Hyperfine interaction in Zn-Al layered double hydroxides intercalated with conducting polymers

Organic-inorganic hybrid materials based on the assembly between inorganic 2D host structure and polymer have received considerable attention in the last few years. This emerging class of materials presents several applications according to their structural and functional properties. Particularly, among others, layered double hydroxides (LDHs) provide the opportunity of preparing new organically modified 2D nanocomposites. Pyrrole carboxylic acid derivatives, namely 4-(lH-pyrrol-1-yl)benzoate, 3-(pyrrol-i-yl)-propanoate,7-(pyrrol-1-yl)-heptanoate, and aniline carboxylic acid derivative, namely 3-aminobenzoic acid, have been intercalated in LDHs of intralamellar composition Zn2Al(OH)(6). The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by powder X-ray diffraction patterns (PXRD), transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and electron spin resonance (ESR). The basal spacing found by the PXRD technique gives evidence of the formation of bilayers of the intercalated anions. ESR spectra present a typical signal with a superhyperfine structure with 6 + 1 lines (g = 2.005 +/- 0.0004), which is assigned to the interaction between a carboxylate radical from the guest molecules and a nearby aluminium nucleus (I = 5/2) from the host structure. Additionally, the ESR data suggest that the monomers are connected to each other in limited number after thermal treatment. (c) 2007 Elsevier Ltd. All rights reserved.

Simultaneous observation of the magnetic and electric behavior in a correlated system near a metal-semiconductor transition: ESR in pellets of conducting polymers

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

The ferromagnetic behaviour of conducting polymers revisited

The magnetic properties of doped pellets of poly(3-methylthiophene) showing room temperature ferromagnetic behaviour have been discussed in a previous article. The magnetic behaviour was attributed to a weak ferromagnetic phase, due to the superexchange interaction of polarons via the dopant anions. The Dzialoshinsky-Morya interaction among canted spins was proposed to explain the ferromagnetism. In this article the main conclusions of that work concerning the magnetic behaviour are revised. The basic assumption now is that the magnetic moments are spin 1/2 polarons that can interact antiferromagnetically and/or ferromagnetically. In the small crystalline regions of the polymer, which are identified with the polymer portion that remains ferromagnetic at room temperature, the interaction gives rise to S = 0 and 1 bipolarons and the S = 1 triplet state is lower in energy. In the disordered region, disorder will prevent the complete S = 1 and 0 coupling and bands of polarons ferromagnetically and antiferromagnetically coupled will appear. Using this approach, all the magnetization data can be qualitatively explained, as well as the electron spin resonance data.

Polarons, bipolarons, and crystallization in conducting polymers: An ESR study

Electron spin resonance (ESR) experiments give extremely important information concerning spin arrangements in conducting polymers. This is evidenced by the behavior of the ESR lines as a function of temperature and microwave power. Our ESR data of pressed pellets of ClO- 4 doped poly(3-methylthiophene) (P3MT) synthesized at 25 °C show the predominance of polarons. Instead, the sample prepared at 5 °C shows the predominance of bipolarons. Besides, for both types of samples, crystallization, observed from the ESR data, has shown a rearrangement of spin species.

Polaronic ferromagnetism in conducting polymers

Ferromagnetic behavior at room temperature is reported in metal-free-conducting polymer samples of poly(3-methylthiophene) doped with ClO 4 -. Magnetic moments associated with spin 1/2 positive polarons are possibly interacting through a Dzialoshinski-Moriya anisotropic superexchange via the dopant anions, giving rise to weak ferromagnetism. © 2001 Elsevier Science B.V. All rights reserved.

Studies on the interaction between humic substances and conducting polymers for sensor application

The interaction between humic substances and poly(o-ethoxyaniline) (POEA), a conducting polymer, was investigated for both solution and self-assembled films. The results have shown that the humic substances induce a doping of POEA by protonation, as indicated by UV-Vis and Raman spectroscopies. The atomic force microscopy (AFM) studies on the self-assembled films have shown that the average roughness of the polymer film has increased after exposing it to humic substances (fulvic and humic acids), consistent with the interaction between POEA and humic substances. However, this change in morphology is reversible by washing the films with water in agreement with the electrical data allowing using this system in sensor applications. Here, the sensor formed by an array of different sensing units was able to detect and distinguish humic substances in aqueous solution, as shown by multivariate analysis (principal component analysis). The motivation to detect humic substance comes due to its importance in terms of quality control of water or soil. ©2005 Sociedade Brasileira de Química.

