Polyaniline/Pillared Montmorillonite Clay Composite Nanofibers

In situ polymerization of aniline is done inside the pillared clay matrix. The nonswellable pillared clay confined matrix allows efficient polymerization that leads to nanofibrous morphology. As a result high polymer order and crystallinity is attained and is evident from XRD patterns. The strong interaction between the clay layers and polyaniline (PANI) is understood from FTIR and DRS spectra. Additionally these analytical results suggest that the prepared PANI is in the doped state. The PANI/pillared clay nanocomposite formation gives additional thermal stability to the polymer backbone and is clear from the DTG curves.

Glucoamylase immobilized on montmorillonite: influence of nature of binding on surface properties of clay-support and activity of enzyme

Glucoamylase was immobilized on acid activated montmorillonite clay via two different procedures namely adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and the activity of immobilized glucoamylase for starch hydrolysis was determined in a batch reactor. XRD shows intercalation of enzyme into the clay matrix during both immobilization procedures. Intercalation occurs via the side chains of the amino acid residues, the entire polypeptide backbone being situated at the periphery of the clay matrix. 27Al NMR studies revealed the different nature of interaction of enzyme with the support for both immobilization techniques. N2 adsorption measurements indicated a sharp drop in surface area and pore volume for the covalently bound glucoamylase that suggested severe pore blockage. Activity studies were performed in a batch reactor. The adsorbed and covalently bound glucoamylase retained 49% and 66% activity of the free enzyme respectively. They showed enhanced pH and thermal stabilities. The immobilized enzymes also followed Michaelis–Menten kinetics. Km was greater than the free enzyme that was attributed to an effect of immobilization. The immobilized preparations demonstrated increased reusability as well as storage stability.

MB 0610 2008-4B

Dark clay matrix. Generally structure-less with a few small clasts.

MB 0610 2008-4A

Clay matrix with a variation in colour (light brown and dark brown). Generally structure-less with a few small clasts.

MB 0610 2008-3B

Dark clay matrix with a few small and large clasts. The clasts range from angular to sub-rounded. Generally structure-less.

Acid activated montmorillonite: an efficient immobilization support for improving reusability, storage stability and operational stability of enzymes

Three enzymes, α-amylase, glucoamylase and invertase, were immobilized on acid activated montmorillonite K 10 via two independent techniques, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, N2 adsorption measurements and 27Al MAS-NMR spectroscopy. The XRD patterns showed that all enzymes were intercalated into the clay inter-layer space. The entire protein backbone was situated at the periphery of the clay matrix. Intercalation occurred through the side chains of the amino acid residues. A decrease in surface area and pore volume upon immobilization supported this observation. The extent of intercalation was greater for the covalently bound systems. NMR data showed that tetrahedral Al species were involved during enzyme adsorption whereas octahedral Al was involved during covalent binding. The immobilized enzymes demonstrated enhanced storage stability. While the free enzymes lost all activity within a period of 10 days, the immobilized forms retained appreciable activity even after 30 days of storage. Reusability also improved upon immobilization. Here again, covalently bound enzymes exhibited better characteristics than their adsorbed counterparts. The immobilized enzymes could be successfully used continuously in the packed bed reactor for about 96 hours without much loss in activity. Immobilized glucoamylase demonstrated the best results.

Fixed bed reactor performance of invertase immobilized on montmorillonite

Invertase was immobilized on acid activated montmorillonite via two independent procedures, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and their activity was tested in a fixed bed reactor. XRD revealed that the enzyme was situated on the periphery of the clay and the side chains of different amino acid residues were involved in intercalation with the clay matrix. NMR demonstrated that tetrahedral Al was linked to the enzyme during adsorption and the octahedral Al was involved during covalent binding. Secondary interaction of the enzyme with Al was also observed. N2 adsorption studies showed that covalent binding of enzymes caused pore blockage since the highly polymeric species were located at the pore entrance. The fixed bed reactor proved to be efficient for the immobilized invertase. The optimum pH and pH stability improved upon immobilization. The kinetic parameters calculated also showed an enhanced efficiency of the immobilized systems. They could be used continuously for long period. Covalently bound invertase demonstrated greater operational stability.

