Influence of cerium (IV) ions on the inorganic and organic phase for preparation of a siloxane-PMMA based film on tin plate substrate

Tinplate is one of the most widely used food canning materials, however, there are significant problems related to the use of tinplate cans, such as alterations in sensory features affecting food quality and corrosion phenomena of the canning material. To avoid corrosion problems different methods have been used for the passivation of tinplate such protective lacquers or different kinds of corrosion inhibitors (chromate and dichromate). However, chromates and dichromates are extremely harmful to the environment and can cause carcinogenic tumors to humans. An option, protective coatings obtained by the sol-gel process, act as a physical barrier, which isolates the surface of metal protecting from the corrosive agents. The aim of this work is to study the influence of addition of cerium (IV) ions in the inorganic and organic part of sol-gel processing in the formation of hybrid coatings based on siloxane-PMMA on tin plate. The coatings were obtained by dip-coating technique and evaluated by open circuit and impedance measurements, linear polarization and polarization curves obtained in 3.5% NaCl solution. The results have clearly shown the improvement on the protective properties of the Ce 4+ modified film when added into the organic phase, which can be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. © 2009 by NACE International.

Inorganic-organic hybrid polymers: Solution-processible coating materials for defined surface functionalization

A new class of inorganic-organic hybrid polymers could successfully been prepared by the combination of different polymerization techniques. The access to a broad range of organic polymers incorporated into the hybrid polymer was realized using two independent approaches.rnIn the first approach a functional poly(silsesquioxane) (PSSQ) network was pre-formed, which was capable to initiate a controlled radical polymerization to graft organic vinyl-type monomers from the PSSQ precursor. As controlled radical polymerization techniques atom transfer radical polymerization (ATRP), as well as reversible addition fragmentation chain transfer (RAFT) polymerization could be used after defined tuning of the PSSQ precursor either toward a PSSQ macro-initiator or to a PSSQ macro-chain-transfer-agent. The polymerization pathway, consisting of polycondensation of trialkoxy-silanes followed by grafting-from polymerization of different monomers, allowed synthesis of various functional hybrid polymers. A controlled synthesis of the PSSQ precursors could successfully be performed using a microreactor setup; the molecular weight could be adjusted easily while the polydispersity index could be decreased well below 2.rnThe second approach aimed to incorporate differently derived organic polymers. As examples, polycarbonate and poly(ethylene glycol) were end-group-modified using trialkoxysilanes. After end-group-functionalization these organic polymers could be incorporated into a PSSQ network.rnThese different hybrid polymers showed extraordinary coating abilities. All polymers could be processed from solution by spin-coating or dip-coating. The high amount of reactive silanol moieties in the PSSQ part could be cross-linked after application by annealing at 130° for 1h. Not only cross-linking of the whole film was achieved, which resulted in mechanical interlocking with the substrate, also chemical bonds to metal or metal oxide surfaces were formed. All coating materials showed high stability and adhesion onto various underlying materials, reaching from metals (like steel or gold) and metal oxides (like glass) to plastics (like polycarbonate or polytetrafluoroethylene).rnAs the material and the synthetic pathway were very tolerant toward different functionalities, various functional monomers could be incorporated in the final coating material. The incorporation of N-isopropylacrylamide yielded in temperature-responsive surface coatings, whereas the incorporation of redox-active monomers allowed the preparation of semi-conductive coatings, capable to produce smooth hole-injection layers on transparent conductive electrodes used in optoelectronic devices.rnThe range of possible applications could be increased tremendously by incorporation of reactive monomers, capable to undergo fast and quantitative conversions by polymer-analogous reactions. For example, grafting active esters from a PSSQ precursor yielded a reactive surface coating after application onto numerous substrates. Just by dipping the coated substrate into a solution of a functionalized amine, the desired function could be immobilized at the interface as well as throughout the whole film. The obtained reactive surface coatings could be used as basis for different functional coatings for various applications. The conversion with specifically tuned amines yielded in surfaces with adjustable wetting behaviors, switchable wetting behaviors or as recognition element for surface-oriented bio-analytical devices. The combination of hybrid materials with orthogonal reactivities allowed for the first time the preparation of multi-reactive surfaces which could be functionalized sequentially with defined fractions of different groups at the interface. rnThe introduced concept to synthesis functional hybrid polymers unifies the main requirements on an ideal coating material. Strong adhesion on a wide range of underlying materials was achieved by secondary condensation of the PSSQ part, whereas the organic part allowed incorporation of various functionalities. Thus, a flexible platform to create functional and reactive surface coatings was achieved, which could be applied to different substrates. rn

