Kinetics of TiO2-catalyzed ultrasonic degradation of rhodamine dyes

The ultrasonic degradation of two dyes, Rhodamine B (C28H31ClN2O3) and Rhodamine Blue (C28H32N2O3), were studied in the absence of catalyst and in the presence of two catalysts (combustion-synthesized anatase TiO2 and commercial Degussa P-25 TiO2. The rate of degradation of catalyzed reaction was higher than that obtained with in the absence of the catalysts. Among the catalysts, combustion-synthesized anatase TiO2 degraded the dyes faster when compared to the degradation with commercial Degussa P-25 catalyst. A Langmuir-Hinshelwood kinetic model was developed and the kinetic rate parameters were determined. The effect of other operating parameters, such as initial concentration, pH, temperature, and power intensity, was also investigated. The degradation rate increased with decreasing pH, increasing temperature, and higher intensity.

Influence of crossed electric and quantizing magnetic fields on the Einstein relation in nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity-to-mobility ratio (DMR) under crossed fields' configuration in nonlinear optical materials on the basis of a newly formulated electron dispersion law by incorporating the crystal field in the Hamiltonian and including the anisotropies of the effective electron mass and the spin-orbit splitting constants within the framework of kp formalisms. The corresponding results for III-V, ternary and quaternary compounds form a special case of our generalized analysis. The DMR has also been investigated for II-VI and stressed materials on the basis of various appropriate dispersion relations. We have considered n-CdGeAs2, n-Hg1-xCdxTe, n-In1-xGaxAsyP1-y lattice matched to InP, p-CdS and stressed n-InSb materials as examples. The DMR also increases with increasing electric field and the natures of oscillations are totally band structure dependent with different numerical values. It has been observed that the DMR exhibits oscillatory dependences with inverse quantizing magnetic field and carrier degeneracy due to the Subhnikov-de Haas effect. An experimental method of determining the DMR for degenerate materials in the present case has been suggested. (C) 2010 Elsevier B.V. All rights reserved.

Microstructure related influence on the electrical properties of pulsed laser ablated (Ba, Sr)TiO3 thin films

The microstructural dependence of electrical properties of (Ba, Sr)TiO3(BST) thin films were studied from the viewpoint of dc and ac electrical properties. The films were grown using a pulsed laser deposition technique in a temperature range of 300 to 600 degrees C, inducing changes in grain size, structure, and morphology. Consequently, two different types of films were realized, of which type I, was polycrystalline, multigrained, while type II was [100] oriented possessing a densely packed fibrous microstructure. Leakage current measurements were done at elevated temperatures to provide evidence of the conduction mechanism present in these films. The results revealed a contribution from both electronic and ionic conduction. In the case of type I films, two trapping levels were identified with energies around 0.5 and 2.73 eV, which possibly originate from oxygen vacancies V-O and Ti3+ centers, respectively. These levels act as shallow and deep traps and are reflected in the current-voltage characteristics of the BST thin films. The activation energy associated with oxygen vacancy motion in this case was obtained as 1.28 eV. On the contrary, type II films showed no evidence of deep trap energy levels, while the identified activation energy associated with shallow traps was obtained as 0.38 eV. The activation energy obtained for oxygen vacancy motion in type II films was around 1.02 eV. The dc measurement results were further elucidated through ac impedance analysis, which revealed a grain boundary dominated response in type I in comparison to type II films where grain response is highlighted. A comparison of the mean relaxation time of the two films revealed three orders of magnitude higher relaxation time in the case of type I films. Due to smaller grain size in type I films the grains were considered to be completely depleted giving rise to only grain boundary response for the bulk of the film. The activation energy obtained from conductivity plots agree very well with that of dc measurements giving values 1.3 and 1.07 eV for type I and type II films, respectively. Since oxygen vacancy transport have been identified as the origin of resistance degradation in BST thin films, type I films with their higher value of activation energy for oxygen ion mobility explains the improvement in breakdown characteristics under constant high dc field stress. The role of microstructure in controlling the rate of degradation is found useful in this instance to enhance the film properties under high electric field stresses. (C) 2000 American Institute of Physics. [S0021-8979(00)00418-7].