Glucoamylase immobilized on montmorillonite: Synthesis, characterization and starch hydrolysis activity in a fixed bed reactor

Glucoamylase from Aspergillus Niger was immobilized on montmorillonite clay (K-10) by two procedures, adsorption and covalent binding. The immobilized enzymes were characterized using XRD, surface area measurements and 27Al MAS NMR and the activity of the immobilized enzymes for starch hydrolysis was tested in a fixed bed reactor (FBR). XRD shows that enzyme intercalates into the inter-lamellar space of the clay matrix with a layer expansion up to 2.25 nm. Covalently bound glucoamylase demonstrates a sharp decrease in surface area and pore volume that suggests binding of the enzyme at the pore entrance. NMR studies reveal the involvement of octahedral and tetrahedral Al during immobilization. The performance characteristics in FBR were evaluated. Effectiveness factor (η) for FBR is greater than unity demonstrating that activity of enzyme is more than that of the free enzyme. The Michaelis constant (Km) for covalently bound glucoamylase was lower than that for free enzyme, i.e., the affinity for substrate improves upon immobilization. This shows that diffusional effects are completely eliminated in the FBR. Both immobilized systems showed almost 100% initial activity after 96 h of continuous operation. Covalent binding demonstrated better operational stability.

Adição de cascalho de perfuração da bacia potiguar em argilas para uso em materiais cerâmicos: influência da concentração e temperatura de queima.

One of waste produced on large scale during the well drilling is the gravel drilling. There are techniques for the treatment of the same, but there isn t consensus on what are the best in terms of economic and environmental. One alternative for disposal of this waste and objective of this paper is the incorporation and immobilization of gravel clay matrix to assess their technological properties. The Raw Materials used were characterized by the following techniques: Chemical Analysis by X-ray fluorescence (XRF), mineralogical analysis by X-ray Diffraction (XRD), Grain Size Analysis (FA) and Thermal Analysis by Thermogravimetry (TG) and thermodiferential (DTA). After characterizing, samples were formulated in the following percentages: 0, 5, 10, 15, 25, 50, 75, 100% (weight) of gravel drilling, then the pieces were pressed, dried (110 ° C) and sintered at temperatures of 850, 950 and 1050 ° C. After sintering, samples were tested for water absorption, linear shrinkage, flexural strength, porosity, density, XRD and test color. The results concluded that the incorporation of gravel drilling is a viable possibility for solid masonry bricks and ceramic blocks manufacture at concentrations and firing temperature described here. Residue incorporation reduces an environmental problem, the cost of raw materials for manufacture of ceramic products

Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

Avaliação da incorporação combinada dos resíduos de cascalho de perfuração de poço de petróleo e de polimento do porcelanato em cerâmica vermelha

Among the industries, those that produce ceramic porcelain for use in construction industry and oil, during the exploration and production period, play an important role in the production of waste. Much research has been carried out both by academia and the productive sector, sometimes reintroducing them in the same production line that generated them, sometimes in areas unrelated to their generation, as in the production of concrete and mortar for the construction, for example, but each one in an isolated way. In this research, the aim is to study the combined incorporation of the waste drill cuttings of oil well and the residue of the polishing of porcelain, generated in the final stage of finishing of this product in a clay matrix, for the production of red pottery, specifically bricks, ceramic blocks and tiles. The clay comes from the municipality of São Gonçalo, RN, the drilling waste is from the Natal basin, in Rio Grande do Norte, and the residue of the polishing proceeds from a ceramic porcelain of the State of Paraíba. For this purpose, we used a mixture of a plastic clay with a non-plastic, in a ratio of 50% each, settling formulations with the addition of these two residues in this clay matrix. In the formulations, both residues were incorporated with a minimum percentage of 2.5% and maximum of 12.5%, varying from 2.5% each, in each formulation, which the sum of the waste be no more than 15%. It should be noted that the residue of the polishing of ceramic porcelain is a IIa class (not inert). The materials were characterized by XRF, XRD, TG, DTA, laser granulometry and the plasticity index. The technological properties of water absorption, apparent porosity, linear shrinkage of burning, flexural tensile strength and bulk density were evaluated after the sintering of the pieces to 850 °C, 950 °C and 1050 °C, with a burning time of 3 hr, 3 hr and 30 minutes, and 3 hr and 50 minutes, respectively, with a heating rate of 10 °C/minute, for all formulations and landing of 30 minutes. To better understand the influence of each residue and temperature on the evaluated properties, we used the factorial planning and its surfaces of response for the interpretation of the results. It was found that the temperature has no statistical significance at a 95% of reliability level in flexural tensile strength and that it decreases the water absorption and the porosity, but increases the shrinkage and the bulk density. The results showed the feasibility of the desired incorporation, but adjusting the temperature to each product and formulation, and that the temperatures of 850 °C and 950 °C were the one that responded to the largest number of formulations