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one factor at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

New end-use application for GFRP recyclates as reinforcement for concrete-polymer materials’

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one-factor-at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and filler replacements for polymer mortar, with significant gain of mechanical properties with regard to non-modified polymer mortars.

Uma metodologia para o projeto teórico de conversores moleculares de luz

Recentlly, we have proposed the representation of lanthanides within AM1 as sparkles for the purpose of obtaing ground state geometries of their complexes. We tested our quantum chemical sparkle model (SMLC/AM1) for the prediction of the crystallographic structure of complexes with coordination number nine, eight and seven. A technique is introduced for the theoretical prediction of eletronic spectra of the organic part of lanthanide complexes by replacing the metal ion by a point charge with the ligands held in their positions as determined by the SMLC/AM1, and by computing the theoretical spectra via the intermediate neglect of differential overlap/spectroscopic-configuration interaction (INDO/S-CI).

Influência da concentração das partículas cristalinas nas propriedades dielétricas do híbrido PVAl/Cds

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interação do complexo luminescente [Eu(tta)3] com sílica mesoporosa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Gestão de resíduos sólidos domiciliares orgânicos: práticas e técnicas para a destinação final na cidade de Rio Claro - SP

The present work is the analysis of the practices and techniques currently used in the final allocation given to organic household solid waste in the city of Rio Claro - SP. As the major part of Rio Claro’s household solid waste is formed by the organic fraction, as well as in the rest of the country, this research proposes a study on what is done with that portion of the waste, its treatment and where finally destined, based on the National Solid Waste Politic, recently approved in 2010. With the use of this organic part, for example: as animal feed supplement or compost embodiment for the purpose of producing organic fertilizer, enables the decrease of the percentage of the total destined to dumps and landfills. This total percentage has already been reduced after the popularization of the beneficial recycling programs in Brazil, which are still growing. As cities and the purchasing power of its individuals grow, there is also a consequent growth of waste production by society. The household whether domestic solid waste are lower than Industrial Solid ( RSI ) waste for the production in million tons ( Mton ) quantities , however, those residues are more visible on a daily basis - in cities and periphery as well, due to the inadequate management, - and also offer , as well as industrial and agricultural wastes , several types of harmful effects to the population when managed incorrectly. Therefore, the research aims to assist in the study of Solid Waste Management (MSW) for efficient Urban and Environmental Planning in a midsize city. Thus, this project aims to analyze in the city of Rio Claro, how the allocation of these materials is done and whether these practices denote effective improvement regarding the proper management of waste, in the same way that the recycling chain would allow this effect

The histological features and physical properties of eroded dental hard tissues.

Erosive demineralisation causes characteristic histological features. In enamel, mineral is dissolved from the surface, resulting in a roughened structure similar to an etching pattern. If the acid impact continues, the initial surface mineral loss turns into bulk tissue loss and with time a visible defect can develop. The microhardness of the remaining surface is reduced, increasing the susceptibility to physical wear. The histology of eroded dentine is much more complex because the mineral component of the tissue is dissolved by acids whereas the organic part is remaining. At least in experimental erosion, a distinct zone of demineralised organic material develops, the thickness of which depends on the acid impact. This structure is of importance for many aspects, e.g. the progression rate or the interaction with active agents and physical impacts, and needs to be considered when quantifying mineral loss. The histology of experimental erosion is increasingly well understood, but there is lack of knowledge about the histology of in vivo lesions. For enamel erosion, it is reasonable to assume that the principal features may be similar, but the fate of the demineralised dentine matrix in the oral cavity is unclear. As dentine lesions normally appear hard clinically, it can be assumed that it is degraded by the variety of enzymes present in the oral cavity. Erosive tooth wear may lead to the formation of reactionary or reparative dentine.