Magnetoresistors based on magnetic composite materials

Describes a new type of magnetoresistor based on magnetic composite material. This device exhibits a magnetoresistance which is comparable to that of conventional magnetoresistors but can be realised with a very low cost technology. The theoretical analysis of the magnetoresistance characteristics of this device is also described.

Steady compressible flow of granular materials through a wedge-shaped hopper: The smooth wall, radial gravity problem

A continuum model based on the critical state theory of soil mechanics is used to generate stress and density profiles, and to compute discharge velocities for the plane flow of cohesionless materials. Two types of yield loci are employed, namely, a yield locus with a corner, and a smooth yield locus. The yield locus with a corner leads to computational difficulties. For the smooth yield locus, results are found to be relatively insensitive to the shape of the yield locus, the location of the upper traction-free surface and the density specified on this surface. This insensitivity arises from the existence of asymptotic stress and density fields, to which the solution tends to converge on moving down the hopper. Numerical and approximate analytical solutions are obtained for these fields and the latter is used to derive an expression for the discharge velocity. This relation predicts discharge velocities to within 13% of the exact (numerical) values. While the assumption of incompressibility has been frequently used in the literature, it is shown here that in some cases, this leads to discharge velocities which are significantly higher than those obtained by the incorporation of density variation.

Kinetics of TiO2-catalyzed ultrasonic degradation of rhodamine dyes

The ultrasonic degradation of two dyes, Rhodamine B (C28H31ClN2O3) and Rhodamine Blue (C28H32N2O3), were studied in the absence of catalyst and in the presence of two catalysts (combustion-synthesized anatase TiO2 and commercial Degussa P-25 TiO2. The rate of degradation of catalyzed reaction was higher than that obtained with in the absence of the catalysts. Among the catalysts, combustion-synthesized anatase TiO2 degraded the dyes faster when compared to the degradation with commercial Degussa P-25 catalyst. A Langmuir-Hinshelwood kinetic model was developed and the kinetic rate parameters were determined. The effect of other operating parameters, such as initial concentration, pH, temperature, and power intensity, was also investigated. The degradation rate increased with decreasing pH, increasing temperature, and higher intensity.

Irradiation effects in graphene and related materials

Nanomaterials with a hexagonally ordered atomic structure, e.g., graphene, carbon and boron nitride nanotubes, and white graphene (a monolayer of hexagonal boron nitride) possess many impressive properties. For example, the mechanical stiffness and strength of these materials are unprecedented. Also, the extraordinary electronic properties of graphene and carbon nanotubes suggest that these materials may serve as building blocks of next generation electronics. However, the properties of pristine materials are not always what is needed in applications, but careful manipulation of their atomic structure, e.g., via particle irradiation can be used to tailor the properties. On the other hand, inadvertently introduced defects can deteriorate the useful properties of these materials in radiation hostile environments, such as outer space. In this thesis, defect production via energetic particle bombardment in the aforementioned materials is investigated. The effects of ion irradiation on multi-walled carbon and boron nitride nanotubes are studied experimentally by first conducting controlled irradiation treatments of the samples using an ion accelerator and subsequently characterizing the induced changes by transmission electron microscopy and Raman spectroscopy. The usefulness of the characterization methods is critically evaluated and a damage grading scale is proposed, based on transmission electron microscopy images. Theoretical predictions are made on defect production in graphene and white graphene under particle bombardment. A stochastic model based on first-principles molecular dynamics simulations is used together with electron irradiation experiments for understanding the formation of peculiar triangular defect structures in white graphene. An extensive set of classical molecular dynamics simulations is conducted, in order to study defect production under ion irradiation in graphene and white graphene. In the experimental studies the response of carbon and boron nitride multi-walled nanotubes to irradiation with a wide range of ion types, energies and fluences is explored. The stabilities of these structures under ion irradiation are investigated, as well as the issue of how the mechanism of energy transfer affects the irradiation-induced damage. An irradiation fluence of 5.5x10^15 ions/cm^2 with 40 keV Ar+ ions is established to be sufficient to amorphize a multi-walled nanotube. In the case of 350 keV He+ ion irradiation, where most of the energy transfer happens through inelastic collisions between the ion and the target electrons, an irradiation fluence of 1.4x10^17 ions/cm^2 heavily damages carbon nanotubes, whereas a larger irradiation fluence of 1.2x10^18 ions/cm^2 leaves a boron nitride nanotube in much better condition, indicating that carbon nanotubes might be more susceptible to damage via electronic excitations than their boron nitride counterparts. An elevated temperature was discovered to considerably reduce the accumulated damage created by energetic ions in both carbon and boron nitride nanotubes, attributed to enhanced defect mobility and efficient recombination at high temperatures. Additionally, cobalt nanorods encapsulated inside multi-walled carbon nanotubes were observed to transform into spherical nanoparticles after ion irradiation at an elevated temperature, which can be explained by the inverse Ostwald ripening effect. The simulation studies on ion irradiation of the hexagonal monolayers yielded quantitative estimates on types and abundances of defects produced within a large range of irradiation parameters. He, Ne, Ar, Kr, Xe, and Ga ions were considered in the simulations with kinetic energies ranging from 35 eV to 10 MeV, and the role of the angle of incidence of the ions was studied in detail. A stochastic model was developed for utilizing the large amount of data produced by the molecular dynamics simulations. It was discovered that a high degree of selectivity over the types and abundances of defects can be achieved by carefully selecting the irradiation parameters, which can be of great use when precise pattering of graphene or white graphene using focused ion beams is planned.