Caracterização de minerais pesados ao longo do Rio Piranhas-Açu/RN distribuição e proveniência

This dissertation deals with the characterization, distribution and provenience of heavy minerals along the Piranhas-Açu River, from the City of Parelhas (Seridó River) to your mouth at the City of Macau-RN. Many heavy minerals species were recorded in this study: clinoamphibole, epidote (including zoisite), garnet, sillimanite, tourmaline, staurolite, andalusite, zircon, rutile, augite, ilmenite, hematite and magnetite. Major transparent minerals, those forming more than 5% of some assemblages, are hornblende, epidote, tourmaline, staurolite and zircon. Predominant opaque mineral is ilmenite. Six assemblages were identified along the river: (i) Garnet-hornblende-tourmaline with sillimanite, when cutting rocks of the Seridó Formation; (ii) Hornblende-garnet-zircon, when crossing rocks of the Caicó gnaisse-migmatitic Complex; (iii) Hornblende-zircon-epidote-staurolite, when draining rocks of the Jucurutu Formation; (iv) Hornblende-zircon-epidote, when cutting rocks of the Açu Formation; (v) Hornblende-zircon-staurolite, on the lowermost Açu River, when crossing limestones of the Jandaíra Formation and (vi) Zircon-tourmaline-staurolite in the Açu River mouth (Cenozoic rocks) where coastal process dominate. Mineral ratios that reflect differences in grain shape, density, and selective chemical decomposition were used in an attempt to isolate the effects of source and process as controls of mineral variability. Reworking of the sediments was regionally effective in selective sorting; the more equant minerals (e.g. epidote) and heavier minerals (e.g. opaques) had a higher probability of being selected for permanent deposition during reworking. The processes of selective decomposition stand out at the river mouth. A priori knowledge of provenance, associated with the assemblage distribution and effects of process were utilized to the interpretations, that points to the follow provenances: hornblende comes from micashists of the Seridó Formation, orthognaisses and amphibolites of the Caico Complex, paragnaisses and paranphibolites of the Jucurutu Formation and granites intrusions; epidote comes from paragnaisses and calciosilicatics of the Jucurutu Formation, granites intrusions (-Npy3al/ca and -Npy3mz, gravels deposits and Açu Formation; Andalusite and staurolite come from the Seridó Formation; Sillimanite, tourmaline and garnet come from micashists of the Seridó Formation, as well as from quartzites of the Equador Formation; Zircon comes from Precambrian rocks (pink and prismatic zircon) and from sediments of several cycles (round zircon); Opaques come from all rocks cutted for the Piranhas-Açu River; Rutile comes from metamorphic rocks, in general; Augite comes from the Ceará-Mirim, Serra do Cuó and Macau volcanisms. The texture of gravels deposits reveals a sediment transport mechanisms by traction-current processes, together with a diagenetic clay matrix suggests a hot-humid environments for deposition. The presence of unstable heavy minerals assemblages, as well as pebbles of different composition and degrees of rounding and esfericity, indicate more than one source. The occurrence of calcio/alkaline granites suites, in areas closed to the gravel deposits, suggests that these intrusions are the main source of sediments. This could explain for instance, the significant amounts of epidote and presence of unstable heavy minerals (e.g. hornblende). The analyses of heavy minerals also show significante variability between the modern (Piranhas-Açu) and ancestral (Açu Formation) river sediments. In general, these variations reflect relatively higher unstable and lower stable heavy minerals contents of the modern Piranhas-Açu sediments. The absence of significant compositional differences probably reflects uniform weathering conditions