Effect of chemical modifications on the electronic structure of poly(3-hexylthiophene)

The widespread use of poly(3-hexylthiophene) (P3HT) in the active layers of organic solar cells indicates that it possesses chemical stability and solubility suitable for such an application. However, it would be desirable to have a material that can maintain these properties but with a smaller bandgap, which would lead to more efficient energy harvesting of the solar spectrum. Fifteen P3HT derivatives were studied using the Density Functional Theory. The conclusion is that it is possible to obtain compounds with significantly smaller bandgaps and with solubility and stability similar to that of P3HT, mostly through the binding of oxygen atoms or conjugated organic groups to the thiophenic ring. © 2013 Wiley Periodicals, Inc.

Wine classification by taste sensors made from ultra-thin films and using neural networks

This paper reports on a sensor array able to distinguish tastes and used to classify red wines. The array comprises sensing units made from Langmuir-Blodgett (LB) films of conducting polymers and lipids and layer-by-layer (LBL) films from chitosan deposited onto gold interdigitated electrodes. Using impedance spectroscopy as the principle of detection, we show that distinct clusters can be identified in principal component analysis (PCA) plots for six types of red wine. Distinction can be made with regard to vintage, vineyard and brands of the red wine. Furthermore, if the data are treated with artificial neural networks (ANNs), this artificial tongue can identify wine samples stored under different conditions. This is illustrated by considering 900 wine samples, obtained with 30 measurements for each of the five bottles of the six wines, which could be recognised with 100% accuracy using the algorithms Standard Backpropagation and Backpropagation momentum in the ANNs. (C) 2003 Elsevier B.V. All rights reserved.

Asymmetrical penetration of microwave in a conducting media and determination of microwave conductivity for very thin samples using electron spin resonance

Dyson's theory of conduction electron spin resonance (CESR) has been used in the limit d less than or equal to delta (d being the thickness of the sample and delta the skin depth of the microwave field) to obtain the microwave conductivity from the (A/B) ratio of the CESR absorbed power derivative. In this work we calculate the CESR absorbed power derivative using Kaplan's approach and show that the (A/B) ratio can be enhanced if asymmetrical penetration of microwave is used, which means that the microwave field enters into the sample from one of the faces. Therefore, the determination of the microwave conductivity from the (A/B) ratio of the CESR line can be performed for thinner samples. Experimentally, asymmetrical penetration can be obtained if one of the sample's faces is covered with a thin gold layer. The determination of microwave conductivity in conducting polymers films is among the possible applications of this method. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Study of the thermomechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work describes the preparation and characterization of composite materials obtained by the combination of natural rubber (NR) and carbon black (CB) in different percentages, aiming to improve their mechanical properties, processability, and electrical conductivity, aiming future applications as transducer in pressure sensors. The composites NR/CB were characterized through optical microscopy (OM), DC conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA), and stress-strain test. The electrical conductivity varied between 10(-9) and 10 S m(-1), depending on the percentage of CB in the composite. Furthermore, a linear (and reversible) dependence of the conductivity on the applied pressure between 0 and 1.6 MPa was observed for the sample with containing 80 wt % of NR and 20% of CB. (C) 2007 Wiley Periodicals, Inc.

Soliton clusters inducing insulator-to-metal transition in polyacetylene: a Su-Schrieffer-Heeger model study

The Su-Schrieffer-Heeger (SSH) Hamiltonian has been one of most used models to study the electronic structure of polyacetylene (PA) chains. It has been reported in the literature that in the SSH framework a disordered soliton distribution can not produce a metallic regime. However, in this work (using the same SSH model and parameters) we show that this is possible. The necessary conditions for true metals (non-vanishing density of states and extended wavefunctions around the Fermi level) are obtained for soliton concentration higher than 6% through soliton segregation (clustering). These results are consistent with recent experimental data supporting disorder as an essential mechanism behind the high conductivity of conducting polymers. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Estrutura eletrônica do polímero orgânico conjugado MEH-PPV em solução sob radiação ionizante

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Síntese e caracterização elétrica de compósitos poliméricos condutores com o poliuretano derivado de óleo de mamona como matriz

Pós-graduação em Ciência dos Materiais - FEIS

Preparação e caracterização de blendas de poliuretano derivado do óleo de mamona e poli (o-metoxianilina) e sua avaliação como sensor

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)