Studies in nonlinear optical materials: structure of di-2-menthyl 2-(N,N'-dimethyl-2-imidazolidinylidene)malonate monohydrate

C28H48N2Oa.H2 O, Mr=494.7, orthorhombic,P2~2~2~, a = 7.634 (2), b = 11.370 (2), c=34. 167 (4) A, V = 2966 (2) A 3, Z = 4, D m = 1.095,D x -- 1. 108 g cm -3, Mo Kct, 2 -- 0.7107 ,/k, ~ =0.43 cm -~, F(000) = 1088.0, T= 293 K, R = 0.061 for 1578 significant reflections. The second-harmonicgeneration (SHG) efficiency of this compound is negligible (1/100th of the urea standard). The observed low second-order nonlinear response has been attributed to the unfavourable packing of the molecules in the crystal lattice.

On the two-dimensional thermoelectric power in quantum wells of non-parabolic materials under magnetic quantization

We present a simplified theoretical formulation of the thermoelectric power (TP) under magnetic quantization in quantum wells (QWs) of nonlinear optical materials on the basis of a newly formulated magneto-dispersion law. We consider the anisotropies in the effective electron masses and the spin-orbit constants within the framework of k.p formalism by incorporating the influence of the crystal field splitting. The corresponding results for III-V materials form a special case of our generalized analysis under certain limiting conditions. The TP in QWs of Bismuth, II-VI, IV-VI and stressed materials has been studied by formulating appropriate electron magneto-dispersion laws. We also address the fact that the TP exhibits composite oscillations with a varying quantizing magnetic field in QWs of n-Cd3As2, n-CdGeAs2, n-InSb, p-CdS, stressed InSb, PbTe and Bismuth. This reflects the combined signatures of magnetic and spatial quantizations of the carriers in such structures. The TP also decreases with increasing electron statistics and under the condition of non-degeneracy, all the results as derived in this paper get transformed into the well-known classical equation of TP and thus confirming the compatibility test. We have also suggested an experimental method of determining the elastic constants in such systems with arbitrary carrier energy spectra from the known value of the TP. (C) 2010 Elsevier Ltd. All rights reserved.