Mineralogy and chemistry of archaeological ceramic fragments from archaeological Dark Earth site in Colombian Amazon

Vários sítios arqueológicos de Terra Preta Arqueológica (TPA) encontrados na floresta Amazônica Colombiana também contêm alto conteúdo de fragmentos cerâmicos semelhantes aqueles da Amazônia Brasileira, como mostra o sítio Quebrada Tacana. Seus fragmentos cerâmicos são amarelo a cinza, exibem matriz argilosa calcinada envolvendo fragmentos de cariapé, carvão e partículas de cinza, grãos de quartzo e micas. A matriz é composta de metacaulinita a material amorfo, quartzo, folhas de micas, clorita e sepiolita. Cariapé e cauixi são constituídos de cristobalita, da mesma forma o carvão e as cinzas. Embora não detectados pela difração de raios x, os fosfatos devem estar presentes, pois foram detectados teores de P2O5 de até 2,90 %, possivelmente como fosfatos de alumínio, já que o conteúdo de Ca está abaixo 0,1 %, o que elimina a possibilidade da presença de apatita. Estas características mineralógicas e químicas permitem relacionar estes fragmentos cerâmicos com aqueles encontrados nos sítios de TPA no Brasil e reforça o fósforo como um importante componente químico, originado pelo contato dos vasos cerâmicos com os alimentos do cotidiano dos povos amazônicos pré-históricos.

A zona de contato entre as formações Motuca e Sambaíba, Permo-Triássico da bacia do Parnaíba, regiões de Filadélfia (TO), Riachão (MA) e Loreto (MA)

O intervalo que compreende o final do Paleozóico e início do Mesozóico foi marcado por mudanças globais paleogeográficas e paleoclimáticas, em parte atribuídas a eventos catastróficos. A intensa continentalização do supercontinente Pangéia, com a implantação de extensos desertos, sucedeu os ambientes costeiros-plataformais do início do Permiano. Os registros desses eventos no norte do Brasil são encontrados nas bacias intracratônicas, particularmente na Bacia do Parnaíba, representados pela zona de contato entre as formações Motuca e Sambaíba. A Formação Motuca é constituída predominantemente por pelitos vermelhos laminados com lentes de gipsita, calcita e marga. Na porção leste da Bacia do Parnaíba, as fácies da Formação Motuca tornam-se mais arenosas com a ocorrência expressiva de arenitos com estratificação cruzada sigmoidal. A Formação Sambaíba consiste em arenitos de coloração creme alaranjada com estratificação plano-paralela e estratificação cruzada de médio a grande porte. Em geral, o contato entre as unidades é brusco, representado pela passagem de arenitos finos com laminação cruzada cavalgante e acamamento flaser/wavy da Formação Motuca para arenitos médios com falhas/microfalhas sinsedimentares e laminações convolutas da Formação Sambaíba. Foram individualizadas 14 fácies sedimentares, agrupadas em quatro associações: AF1 – Lacustre raso / Planície de lama (mudflat), AF2 – “Panela” salina (saline pan), AF3 – Lençol de areia e AF4 – Campo de dunas. A AF1 foi depositada dominantemente por processos de decantação em um extenso ambiente lacustre raso de baixa energia, influenciado por influxos esporádicos de areias oriundos de rios efêmeros. Este sistema lacustre foi, provavelmente, influenciado por períodos de contração e expansão, devido às variações das condições climáticas predominantemente áridas. Os mais expressivos períodos de contração ocorreram na porção oeste da Bacia do Parnaíba, representados pelo desenvolvimento de planícies de lama (mudflats) associadas a lagoas efêmeras saturadas em carbonatos e a “panelas” salinas (saline pans- AF2). Os lençóis de areia (AF3) são planícies arenosas extensas, localmente com área úmidas, intensamente retrabalhadas por processos eólicos. A AF4 é interpretada como parte de um erg composto por dunas/draas em zona saturada em areia, com interdunas secas subordinadas. Intervalos deformados lateralmente contínuos por centenas de quilômetros ocorrem na zona de contato entre as formações Motuca e Sambaíba. Pelitos com camadas contorcidas e brechadas (Formação Motuca) e arenitos com falhas/microfalhas sinsedimentares, laminação convoluta e diques de injeção preenchidos por argilitos (Formação Sambaíba) são interpretados como sismitos induzidos por terremotos de alta magnitude (>8 na escala Ritcher). Anomalias geoquímicas de elementos traços como Mn, Cr, Co, Cu e Ni na zona de contato entre as formações, juntamente com a presença de micropartículas de composição metálica na matriz argilosa dos sismitos, corroboram com impactos de meteoritos no limite c, possivelmente do astroblema Riachão.

