Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150��C) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron M��ssbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Interactions between oligoamines and superoxide anion

1- Oligoamines and EDTA inhibited the reduction of cytochrome-C and nitrobule tetrazolium (NBT) induced by the hypoxanthine/xanthine oxidase superoxide anion generating system in the following order of effectiveness: putrescine > diaminopropane > spermidine > EDTA > spermine > cadaverine. 2- Oligoamines and EDTA did not affect the rate of urate formation from the hypoxanthine/xanthine oxidase system. 3- Oligoamines and EDTA inhibited the reduction of cytochrome-C induced by stimulated PMNL's in the same order of effectiveness as mentioned before. 4- Oligoamines and EDTA inhibited luminol dependent stimulated PMNL's chemiluminescence. 5- Oligoamines and EDTA inhibited the aerobic photoreduction of NBT. 6- Oligoamines-copper sulphate complexes inhibited the reduction of cytochrome-C induced by the hypoxanthine/xanthine oxidase system more effectively than oligoamines or copper sulphate individually. 7- Superoxide anion, hydrogen peroxide and hydroxyl radical induced breakdown of isolated intact guinea pig liver lysosomes. 8- Oligoamines and EDTA protected isolated intact guinea pig liver lysosomes from the lytic effect of superoxide anion generated either by the hypoxanthine/xanthine oxidase system or by stimulated PMNL's. 9- Oligoamines and EDTA have no stabilizing effect on isolated intact guinea pig liver lysosomes. 10- The uptake of oligoamines by lysosomes was in the following order: putrescine > spermidine > spermine. 11- Oligoamines were metabolised into aldehyde compounds either by the hypoxanthine/xanthine oxidase system or stimulated PMNL's. 12- Oligoamines and EDTA have no effect on the activities of free lysosomal enzymes (acid phosphatase and -glucosaminidase). 13- Oligoamines and EDTA inhibited lipid peroxidation in guinea pig liver lysosomes induced either by the hypoxanthine/xanthine oxidase or ascorbic acid-ferrous sulphate. 14- Oligoamines and EDTA have no effect on the release of PGE_2 from stimulated peritoneal guinea pig PMNL's. 15- Oligoamines increased the uptake of (^3H)thymidine and (^3H)leucine by stimulated peritoneal guinea pig macrophages in the following order of effectiveness: spermine > spermidine > putrescine > cadaverine. 16- PGE_2, dibutyryl Cyclic AMP, and theophylline inhibited luminol dependent stimulated peritoneal guinea pig PMNL's chemiluminescence.

The creep properties of a series of zinc-rich zinc-aluminium alloys

The compressive creep behaviour of six sand cast zinc-rich alloys: No3 and No5, corresponding to BS 1004A and BS 1004B, respectively, alloy No2, ILZRO,.16 and two newer alloys ACuZinc5 and ACuZinc10 was investigated. The total creep contraction of the alloys was found to be well correlated using an empirical equation. On the basis of this equation, a parametrical relationship was derived which allowed the total creep contraction to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of compressive creep of the alloys could be made under different testing conditions. The primary creep and secondary creep rates were found for the alloys at different temperatures and stresses. Generally, the primary creep contraction was found to increase with copper content, whereas secondary creep rates decreased in the order No3, ACuZinc10, ACuZinc5 and No2. ILZRO.16 was tested only at the highest stress and two higher temperatures. The results showed that ILZRO.16 had higher creep resistance than all the other alloys. Thus, based on the above empirical equation, alloy No2 was found to have a substantially better total creep resistance than alloys No3 and No5, and slightly better than ACuZinc5 and ACuZinc10 for strains up to 1%. Both ACuZinc alloys had higher creep strength than commercial alloys No3 and No5. Alloy No5 had much higher creep resistance than alloy No3 under all conditions. The superior creep resistance of alloy No2 was considered to be due to the presence of small precipitates of -phase in the zinc matrix and a regular eutectic morphology. The stress exponents and activation energies for creep under different testing conditions were found to be consistent with some established creep-controlling mechanisms; i.e. dislocation climb for alloy No3, dislocation climb over second phase particles for alloys No5, No2, ACuZinc10, controlled by lattice diffusion in the zinc-rich phase. The lower creep resistance of alloy No3 was mainly due to the lower creep strength of copper-free primary particles having greater volume than eutectic in the microstructure. Alloys No5, ACuZinc5 and ACuZinc10 showed much better creep resistance than alloy No3, based on the precipitation-hardening due to the presence of small -phase precipitates. The primary dendrites in both ACuZinc alloys however were not of much benefit in improving the creep resistance of the alloys.