Microwave Assisted Synthesis of Nanostructured Titanium Dioxide with High Photocatalytic Activity

TiO2 (anatase) was synthesized using a microwave-irradiation-assisted chemical method. The reaction conditions were varied to obtain unique nanostructures of TiO2 comprising nanometric spheres giving the materials a very porous morphology. The oxide was characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). The specific surface area and porosity were quantified by the BET method, and the degradation of dyes was carried out using these materials. The photocatalytic activity of the nanometric TiO2 was significantly higher than that of commercially available TiO2 (Degussa P25) for the degradation of the dyes.

Ultra-fine Grain Materials by Severe Plastic Deformation: Application to Steels

Severe plastic deformation techniques are known to produce grain sizes up to submicron level. This leads to conventional Hall-Petch strengthening of the as-processed materials. In addition, the microstructures of severe plastic deformation processed materials are characterized by relatively lower dislocation density compared to the conventionally processed materials subjected to the same amount of strain. These two aspects taken together lead to many important attributes. Some examples are ultra-high yield and fracture strengths, superplastic formability at lower temperatures and higher strain rates, superior wear resistance, improved high cycle fatigue life. Since these processes are associated with large amount of strain, depending on the strain path, characteristic crystallographic textures develop. In the present paper, a detailed account of underlying mechanisms during SPD has been discussed and processing-microstructure-texture-property relationship has been presented with reference to a few varieties of steels that have been investigated till date.

Non-enzymatic Degradation of (1→3)(1→4)-β-D-glucan in Aqueous Processing of Oats

Cereal water-soluble β-glucan [(1→3)(1→4)-β-D-glucan] has well-evidenced health benefits and it contributes to the texture properties of foods. These functions are characteristically dependent on the excellent viscosity forming ability of this cell wall polysaccharide. The viscosity is affected by the molar mass, solubility and conformation of β-glucan molecule, which are further known to be altered during food processing. This study focused on demonstrating the degradation of β-glucan in water solutions following the addition of ascorbic acid, during heat treatments or high pressure homogenisation. Furthermore, the motivation of this study was in the non-enzymatic degradation mechanisms, particularly in oxidative cleavage via hydroxyl radicals. The addition of ascorbic acid at food-related concentrations (2-50 mM), autoclaving (120°C) treatments, and high pressure homogenisation (300-1000 bar) considerably cleaved the β-glucan chains, determined as a steep decrease in the viscosity of β-glucan solutions and decrease in the molar mass of β-glucan. The cleavage was more intense in a solution of native β-glucan with co-extracted compounds than in a solution of highly purified β-glucan. Despite the clear and immediate process-related degradation, β-glucan was less sensitive to these treatments compared to other water-soluble polysaccharides previously reported in the literature. In particular, the highly purified β-glucan was relatively resistant to the autoclaving treatments without the addition of ferrous ions. The formation of highly oxidative free radicals was detected at the elevated temperatures, and the formation was considerably accelerated by added ferrous ions. Also ascorbic acid pronounced the formation of these oxidative radicals, and oxygen was simultaneously consumed by ascorbic acid addition and by heating the β-glucan solutions. These results demonstrated the occurrence of oxidative reactions, most likely the metal catalysed Fenton-like reactions, in the β-glucan solutions during these processes. Furthermore, oxidized functional groups (carbonyls) were formed along the β-glucan chain by the treatments, including high pressure homogenisation, evidencing the oxidation of β-glucan by these treatments. The degradative forces acting on the particles in the high pressure homogenisation are generally considered to be the mechanical shear, but as shown here, carbohydrates are also easily degraded during the process, and oxidation may have a role in the modification of polysaccharides by this technique. In the present study, oat β-glucan was demonstrated to be susceptible to degradation during aqueous processing by non-enzymatic degradation mechanisms. Oxidation was for the first time shown to be a highly relevant degradation mechanism of β-glucan in food processing.