Sviluppo di biosensori: modifiche di superfici elettrodiche e sistemi di immobilizzazione enzimatica

An amperometric glucose biosensor was developed using an anionic clay matrix (LDH) as enzyme support. The enzyme glucose oxidase (GOx) was immobilized on a layered double hydroxide Ni/Al-NO3 LDH during the electrosynthesis, which was followed by crosslinking with glutaraldehyde (GA) vapours or with GA and bovine serum albumin (GABSA) to avoid the enzyme release. The electrochemical reaction was carried out potentiostatically, at -0.9V vs. SCE, using a rotating disc Pt electrode to assure homogeneity of the electrodeposition suspension, containing GOx, Ni(NO3)2 and Al(NO3)3 in 0.3 M KNO3. The mechanism responsible of the LDH electrodeposition involves the precipitation of the LDH due to the increase of pH at the surface of the electrode, following the cathodic reduction of nitrates. The Pt surface modified with the Ni/Al-NO3 LDH shows a much reduced noise, giving rise to a better signal to noise ratio for the currents relative to H2O2 oxidation, and a linear range for H2O2 determination wider than the one observed for bare Pt electrodes. We pointed out the performances of the biosensor in terms of sensitivity to glucose, calculated from the slope of the linear part of the calibration curve for enzimatically produced H2O2; the sensitivity was dependent on parameters related to the electrodeposition in addition to working conditions. In order to optimise the glucose biosensor performances, with a reduced number of experimental runs, we applied an experimental design. A first screening was performed considering the following variables: deposition time (30 - 120 s), enzyme concentration (0.5 - 3.0 mg/mL), Ni/Al molar ratio (3:1 or 2:1) of the electrodeposition solution at a total metals concentration of 0.03 M and pH of the working buffer solution (5.5-7.0). On the basis of the results from this screening, a full factorial design was carried out, taking into account only enzyme concentration and Ni/Al molar ratio of the electrosynthesis solution. A full factorial design was performed to study linear interactions between factors and their quadratic effects and the optimal setup was evaluated by the isoresponse curves. The significant factors were: enzyme concentration (linear and quadratic terms) and the interaction between enzyme concentration and Ni/Al molar ratio. Since the major obstacle for application of amperometric glucose biosensors is the interference signal resulting from other electro-oxidizable species present in the real matrices, such as ascorbate (AA), the use of different permselective membranes on Pt-LDHGOx modified electrode was discussed with the aim of improving biosensor selectivity and stability. Conventional membranes obtained using Nafion, glutaraldehyde (GA) vapours, GA-BSA were tested together with more innovative materials like palladium hexacyanoferrate (PdHCF) and titania hydrogels. Particular attention has been devoted to hydrogels, because they possess some attractive features, which are generally considered to favour biosensor materials biocompatibility and, consequently, the functional enzyme stability. The Pt-LDH-GOx-PdHCF hydrogel biosensor presented an anti-interferant ability so that to be applied for an accurate glucose analysis in blood. To further improve the biosensor selectivity, protective membranes containing horseradish peroxidase (HRP) were also investigated with the aim of oxidising the interferants before they reach the electrode surface. In such a case glucose determination was also accomplished in real matrices with high AA content. Furthermore, the application of a LDH containing nickel in the oxidised state was performed not only as a support for the enzyme, but also as anti-interferant sistem. The result is very promising and it could be the starting point for further applications in the field of amperometric biosensors; the study could be extended to other oxidase enzymes.