The effect of care solutions on the bulk and surface properties of soft contact lenses

Purpose: Soft contact lenses for continuous wear require the use of cleaning regimes which utilise hydrogen peroxide systems or multipurpose cleaning solutions (MPS). The compositions of MPS are becoming increasingly complex and often include disinfectants, cleaning agents, preservatives, wetting agents, demulcents, chelating and buffering agents. Recent research on solution���lens interactions has focused on specific ocular parameters such as corneal staining. However the effect of a solution on the lens, particularly silicone hydrogel lenses, itself has received less attention. The purpose of this work was to establish and understand the effects that care solutions have on selected bulk and surface material properties. Methods: Selected bulk and surface properties of each material (etafilcon A, vifilcon A, balafilcon A, senofilcon A, lotrafilcon A and lotrafilcon B, galyfilcon A) were measured after a 24 h soak in a variety of care solutions. Additionally the lenses were soaked for 24 h in hyperosmolar (680 mOsm L-1) and hyposmolar (170 mOsm L-1) PBS. A bulk property parameter the total diameter (TD) was measured using an Optimec contact lens analyser. The surface property related CoF of soaked lenses was measured on a nano-tribometer with conditions of load 30 mN, at a distance of 20 mm and speed 30 mm/min. Results: In terms of bulk properties, change is related to the EWC of the lens, the higher the EWC of the lens the greater the TD changes. Silicone hydrogel lenses have EWCs of <47% and little or no TD changes were observed; lotrafilcon A exhibited no change irrespective of the cleaning solution. Conventional contact lenses have higher EWCs (58% for etafilcon A and 55% for vifilcon A) and the TD was seen to change to a greater extent, for example the etafilcon A material in ReNu MPS had an increase to 14.45�� 0.07 mm from the cited 14.2 mm. Other lenses increased or decreased in TD depending on the solution used. The osmolarity of the solution although important is not the only factor governing change in the TD, for example soaking senofilcon A in hyperosmolar PBS (680 mOsm L-1) for 24 h increased the TD of the lens (+0.25 �� 0.07 mm), however when the same lens type was soaked for 24 h in a MPS with a lower osmolarity there was a similar effect. Biotribology measurements demonstrated that some solution���lens combinations can reduce the CoF by 55%, when compared with biotribology with the native packing solution. An increase in the CoF was observed for other solution���lens combinations. Conclusions: There is a dramatic difference in bulk and surface performance of specific lens materials with particular care solutions. Individual components of the care solutions have effects on the bulk and surface properties of contact lenses. The affects are not as great with the silicone hydrogel as compared with conventional hydrogels.

Endothelial Nox4 NADPH oxidase enhances vasodilatation and reduces blood pressure in vivo

Objective- Increased reactive oxygen species (ROS) production is involved in the pathophysiology of endothelial dysfunction. NADPH oxidase-4 (Nox4) is a ROS-generating enzyme expressed in the endothelium, levels of which increase in pathological settings. Recent studies indicate that it generates predominantly hydrogen peroxide (H O ), but its role in vivo remains unclear. Methods and Results- We generated transgenic mice with endothelium-targeted Nox4 overexpression (Tg) to study the in vivo role of Nox4. Tg demonstrated significantly greater acetylcholine- or histamine-induced vasodilatation than wild-type littermates. This resulted from increased H O production and H O -induced hyperpolarization but not altered nitric oxide bioactivity. Tg had lower systemic blood pressure than wild-type littermates, which was normalized by antioxidants. Conclusion- Endothelial Nox4 exerts potentially beneficial effects on vasodilator function and blood pressure that are attributable to H O production. These effects contrast markedly with those reported for Nox1 and Nox2, which involve superoxide-mediated inactivation of nitric oxide. Our results suggest that therapeutic strategies to modulate ROS production in vascular disease may need to separately target individual Nox isoforms. �� 2011 American Heart Association, Inc.