Effect of water vapour stabilization of raw materials on the quality of the inhalation product

Generation of raw materials for dry powder inhalers by different size reduction methods can be expected to influence physical and chemical properties of the powders. This can cause differences in particle size, size distribution, shape, crystalline properties, surface texture and energy. These physical properties of powders influence the behaviour of particles before and after inhalation. Materials with an amorphous surface have different surface energy compared to materials with crystalline surface. This can affect the adhesion and cohesion of particles. Changes in the surface nature of the drug particles results in a change in product performance. By stabilization of the raw materials the amorphous surfaces are converted into crystalline surfaces. The primary aim of the study was to investigate the influence of the surface properties of the inhalation particles on the quality of the product. The quality of the inhalation product is evaluated by measuring the fine particle dose (FPD). FDP is the total dose of particles with aerodynamic diameters smaller than 5,0 μm. The secondary aim of this study was to achieve the target level of the FPD and the stability of the FPD. This study was also used to evaluate the importance of the stabilization of the inhalation powders. The study included manufacturing and analysing drug substance 200 μg/dose inhalation powder batches using non-stabilized or stabilized raw materials. The inhaler formulation consisted of micronized drug substance, lactose <100μm and micronized lactose <10μm. The inhaler device was Easyhaler®. Stabilization of the raw materials was done in different relative humidity, temperature and time. Surface properties of the raw materials were studied by dynamic vapour sorption, scanning electron microscopy and three-point nitrogen adsorption technique. Particle size was studied by laser diffraction particle size analyzer. Aerodynamic particle size distribution from inhalers was measured by new generation impactor. Stabilization of all three raw materials was successful. A clear difference between nonstabilized and stabilized raw materials was achieved for drug substance and lactose <10μm. However for lactose <100μm the difference wasn’t as clear as wanted. The surface of the non-stabilized drug substance was more irregular and the particles had more roughness on the surface compared to the stabilized drug substances particles surface. The surface of the stabilized drug particles was more regular and smoother than non-stabilized. Even though a good difference between stabilized and non-stabilized raw materials was achieved, a clear evidence of the effect of the surface properties of the inhalation particles on the quality of the product was not observed. Stabilization of the raw materials didn’t lead to a higher FPD. Possible explanations for the unexpected result might be too rough conditions in the stabilization of the drug substance or smaller than wanted difference in the degree of stabilization of the main component of the product <100μm. Despite positive effects on the quality of the product were not seen there appears to be some evidence that stabilized drug substance results in smaller particle size of dry powder inhalers.

Nanoscale studies of materials using x-ray synchrotron radiation and mesoscopic modelling

X-ray synchrotron radiation was used to study the nanostructure of cellulose in Norway spruce stem wood and powders of cobalt nanoparticles in cellulose support. Furthermore, the growth of metallic clusters was modelled and simulated in the mesoscopic size scale. Norway spruce was characterized with x-ray microanalysis at beamline ID18F of the European Synchrotron Radiation Facility in Grenoble. The average dimensions and the orientation of cellulose crystallites was determined using x-ray microdiffraction. In addition, the nutrient element content was determined using x-ray fluorescence spectroscopy. Diffraction patterns and fluorescence spectra were simultaneously acquired. Cobalt nanoparticles in cellulose support were characterized with x-ray absorption spectroscopy at beamline X1 of the Deutsches Elektronen-Synchrotron in Hamburg, complemented by home lab experiments including x-ray diffraction, electron microscopy and measurement of magnetic properties with a vibrating sample magnetometer. Extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray diffraction were used to solve the atomic arrangement of the cobalt nanoparticles. Scanning- and transmission electron microscopy were used to image the surfaces of the cellulose fibrils, where the growth of nanoparticles takes place. The EXAFS experiment was complemented by computational coordination number calculations on ideal spherical nanocrystals. The growth process of metallic nanoclusters on cellulose matrix is assumed to be rather complicated, affected not only by the properties of the clusters themselves, but essentially depending on the cluster-fiber interfaces as well as the morphology of the fiber surfaces. The final favored average size for nanoclusters, if such exists, is most probably a consequence of these two competing tendencies towards size selection, one governed by pore sizes, the other by the cluster properties. In this thesis, a mesoscopic model for the growth of metallic nanoclusters on porous cellulose fiber (or inorganic) surfaces is developed. The first step in modelling was to evaluate the special case of how the growth proceeds on flat or wedged surfaces.