Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

Polyaniline/layered zirconium phosphate nanocomposites: Secondary-like doped polyaniline obtained by the layer-by-layer technique

In the present work, nanocomposites of polyaniline (PANI) and layered alpha-Zr(HPO4)(2).H2O (alpha-ZrP) were prepared using two different approaches: (i) the in situ aniline polymerization in the presence of the layered inorganic material and (ii) the layer-by-layer (LBL) assembly using an aqueous solution of the polycation emeraldine salt (ES-PANI) and a dispersion of exfoliated negative slabs of alpha-ZrP. These materials were characterized spectroscopically using mainly resonance Raman scattering at four exciting radiations and electronic absorption in the UV-VIS-NIR region. Structural and textural characterizations were carried out using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The polymer obtained by the in situ aniline polymerization is located primarily in the external surface of the inorganic material although aniline monomers were intercalated between alpha-ZrP interlayer regions before oxidative polymerization. Through resonance Raman spectroscopy, it was observed that the formed polymer has semiquinone units (ES-PANI) and also azo bonds (-N = N-), showing that this method results in a polymer with a different structure from the usual ""head-to-tail"" ES-PANI. The LBL assembly of pre-formed ES-PANI and exfoliated alpha-ZrP particles produces homogeneous films with reproducible deposition from layer to layer, up to 20 bilayers. Resonance Raman (lambda(0) = 632.8 nm) spectrum of PANI/ZrP LBL film shows an enhancement in the intensity of the polaronic band at 1333 cm(-1) (nu C-N center dot+) and the decrease of the band intensity at 1485 cm(-1) compared to bulk ES-PANI. Its UV-VIS-NIR spectrum presents an absorption tail in the NIR region assigned to delocalized free charge carrier. These spectroscopic features are characteristic of highly conductive secondary doped PANI suggesting that polymeric chains in PANI/ZrP LBL film have a more extended conformation than in bulk ES-PANI.

Spectroscopic investigation of conjugated polymers derived from nitroanilines

For the first time, the resonance Raman spectroscopy was used to characterize polymers derived from meta- and para-nitroanilines. In order to improve the polymer structure analysis, other techniques were also used such as FTIR, UV-vis, XRD, XPS, EPR and N K-XANES. The insertion of strong electron-withdrawing groups (NO2) in polyaniline (PANI)-like backbone causes drastic changes in the lower energy charge transfer states, related to the polymer effective conjugation length. The resonance Raman data show that the NO2 moiety has a minor contribution on the CT state in poly(meta-nitroaniline), PMN, while in the poly(para-nitroaniline), PPN, the quinoid structure induced by para-substitution increases the charge density of NO2 groups, causing a more localized chromophore. The characterization of the imine nitrogen and of the protonated segments was done by XPS, N K-XANES and EPR spectroscopies and the lower polymerization degree of PPN, in comparison to PMN, is confirmed by XRD and TG data. (C) 2007 Elsevier B.V. All rights reserved.

Spectroscopic characterization of the structural changes of polyaniline nanofibers after heating

The thermal behavior of PANI nanofibers doped with beta-naphthalenesulfonic acid (beta-NSA) was investigated and their morphological and structural changes after heating were monitored by SEM, XRD and Raman techniques, respectively. By using electron-scanning microscopy it is possible to verify that the nanofiber morphology is stable and no polymer degradation is observed in thermogravimetric (TG) data up to 200 degrees C. Nevertheless, the heating promotes the formation of cross-linking structures (phenazine and/or oxazine-like rings), that is clearly demonstrated by the presence of bands at ca. 578, 1398, and 1644 cm(-1) in resonance Raman spectra of heated PANI-NSA samples. The most important consequence of the formation of cross-linking structures in PANI-NSA samples is that these samples retain their nanofiber morphology upon HCl doping in contrast to PANI-NSA nanofibers without heating. (c) 2007 Elsevier Ltd. All rights reserved.