Soot measurements in steady and pulsed ethylene/air diffusion flames using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0�� ��� 360��) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (fvRe-1 = a + b��Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

Characterization of recombinant chloroperoxidase, and F103A and C29H/C79H/C87H mutants

Mechanistically and structurally chloroperoxidase (CPO) occupies a unique niche among heme containing enzymes. Chloroperoxidase catalyzes a broad range of reactions, such as oxidation of organic substrates, dismutation of hydrogen peroxide, and mono-oxygenation of organic molecules. To expand the synthetic utility of CPO and to appreciate the important interactions that lead to CPO���s exceptional properties, a site-directed mutagenesis study was undertaken. ^ Recombinant CPO and CPO mutants were heterologously expressed in Aspergillus niger. The overall protein structure was almost the same as that of wild type CPO, as determined by UV-vis, NMR and CD spectroscopies. Phenylalanine103, which was proposed to regulate substrate access to the active site by restricting the size of substrates and to control CPO���s enantioselectivity, was mutated to Ala. The ligand binding affinity and most importantly the catalytic activity of F103A was dramatically different from wild type CPO. The mutation essentially eliminated the chlorination and dismutation activities but enhanced, 4-10 fold, the epoxidation, peroxidation, and N-demethylation activities. As expected, the F103A mutant displayed dramatically improved epoxidation activity for larger, more branched styrene derivatives. Furthermore, F103A showed a distinctive enantioselectivity profile: losing enantioselectivity to styrene and cis-��-methylstyrene; having a different configuration preference on ��-methylstyrene; showing higher enantioselectivites and conversion rates on larger, more branched substrates. Our results show that F103 acts as a switch box that controls the catalytic activity, substrate specificity, and product enantioselectivity of CPO. Given that no other mutant of CPO has displayed distinct properties, the results with F103A are dramatic. ^ The diverse catalytic activity of CPO has long been attributed to the presence of the proximal thiolate ligand. Surprisingly, a recent report on a C29H mutant suggested otherwise. A new CPO triple mutant C29H/C79H/C87H was prepared, in which all the cysteines were replaced by histidine to eliminate the possibility of cysteine coordinating to the heme. No active form protein was isolated, although, successful transformation and transcription was confirmed. The result suggests that Cys79 and Cys87 are critical to maintaining the structural scaffold of CPO. ^ In vitro biodegradation of nanotubes by CPO were examined by scanning electron microscope method, but little oxidation was observed. ^

Soot Measurements in Steady and Pulsed Ethylene/Air Diffusion Flames Using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0��- 360��) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (��v Re��1 = a+b�� Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

Desenvolvimento de novos biolubrificantes hidr��ulicos derivados dos ��leos de maracuj�� e de moringa in natura e epoxidados

