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 study of the polymerization of intercalated anilinium ions in different montmorillonite clays

The polymerization of the intercalated aniline ions was studied in three different clays, Swy2-montmorillonite (MMT), synthetic mica-montmorillonite (Synl) and pillarized Swy2-montmorillonite (PILC). PANI is formed between the MMT and Syn1 clay layers, being confirmed by the shift of d(001) peak in the X-ray pattern. X-ray Absorption near to Si K edge (Si K XANES) data show that the structures of clays are preserved after the polymerization process and in addition to the SEM images show that morphologies of the clays are maintained after polymerization, indicating no polymerization in their external surface. UV-vis-NIR and resonance Raman data display that the PANI formed in Syn1 galleries has higher amount of phenazinic rings than observed for PANI intercalated in montmorillonite (MMT) clay. No polymer formation was detected in the PILC. N K XANES and EPR spectroscopies show the presence of azo and radical nitrogen in intercalated PAN! chains. Hence, the results are rationalized considering the structural differences between the clays for understanding the role of the anilinium polymerization within the clays galleries. (C) 2011 Elsevier B.V. All rights reserved.

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Ni catalysts with Mo promoter for methane steam reforming

NiO/Al(2)O(3) catalyst precursors were prepared by simultaneous precipitation, in a Ni:Al molar ratio of 3:1, promoted with Mo oxide (0.05, 0.5, 1.0 and 2.0 wt%). The solids were characterized by adsorption of N(2), XRD, TPR, Raman spectroscopy and XPS, then activated by H(2) reduction and tested for the catalytic activity in methane steam reforming. The characterization results showed the presence of NiO and Ni(2)AlO(4) in the bulk and Ni(2)AlO(4) and/or Ni(2)O(3) and MoO(4)(-2) at the surface of the samples. In the catalytic tests, high stability was observed with a reaction feed of 4:1 steam/methane. However, at a steam/methane ratio of 2: 1, only the catalyst with 0.05% Mo remained stable throughout the 500 min of the test. The addition of Mo to Ni catalysts may have a synergistic effect, probably as a result of electron transfer from the molybdenum to the nickel, increasing the electron density of the catalytic site and hence the catalytic activity. (C) 2009 Elsevier Ltd. All rights reserved.

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Modificação superficial do tecido 100% algodão tratado com plasma

The 100% cotton fabric (CO)* treated with plasma of methane CH4 has direct application in all areas that needs of aqueous solutions repellent material like coatings and uniforms applied biomedical, aeronautics, and automobile between others. 100% cotton fabric (CO) samples were treated by plasma with two differents atmosphere: Methane gas (CH4), treatment time was varied in 10 in 10 min. until 60 min., and mixture methane/argon (CH4/Ar), it was varied the proportion 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 e 9:1, with treatment time of 30 minutes. In both, the fluxe was 5 sccm (second cubic centimeter), pressure 6 mbar, voltage 490 V and current 0,15A. The objective of work was measure the superficial tension of 100% CO then it treated with plasma, using contact angle measures of water and glycerol with the surface. The samples were tested after treatment, with 8 and 12 months to verify the superficial modification effects. It was verified an increase of hydrophobility with the Sessile drop values varied between 116,69º to 137,85º and it carried on after 12 months. The no treated samples shows contact angle equal 0º. OES analysis and Raman spectroscopy were accomplished. In the SEM analysis was verified oligomers. The plasma treatment is correct environmental, It turning greater than conventional treatments

Langmuir and Langmuir-Blodgett films of poly[2-methoxy-5-(n-hexyloxy)-p-phenylenevinylene]

Langmuir films have been fabricated from poly[(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene] (OC1OC6-PPV). The stability and the area per monomer for condensed films indicate the formation of true monolayers with a very small extent of aggregation, which is unusual for polymer films. This is attributed to the linearity of the alkyl side chain. The Y-type Langmuir-Blodgett (LB) films produced from Langmuir films of OC1OC6-PPV have distinctive features compared to those of cast films, probably due to the organization in the LB films whereas the molecules are randomly oriented in cast films. Infrared absorption spectra recorded for both transmission and reflection modes indicate that OC1OC6-PPV molecules are anchored to the substrate by the lateral groups. This is confirmed by the Raman spectrum, in which a distortion of the vinylene group was observed, and by surface enhanced fluorescence (SEF) on an LB monolayer deposited onto Ag nanoparticles. The more homogeneous nature of the LB films in comparison with the case of cast films was demonstrated by optical microscopy and fluorescence measurements where the emission spectra were essentially the same for different regions of an LB film but showed dispersion in cast films. The LB films also displayed reversible photoconductivity.

Vibrational spectroscopy applied to the study of archeological ceramic artifacts from Guarani culture in Brazil

An archeological artifact can be seen as a chronological element, which helps to determine the age of certain society and to understand the thinking, values and the way of life of this society. Thus, the classification of archeological artifacts is one of the approaches used to study the cultural system of antique societies trying to reconstruct their history. The "Centro de Museologia, Antropologia e Argueologia (CEMAARQ)" of the "Unesp Univ Estadual Paulista" in Presidente Prudente, São Paulo state, Brazil, develops projects within this context (identification and preservation). This is the case of the archeological site named "Lagoa São Paulo-02" discovered in 1993 at the margins of the Parana river in the region of Presidente Epitacio city, São Paulo state, Brazil. This site has ceramic fragments of different shapes and sizes that have a strong influence of traces of the Guarani culture, which is one of the Brazilian native populations. These samples were basically characterized via micro-Raman scattering and Fourier transform infrared absorption (FTIR) spectroscopies. The main objective was to identify the pigments used in the manufacture of the ceramic artifacts and to analyze the composition of the ceramic body to understand how the artifacts were made. Three pigments were found: red, black and white. For the red pigment were identified characteristic bands of hematite, an iron oxide found in the red rocks of the river banks that were eroded by water. The black pigment, probably, is due to the use of vegetal charcoal, which is found in nature as the product of burning organic material such as wood. For the white pigment, the FTIR spectra suggested the use of kaolin, either in the ceramic body or in the proper white pigment, due to the presence of the characteristic bands of the kaolinite. Complementary, the additives applied as anti-plastics were identified as charcoal and quartz, being the latter found in the rocks present in the archeological site. (C) 2010 Elsevier B.V. All rights reserved.

Effects of Etching on Zircon Grains and Its Implications for the Fission Track Method

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

Thermal inkjet printing of polyaniline on paper

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

Combining SERRS and electrochemistry to characterize sensors based on biomembrane mimetic models formed by phospholipids

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

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

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

Exploiting Distinct Molecular Architectures of Ultrathin Films Made with Iron Phthalocyanine for Sensing

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