Study of ethanol electro-oxidation in acid environment on Pt(3)Sn/C anode catalysts prepared by a modified polymeric precursor method under controlled synthesis conditions

A carbon-supported binary Pt(3)Sn catalyst has been prepared using a modified polymeric precursor method under controlled synthesis conditions This material was characterized using X-ray diffraction (XRD). and the results indicate that 23% (of a possible 25%) of Sn is alloyed with Pt, forming a dominant Pt(3)Sn phase. Transmission election microscopy (TEM) shows good dispersion of the electrocatalyst and small particle sizes (3 6 nm +/- 1 nm) The polarization curves for a direct ethanol fuel cell using Pt(3)Sn/C as the anode demonstrated Improved performance compared to that of a PtSn/C E-TEK. especially in the intrinsic resistance-controlled and mass transfer regions. This behavior is probably associated with the Pt(3)Sn phase. The maximum power density for the Pt(3)Sn/C electrocatalyst (58 mW cm(-2)) is nearly twice that of a PtSn/C E-TEK electrocatalyst (33 mW cm(-2)) This behavior is attributed to the presence of a mixed Pt(9)Sn and Pt(3)Sn alloy phase in the commercial catalysts (C) 2009 Elsevier B V All rights reserved

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

Nanocatalysts for sustainable industrial processses

In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

Otimização de uma metodologia para análise mineralógica racional de argilominerais

VARELA, M.L. et al. Otimização de uma metodologia para análise mineralógica racional de argilominerais. Cerâmica, São Paulo, n. 51, p. 387-391, 2005.

Estudo da síntese e sinterização de pós compósitos do sistema Ta-Cu

Ta-Cu bulk composites combine high mechanical resistance of the Ta with high electrical and thermal conductivity of the Cu. These are important characteristics to electrical contacts, microwave absorber and heat skinks. However, the low wettability of Ta under Cu liquid and insolubility mutual these elements come hard sintering this composite. High-energy milling (HEM) produces composite powders with high homogeneity and refines the grain size. This work focus to study Ta-20wt%Cu composite powders prepared by mechanical mixture and HEM with two different conditions of milling in a planetary ball mill and then their sintering using hydrogen plasma furnace and a resistive vacuum furnace. After milling, the powders were pressed in a steel dye at a pressure of 200 MPa. The cylindrical samples pressed were sintered by resistive vacuum furnace at 10-4torr with a sintering temperature at 1100ºC / 60 minutes and with heat rate at 10ºC/min and were sintered by plasma furnace with sintering temperatures at 550, 660 and 800ºC without isotherm under hydrogen atmosphere with heat rate at 80ºC/min. The characterizations of the powders produced were analyzed by scanning electron microscopy (SEM), x-ray diffraction (XRD) and laser granulometry. After the sintering the samples were analyzed by SEM, XRD and density and mass loss tests. The results had shown that to high intense milling condition produced composite particles with shorter milling time and amorphization of both phases after 50 hours of milling. The composite particles can produce denser structure than mixed powders, if heated above the Cu melting point. After the Cu to arrive in the melting point, liquid copper leaves the composite particles and fills the pores

Desenvolvimento de cerâmica vermelha utilizando rejeitos da construção civil

The Industry of the Civil Construction has been one of the sectors that most contribute to the pollution of the environment, due to the great amount of residues generated by the construction, demolition and the extraction of raw material. As a way of minimizing the environmental impacts generated by this industry, some governmental organizations have elaborated laws and measures about the disposal of residues from the building construction (CONAMA - resolution 307). This work has as objective the reutilization of residues compound of sand, concrete, cement, red bricks and blocks of cement and mortar for the production of red ceramic, with the objective of minimizing costs and environmental impacts. The investigated samples contained 0% to 50% of residues in weight, and they were sintered at temperatures of 950°C, 1000°C, 1050°C, 1100°C and 1150°C. After the sinterization, the samples were submitted to tests of absorption of water, linear retraction, resistance to bending, apparent porosity, specific density, XRD and SEM. Satisfactory results were obtained in all studied compositions, with the possible incorporation of up to 50% of residues in ceramic mass without great losses in the mechanical strength, giving better results to the incorporation of 30% of residues in the fabrication of ceramic parts, such as roofing tiles, bricks masonry and pierced bricks