With the increasing environmental awareness, maximizing biodegradability and minimizing ecotoxicity is the main driving force for new technological developments. Thus, can be developed new biodegradable lubricants for use in environmentally sensitive areas. The aim of this study was to obtain new bio-lubricants from passion fruit (Passiflora edulis Sims f. flavicarpa Degener) and moringa (Moringa oleifera Lamarck) epoxidized oils and develop a new additive package using experimental design for their use as a hydraulic fluid. In the first stage of this work was performed the optimization of the epoxidation process of the oils using fractional experimental design 24-1 , varying the temperature, reaction time, ratio of formic acid and hydrogen peroxide. In the second step was investigated the selectivity, thermodynamics and kinetics of the reaction for obtaining the two epoxides at 30, 50 and 70 ��C. The result of the experimental design confirmed that the epoxidation of passion fruit oil requires 2 hours of reaction, 50 ��C and a ratio H2O2/C=C/HCOOH (1:1:1). For moringa oil were required 2 hours reaction, 50 ��C and a ratio of H2O2/C=C/HCOOH (1:1:1.5). The results of the final conversions were equal to 83.09% (�� 0.3) for passion fruit oil epoxide and 91.02 (��0,4) for moringa oil epoxide. Following was made the 23 factorial design to evaluate which are the best concentrations of corrosion inhibitor and anti-wear (IC), antioxidant (BHA) and extreme pressure (EP) additives. The bio-lubricants obtained in this step were characterized according to DIN 51524 (Part 2 HLP) and DIN 51517 (Part 3 CLP) standards. The epoxidation process of the oils was able to improve the oxidative stability and reduce the total acid number, when compared to the in natura oils. Moreover, the epoxidized oils best solubilized additives, resulting in increased performance as a lubricant. In terms of physicochemical performance, the best lubricant fluid was the epoxidized moringa oil with additives (EMO-ADI), followed by the epoxidized passion fruit oil with additives (EPF-ADI) and, finally, the passion fruit in natura oil without additives (PFO). Lastly, was made the investigation of the tribological behavior under conditions of boundary lubrication for these lubricants. The tribological performance of the developed lubricants was analyzed on a HFRR equipment (High Frequency Reciprocating Rig) and the coefficient of friction, which occurs during the contact and the formation of the lubricating film, was measured. The wear was evaluated through optical microscopy and scanning electron microscopy (SEM). The results showed that the addition of extreme pressure (EP) and anti-wear and corrosion inhibitor (CI) additives significantly improve the tribological properties of the fluids. In all assays, was formed a lubricating film that is responsible for reducing the coefficient of metal-to-metal wear. It was observed that the addition of EP and IC additives in the in natura vegetable oils of passion fruit and moringa did not favor a significant reduction in wear. The bio-lubricants developed from passion fruit and moringa oils modified via epoxidation presented satisfactory tribological properties and shown to be potential lubricants for replacement of commercial mineral-based fluids.

Aplica����o de agentes remineralizantes sobre o esmalte clareado: efic��cia contra o manchamento por caf��

The aim of this study was to evaluate the influence of remineralizing agents on the susceptibility of enamel cleared by the coffee pigmentation during office bleaching. Fifty bovine incisors were selected and randomly assigned into 5 groups (n = 10) on the basis of remineralizing agents: G1 gel hydrogen peroxide to 35% (control group); G2, hydrogen peroxide gel and a 35% gel 2% neutral fluorine; G3, hydrogen peroxide gel and a 35% nanostructured calcium phosphate gel, G4, hydrogen peroxide gel and a 35% casein fosfopt��dia-phosphate and amorphous calcium folder; G5 hydrogen peroxide gel to 35% without mineralizing agent. All groups exception G1 (control group) were subjected to pigmentation soluble coffee according to the manufacturer's guidelines. The samples were immersed in coffee at temperature of 55�� C, 1 time a day for 4 minutes. Color changes were performed by Easyshade spectrophotometer at CIE Lab method before and after 3 whitening sessions. Data were analyzed by analysis of variance ANOVA. The results showed statistically significant differences between the remineralizing substances for the parameters L *, a *, b * ��E (p <0.0001). The L * values for the group G5, and the b * for G2 and G5 groups differed from the control group. After the 3rd whitening session, Fluor's group (G2) and that without mineralizing agent (G5) showed ��E values less than the control group that did not undergo pigmentation. It was concluded that only the nanoclusters remineralizing agents Phosphopeptides Casein-Amorphous Calcium Phosphate and Calcium Amorphous phosphate were able to reduce the coffee interference whitening efficacy of hydrogen peroxide.