Tratamiento de lesiones incipientes

Como sabemos, la caries es una enfermedad infecciosa, transmisible de los dientes, que se caracteriza por la desintegración de sus tejidos calcificados. La lesión cariosa es definida como DINÁMICA. Es por esto que debemos establecer si el fenómenos DES/RES se encuentra en equilibrio o la desmineralización ha alcanzado un papel preponderante, dando como resultado pérdida de la porción mineral y la subsecuente disgregación de la parte orgánica. Así es como el diagnóstico finaliza, poniéndose en auge la función terapéutica. Durante el desarrollo de estos casos clínicos las lesiones de mancha blanca fueron tratadas con sustancias a base de fosfatos y calceinatos.

Experiment: changing carbonate chemistry influence on coccoliths formed by Emiliania huxleyi

The coccolithophore Emiliania huxleyi is a marine phytoplankton species capable of forming small calcium carbonate scales (coccoliths) which cover the organic part of the cell. Calcification rates of E. huxleyi are known to be sensitive to changes in seawater carbonate chemistry. It has, however, not yet been clearly determined how these changes are reflected in size and weight of individual coccoliths and which specific parameter(s) of the carbonate system drive morphological modifications. Here, we compare data on coccolith size, weight, and malformation from a set of five experiments with a large diversity of carbonate chemistry conditions. This diversity allows distinguishing the influence of individual carbonate chemistry parameters such as carbon dioxide (CO2), bicarbonate (HCO3- ), carbonate ion (CO32-), and protons (H+) on the measured parameters. Measurements of fine-scale morphological structures reveal an increase of coccolith malformation with decreasing pH suggesting that H+ is the major factor causing malformations. Coccolith distal shield area varies from about 5 to 11 µm2. Changes in size seem to be mainly induced by varying [HCO3- ] and [H+] although influence of [CO32-] cannot be entirely ruled out. Changes in coccolith weight were proportional to changes in size. Increasing CaCO3 production rates are reflected in an increase in coccolith weight and an increase of the number of coccoliths formed per unit time. The combined investigation of morphological features and coccolith production rates presented in this study may help to interpret data derived from sediment cores, where coccolith morphology is used to reconstruct calcification rates in the water column.

The turnover of organic carbon in subsoils. Part 2. Modelling carbon turnover

A new model, RothPC-1, is described for the turnover of organic C in the top metre of soil. RothPC-1 is a version of RothC-26.3, an earlier model for the turnover of C in topsoils. In RothPC-1 two extra parameters are used to model turnover in the top metre of soil: one, p, which moves organic C down the profile by an advective process, and the other, s, which slows decomposition with depth. RothPC-1 is parameterized and tested using measurements (described in Part 1, this issue) of total organic C and radiocarbon on soil profiles from the Rothamsted long-term field experiments, collected over a period of more than 100 years. RothPC-1 gives fits to measurements of organic C and radiocarbon in the 0-23, 23-46, 46-69 and 69-92 cm layers of soil that are almost all within (or close to) measurement error in two areas of regenerating woodland (Geescroft and Broadbalk Wildernesses) and an area of cultivated land from the Broadbalk Continuous Wheat Experiment. The fits to old grassland (the Park Grass Experiment) are less close. Two other sites that provide the requisite pre- and post-bomb data are also fitted; a prairie Chernozem from Russia and an annual grassland from California. Roth-PC-1 gives a close fit to measurements of organic C and radiocarbon down the Chernozem profile, provided that allowance is made for soil age; with the annual grassland the fit is acceptable in the upper part of the profile, but not in the clay-rich Bt horizon below. Calculations suggest that treating the top metre of soil as a homogeneous unit will greatly overestimate the effects of global warming in accelerating the decomposition of soil C and hence on the enhanced release of CO2 from soil organic matter; more realistic estimates will be obtained from multi-layer models such as RothPC-1.

Hydrothermal syntheses of ETS-10 like vanadosilicates using chiral organic molecules. Part I

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Radiocarbon Analysis of Elemental and Organic Carbon in Switzerland during Winter-Smog Episodes from 2008 to 2012 – Part I: Source Apportionment and Spatial Variability

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.