Influência do lodo de ETE na massa para fabricação de cerâmica vermelha

The WTP produce many kinds of residue on your treatment stages, but the sludge is the more problematic from the final disposition point view. The actual rate of residue production deriving from technological evolution and the crescent population needs prevents the subtle equilibrium generation between consumption and recycling/reuse, creating problems of pollution resulting from inappropriate management of residues. Thus, is necessary achieve a new equilibrium between the grow from raw materials and energy and the residue generation. This equilibrium should be achieved by technical and economic feasibility of environmental supported models through recycling and reuse. The red ceramic industry stand out in residue absorption question as raw material due their clay mass heterogeneity, constituted by clay minerals and non-clay minerals with wide mineralogical variation, allowing residue inclusion which act like plastic or non-plastic materials, contributing to retain heavy metals contained in residues in the vitreous mass formed during the burning of the ceramic bodies. This work propose the study of the influence of incorporation of 25 wt.% sludge from wastewater treatment plant, according preliminary results, in the mass to produce ceramic bodies. The raw materials was characterized through chemical composition analyses by XRF, mineralogical analyses by XRD, thermal analyses by TG and DTA, Atterberg limits and thermodilatometry. Subsequently was composed the mass with 75 wt.% of clay and 25 wt.% of dried wastewater sludge from UFRN WWTP. Samples with 6,0 x 2,0 x 0,5 cm was produced with unidirectional compacting under pressure of 20MPa and burned in temperatures between 950 and 1,200ºC. After fired, the ceramic bodies have been submitted to physical and mechanical analyses through the measure of firing shrinkage, water absorption, density, apparent porosity and flexural strength; crystallographic analyses through XRD and microstructure analyses by SEM. The technological properties obtained was satisfactory to production of roof tiles with 25 wt.% at 1,200 ºC, but the production of others products at lower temperatures was not feasible

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

Obtenção de filtro cerâmico a partir da diatomita e casca de arroz carbonizada visando tratamento de efluente têxtil

The effluents released by the textile industry have high concentrations of alkali, carbohydrates, proteins, in addition to colors containing heavy metals. Therefore, a filter was prepared aiming primarily to the removal of color. In order to prepare this filter, rice hulls and diatomite were used, which have in their structure, basically amorphous hydrated silica. The silica exists in three crystalline forms: quartz, tridymite and cristobalite. In accordance with the above considerations, this study was divided into two stages; the first corresponds to the preparation of the filter and the second to carry out the tests in the effluent/filter in order to verify the efficiency of the color removal. First, the raw material was subjected to a chemical analysis and XRD, and then the diatomite was mixed, via humid, with a planetarium windmill with 20 %, 40 %, 60 % and 80 % of rice husk ash. To the mixture, 5 % carboxymethylcellulose (CMC) was added as a binder at room temperature. The samples were uniaxially compacted into metallic matrix of 0.3 x 0.1 cm² of area at a pressure of 167 MPa by means of hydraulic press and then sintered at temperatures of 1,000 °C, 1,200 °C and 1,400 °C for 1 h and submitted to granulometry test using laser, linear retraction, water absorption, apparent porosity and resistance to bending, DTA, TMA and XRD. To examine the pore structure of the samples scanning electron microscope (SEM) was used. Also tests were carried out in a mercury porosimeter to verify the average size of the pores and real density of the samples. In the second stage, samples of the effluent were collected from a local industry, whose name will be preserved, located in Igapó, in the State of Rio Grande do Norte - RN. The effluent was first pretreated before filtration and then subjected to a treatment of flotation. The effluent was then characterized before and after filtration, with parameters of color, turbidity, suspended solids, pH, chemical and biochemical oxygen demand (COD and BOD). Thus, through the XRD analysis the formation of cristobalite α in all samples was observed. The best average size of pore was found to be 1.75 μm with 61.04 % apparent porosity, thus obtaining an average 97.9 % color removal and 99.8 % removal of suspended solid

Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

Utilização de nanosílica como aditivo estendedor para pastas cimentantes de baixa densidade destinadas à cimentação de poços petrolíferos

Cementing operations are conducted at different times of the well s life and they have high importance, because the functions are fundamental to keep good properties during a long life of the well, such as, maintain the mechanical stability of the well, to promote the isolation hydraulic and support the tubing. In some situations, the rocky zones have low fractures pressures and require the use of lightweight slurries to prevent the hydrostatic pressure in the formation is greater than the pressure of fracture. There are three ways to reduce the density of cement slurries: exterders water additives, microspheres and foamed slurries. The most used extender water additive is sodium bentonite, which is a clay with a good capacity of water absorption and expansion of its volume, the main disadvantage of this additive is the reduction of the strength. Currently, the use of nanoscale particles has received special attention, mainly because they get new functionalities. Following this trend, this paper aims to use a colloidal solution of nano-silica as an exterders water additives for use in oil wells. Slurries were designed with fixed 13lb/gal density and concentration of nano silica 0.1 gpc; 0.4 gpc; 0.7 and 1gpc, the influence of nano-silica was studied at these levels in isolation and combined varying concentrations of CaCl2,. Tests including rheology, stability, strength, thickening time, porosity and permeability. Besides the API tests, microstructural characterizations were performed after 28 days of the slurries, X-ray diffraction (XRD) and scanning electron microscopy (SEM)