Extra����o, caracteriza����o e prospec����o de atividades farmacol��gicas de polissacar��deos sulfatados da macroalga verde Caulerpa prolifera

This study aimed to extract, characterize and conduct a prospective analysis of pharmacological activities of sulfated polysaccharides from green seaweed Caulerpa prolifera. Seven fractions (CP-0.3/CP-0.5/CP-0.7/CP-0.9/CP-1.1/CP-1.5/CP-2.0) were obtained from C. prolifera by alkaline proteolysis followed by sequential precipitation in acetone. The physicochemical analyzes indicated that C. prolifera synthesizes a homogalactan (CP-0.9) and different populations of sulfated heteropolysaccharides. In the analysis of anticoagulant activity, all fractions except CP-0.3, influenced the intrinsic coagulation pathway. All fractions showed antioxidant activity in six different assays being more pronounced in hydrogen peroxide scavenging assay, especially CP-0.3, CP-0.7 and CP-0.9 (which obtained 61% of hydrogen peroxide scavenging), in ferric chelation assay (especially CP-0.9 with 56% chelation) and cupric chelation assay (especially CP-2.0 with 78% chelation). With respect to immunomodulatory activity, the presence of CP-0.3, CP-0.7 and CP-0.9 showed an immunogenic potential, increasing the production of nitric oxide (NO) by 48, 142 and 163 times, respectively. Conversely, the NO synthesis fell 73% after the activation of macrophages by LPS, incubated concurrently with CP-2.0. The anti-adipogenic activity of the fractions was also evaluated and CP-1.5 was able to reduce the differentiation of pre-adipocytes (3T3-L1) into adipocytes by 60%, without affecting the cell viability. The fractions CP-0.3, CP-0.5 and CP-0.9 reduced the viability of the HeLa cells (human cervical adenocarcinoma) by 55% and CP-1.5 reduced the viability of the 786-0 cells (human renal adenocarcinoma) by 75%. Leishmanicidal activity and microbicide effect against Carbapenem-resistant Klebsiella pneumoniae (KPC) have not been identified. However, the viability of Staphylococcus epidermidis was reduced by 23.8% in the presence of CP -1.5. All fractions were able to change the formation of calcium oxalate crystals. CP-0.3, CP-0.5 and CP-1.1 only promoted the formation of COD type crystals with a very small size (1 ��m). Confocal microscopy and zeta potential data of crystals formed in the presence of the samples showed that the polysaccharides present in the fractions must interact with calcium ions present throughout the crystal lattice, affecting the growth and morphology of crystals The results described herein indicate that the fractions rich in polysaccharides obtained from the green seaweed C. prolifera present a multi therapeutic potential, and subsequent purification steps, as well as research on the mechanisms of action by which these polymers act should be investigated.

An��lise de microestrutura e de caracter��sticas geot��cnicas de misturas de res��duo de polimento de porcelanato e solo

Brazil is a country in development, rich in natural resources. In order to grow sustainably, it is necessary to Brazil to preserve its environment, which is an expressive challenge, especially to industries, such as those producing ceramic materials. This study was developed using Porcelain Tile Polishing Residue (RPP) in blends with soil to build compacted fills. This residue is a slurry generated during the polishing process of porcelain tiles and contains powdery material from the polished tile, the abrasives used during the process and cooling water. The RPP was collected from a private company located in Conde/PB and it was mixed with a sandy-clayey soil, to build the fills. Laboratorial tests were conducted with pure soil, pure RPP and blends in proportions of 5%, 10%, 15% and 20% of RPP in addition to the dry mass of pure soil. The Chemical and Physical Characterization tests performed were: specific solid weight, grain size distribution, laser analysis of grain size distribution, Atterberg limits, X ray fluorescence, X ray diffraction, scanning electron microscopy and soil compaction,. The materials and blends were also compacted and direct shear tests and plate load tests were performed. Plate load tests were conducted using a circular plate with 30 cm diameter, on specimens of pure soil and 5% blend, compacted in a metallic box inside the Soil Mechanics Laboratory of the Federal University of Rio Grande do Norte, Brazil. Both mechanical tests performed were conducted under inundated conditions, willing to reduce the influence of soil suction. An evaluation of the results of the tests performed shows that RPP is a fine material, with grain size distribution smaller than 0,015mm, composed mainly of silica and alumina, and particles in angular shape. The soil was characterized as a clayey sand, geologically known as a lateritic soil, with high percentages of alumina and iron oxide, and particles with rounded shape. Both the Soil and the blends presented low plasticity, while the residue showed a medium plasticity. Direct shear tests showed that the addition of RPP did not cause major changes into blends��� friction angle data, however, it was possible to note that, for the proportions studied, that is a tendency of obtain lower shear stresses for higher percentages of RPP in the blends. Both pure soil and 5% mixture showed a punching disruption for the Plate load test. For this same test, the allowable stress for 5% mixture was 44% higher than the pure soil, and smaller vertical settlement results for all stresses.

