characterized by the sound of visual cracks. Finally, we calculate stresses induced by laser heating. The analysis of stress indicates that the damage of BK7 is due to the stresses induced by laser heating. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Damage on HfO2/SiO2 high-reflecting coatings under single and multiple Nd:YAG laser pulse irradiation

The single- and multi-shot damage behaviors of HfO2/SiO2 high-reflecting (HR) coatings under Nd:YAG laser exposure were investigated. Fundamental aspects of multi-shot laser damage, such as the instability due to pulse-to-pulse accumulation of absorption defect and structural defect effect, and the mechanism of laser induced defect generation, are considered. It was found in multi-shot damage, the main factors influencing laser-induced damage threshold (LIDT) are accumulation of irreversible changes of structural defects and thermal stress that induced by thermal density fluctuations.

Neutron irradiation effect in two-dimensional electron gas of AlGaN/GaN heterostructures

AlGaN/GaN heterostructures have been irradiated by neutrons with different influences and characterized by means of temperature-dependent Hall measurements and Micro-Raman scattering techniques. It is found that the carrier mobility of two-dimensional electron gas (2DEG) is very sensitive to neutrons. At a low influence of 6.13 x 10(15) cm(-2), the carrier mobility drops sharply, while the sheet carrier density remains the same as that of an unirradiated sample. Moreover, even for a fluence of up to 3.66 x 10(16) cm(-2), the sheet carrier density shows only a slight drop. We attribute the degradation of the figure-of-merit (product of n(s) x mu) of 2DEG to the defects induced by neutron irradiation. Raman measurements show that neutron irradiation does not yield obvious change to the strain state of AlGaN/GaN heterostructures, which proves that degradation of sheet carrier density has no relation to strain relaxation in the present study. The increase of the product of n(s) x mu of 2DEG during rapid thermal annealing processes at relatively high temperature has been attributed to the activation of Ge-Ga transmuted from Ga and the recovery of displaced defects.