An��lise de microestrutura e de caracter��sticas geot��cnicas de misturas de res��duo de polimento de porcelanato e solo

Brazil is a country in development, rich in natural resources. In order to grow sustainably, it is necessary to Brazil to preserve its environment, which is an expressive challenge, especially to industries, such as those producing ceramic materials. This study was developed using Porcelain Tile Polishing Residue (RPP) in blends with soil to build compacted fills. This residue is a slurry generated during the polishing process of porcelain tiles and contains powdery material from the polished tile, the abrasives used during the process and cooling water. The RPP was collected from a private company located in Conde/PB and it was mixed with a sandy-clayey soil, to build the fills. Laboratorial tests were conducted with pure soil, pure RPP and blends in proportions of 5%, 10%, 15% and 20% of RPP in addition to the dry mass of pure soil. The Chemical and Physical Characterization tests performed were: specific solid weight, grain size distribution, laser analysis of grain size distribution, Atterberg limits, X ray fluorescence, X ray diffraction, scanning electron microscopy and soil compaction,. The materials and blends were also compacted and direct shear tests and plate load tests were performed. Plate load tests were conducted using a circular plate with 30 cm diameter, on specimens of pure soil and 5% blend, compacted in a metallic box inside the Soil Mechanics Laboratory of the Federal University of Rio Grande do Norte, Brazil. Both mechanical tests performed were conducted under inundated conditions, willing to reduce the influence of soil suction. An evaluation of the results of the tests performed shows that RPP is a fine material, with grain size distribution smaller than 0,015mm, composed mainly of silica and alumina, and particles in angular shape. The soil was characterized as a clayey sand, geologically known as a lateritic soil, with high percentages of alumina and iron oxide, and particles with rounded shape. Both the Soil and the blends presented low plasticity, while the residue showed a medium plasticity. Direct shear tests showed that the addition of RPP did not cause major changes into blends��� friction angle data, however, it was possible to note that, for the proportions studied, that is a tendency of obtain lower shear stresses for higher percentages of RPP in the blends. Both pure soil and 5% mixture showed a punching disruption for the Plate load test. For this same test, the allowable stress for 5% mixture was 44% higher than the pure soil, and smaller vertical settlement results for all stresses.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers��� submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.

Synergistischer photoinduzierter Schadstoffabbau mittels eines Porphyrazin-Titandioxid-Hybrids

Die zunehmende Luftverschmutzung aufgrund des steigenden Energiebedarfs und Mobilit��tsanspruchs der Bev��lkerung, insbesondere in urbanen Gebieten, erh��ht das Gef��hrdungspotential f��r die Gesundheit und verschlechtert so die Lebensqualit��t. Neben der Vermeidung von Emissionen toxischer Gase als mittel- und langfristig optimale Ma��nahme zur Verbesserung der Luftqualit��t, stellt der Abbau emittierter Luftschadstoffe ein geeignetes und kurzfristig wirksames Mittel dar. Ein solcher Abbau kann durch Photokatalyse erzielt werden, allerdings nutzen Photokatalysatoren, die auf dem Halbleiter Titandioxid (TiO2) basieren, das solare Emissionsspektrum nur geringf��fig aus und sind in Innenr��umen und anderen UV-schwachen Bereichen nicht wirksam. Um diese Nachteile zu ��berwinden, wurde ein Photokatalysator entwickelt und hergestellt, der aus TiO2 (P25) als UV-aktiver Photokatalysator und als Tr��germaterial sowie einem seinerseits im Vis-Bereich photoaktiven Porphyrazin-Farbstoff als Beschichtung besteht. Die sterisch anspruchsvollen und in der Peripherie mit acht Bindungsmotiven f��r TiO2 versehenen Farbstoffmolek��le wurden zu diesem Zweck auf der Halbleiteroberfl��che immobilisiert. Die so gebildeten Porphyrazin-Titandioxid-Hybride wurde ausf��hrlich charakterisiert. Dabei wurden unter anderem die Bindung der Farbstoffe auf der Titandioxidoberfl��che mittels Adsorptionsisothermen und die UV/Vis-spektroskopischen Eigenschaften des Hybridmaterials untersucht. Zur Bestimmung der photokatalytischen Aktivit��ten der Einzelkomponenten und des Hybridmaterials wurden diese auf die F��higkeit zur Bildung von Singulett-Sauerstoff, Wasserstoffperoxid und Hydroxylradikalen hin sowie in einem an die ISO-22197-1 angelehnten Verfahren auf die F��higkeit zum Abbau von NO hin jeweils bei Bestrahlung in drei Wellenl��ngenbereichen (UV-Strahlung, blaues Licht und rotes Licht) gepr��ft. Dar��ber hinaus konnte die Aktivit��t des Hybridmaterials bei der Photodynamischen Inaktivierung (PDI) von Bakterien unter UV- und Rotlichtbestrahlung im Vergleich zum reinen Ttandioxid bestimmt werden. Die Charakterisierung des Hybridmaterials ergab, dass die Farbstoffmolek��le in einer neutralen Suspension nahezu irreversibel in einer monomolekularen Schicht mit einer Bindungsenergie von -41.43 kJ/mol an die Oberfl��che gebunden sind und das Hybridmaterial mit hohen Extinktionskoeffizienten von bis zu 105 M-1cm-1 in gro��en Bereichen des UV/Vis-Spektrums Photonen absorbiert. Das Spektrum des Hybridmaterials setzt sich dabei additiv aus den beiden Einzelspektren zusammen. Die Auswirkungen der Charakterisierungsergebnisse auf die Bildung reaktiver Sauerstoffspezies wurden ausf��hrlich diskutiert. Der Vergleich der Aktivit��ten in Bezug auf die Bildung der reaktiven Sauerstoffspezies zeigte, dass die Aktivit��t des Hybridmaterials bis auf die bei der Bildung von Hydroxylradikalen unter UV-Bestrahlung in allen Versuchen deutlich h��her war als die Aktivit��t des reinen Titandioxids. Im Gegensatz zu reinem Titandioxid erzeugte das Hybridmaterial in allen untersuchten Wellenl��ngenbereichen Mengen an Singulett-Sauerstoff, die photophysikalisch eindeutig detektierbar waren. Zur Erkl��rung und Deutung dieser Beobachtungen wurde eine differenzierte Diskussion gef��hrt, die die Ergebnisse der Hybridpartikelcharakterisierung aufgreift und implementiert. Der Vergleich der NO-Abbaueffizienzen ergab bei allen Experimenten durchg��ngig deutlich h��here Werte f��r das Hybridmaterial. Zudem wurden durch das Hybridmaterial nachgewiesenerma��en wesentlich geringere Mengen des unerw��nschten Nebenprodukts des Abbaus (NO2) gebildet. Im Zuge der Diskussion wurden verschiedene m��gliche Mechanismen der ���sauberen��� Oxidation zu Nitrat durch das Hybridmaterial vorgestellt. Untersuchungen zur Photodynamischen Inaktivierung verschiedener Bakterien ergaben, dass das Hybridmaterial neben einer zu P25 ��hnlichen Aktivit��t unter UV-Bestrahlung, anders als P25, auch eine PDI verschiedener Bakterien unter Rotlichtbestrahlung erreicht.