Recent developments in characterising electrodeposition of anti-corrosion coatings using the wire beam electrode method

New progresses have been made during recent years in the application of the wire beam electrode (WBE, a coupled multielectrode array) for studying electroplating of metallic coatings, for monitoring the electrodeposition of polymer coatings, and for evaluating the performance of anti-corrosion coatings. The WBE allows localized electrode processes to occur over different locations of its surface under external anodic or cathodic polarization and permits monitoring of nonuniform electrodeposition processes. Several typical experiments are presented in this paper. One sample experiment is the characterization of nonuniform electroplating of nickel coating, which was achieved by mapping the distributions of currents over a WBE surface that was under cathodic polarization. Various characteristic current distribution patterns, which indicate different electrodeposition mechanisms or low covering-power, have been observed. These patterns were found to correlate with the effects of several affecting factors such as electrolyte concentration, temperature and agitation flow. Another sample experiment is the investigation of nonuniform anodic electrodeposition of polyaniline (PANI) coatings and the understanding of their anti-corrosion performance and mechanisms. Anodic polarization currents were measured from various locations over the WBE surface in order to produce anodic polarization current maps under PANI deposition.

Voltammetric immunoassay for the detection of protein biomarkers

A strategy for a fast (ca. 20 min), specific, electrochemical immunoassay for the cardiac biomarker creatine kinase (CK) and the human cytokine interleukin 10 (IL10) has been developed in this paper. The polyaniline modified gold surface formed from electrochemical reduction of diazonium salt supplies a solid substrate to link the activated carboxylic acid groups from the antibodies, which were labelled with ferrocene. The direct electrochemistry of ferrocene allows the analysis of protein markers with good sensitivity. The creatine kinase sensor demonstrates limit of detection of 0.5 pg mL−1 in a physiological Krebs-Henseleit solution. The anti-IL10 antibody retained fluorescence activity after further coupling to ferrocene and covalent immobilization on to a gold electrode, showing a linear detection range for IL-10 from 0.001 ng mL−1 to 50 ng mL−1 in PBS. We attribute the high sensitivity to the well-controlled modified surface which results in end–on antibodies that can specifically capture the antigen with ease.

Strain-responsive polyurethane/PEDOT:PSS elastomeric composite fibers with high electrical conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain-sensing applications. The preparation of homogenous composite formulations from polyurethane (PU) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet-spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re-arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented. Conducting elastomeric fibers based on a composite of polyurethane (PU) and PEDOT:PSS, produced by a wet-spinning method, have high electrical conductivity and stretchability. These fibers can sense large strains by changes in resistance. The PU/PEDOT:PSS fiber is optimized to achieve the best strain sensing. PU/PEDOT:PSS fibers can be produced on a large scale and integrated into conventional textiles by weaving or knitting. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gamma-irradiated carbon nanotube yarn as substrate for high-performance fiber supercapacitors

As an electrical double layer capacitor, dry-spun carbon nanotube yarn possesses relatively low specific capacitance. This can be significantly increased as a result of the pseudocapacitance of functional groups on the carbon nanotubes developed by oxidation using a gamma irradiation treatment in the presence of air. When coated with high-performance polyaniline nanowires, the gamma-irradiated carbon nanotube yarn acts as a high-strength reinforcement and a high-efficiency current collector in two-ply yarn supercapacitors for transporting charges generated along the long electrodes. The resulting supercapacitors demonstrate excellent electrochemical performance, cycle stability, and resistance to folding-unfolding that are required in wearable electronic textiles.

Core-spun carbon nanotube yarn supercapacitors for wearable electronic textiles

Linear (fiber or yarn) supercapacitors have demonstrated remarkable cyclic electrochemical performance as power source for wearable electronic textiles. The challenges are, first, to scale up the linear supercapacitors to a length that is suitable for textile manufacturing while their electrochemical performance is maintained or preferably further improved and, second, to develop practical, continuous production technology for these linear supercapacitors. Here, we present a core/sheath structured carbon nanotube yarn architecture and a method for one-step continuous spinning of the core/sheath yarn that can be made into long linear supercapacitors. In the core/sheath structured yarn, the carbon nanotubes form a thin surface layer around a highly conductive metal filament core, which serves as current collector so that charges produced on the active materials along the length of the supercapacitor are transported efficiently, resulting in significant improvement in electrochemical performance and scale up of the supercapacitor length. The long, strong, and flexible threadlike supercapacitor is suitable for production of large-size fabrics for wearable electronic applications.

Self-assembled multimicellar vesicles via complexation of a rigid conjugated polymer with an amphiphilic block copolymer

A viable method of encapsulating block copolymer micelles inside vesicles using a conjugated polymer is reported in this study. Self-assembly and complexation between an amphiphilic block copolymer poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) and a rod-like conjugated polymer polyaniline (PANI) in aqueous solution were studied using transmission electron microscopy, atomic force microscopy and dynamic light scattering. The complexation and morphology transformation were driven by electrostatic interaction between PANI and the PAA block of the block copolymer. Addition of PANI to PMMA-b-PAA induced the morphology transformation from micelles to irregular vesicles through vesicles, thick-walled vesicles (TWVs) and multimicellar vesicles (MMVs). Among the observed morphologies, MMVs were observed for the first time. Morphology transformation was studied as a function of aniline/acrylic acid molar ratio ([ANI]/[AA]). Micelles were observed for the pure block copolymer, while vesicles and TWVs were observed at [ANI]/[AA] = 0.1 and 0.3, respectively. MMVs were observed at [ANI]/[AA] = 0.5 and irregular vesicles were observed for molar ratios at 0.7 and above. Clearly, a conjugated polymer like polyaniline can induce a morphology transformation even at its lower concentrations and produce complex morphologies.

Large compound vesicles from amphiphilic block copolymer/rigid-rod conjugated polymer complexes

Morphology evolution in complexes of amphiphilic block copolymers poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) and poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) in the presence of polyaniline (PANI) in aqueous solution is reported. Transmission electron microscopy, atomic force microscopy, and dynamic light scattering techniques were used to study the morphologies at various PANI contents [aniline]/[acrylic acid] ([ANI]/[AA]) ranging from 0.1 to 0.7. The interpolyelectrolyte complex formed between PAA and PANI plays a key role in the morphology transformation. Spherical micelles formed from pure block copolymers were transformed into large compound vesicles upon increasing PANI concentration due to internal block copolymer segregation. In addition to varying PANI content, the kinetic pathway of nanoparticle formation was controlled through different water addition methods and was critical in the formation of multigeometry nanoparticles.

Development of high performance materials based on smart elastomer nanocomposites

 The present thesis explores the fabrication of technologically relevant nanocomposites out of a few elastomers and conducting fillers like carbon nanotubes, graphene and polyaniline. The developed materials have good applications in sensors, shape memory devices and capacitors. Different characterization methods reveal the influence of filler-elastomer interactions on the various properties of the obtained nanocomposites as well.

Synthesis and self-assembly of block copolymer/conjugated polymer complexes

 This thesis describes the procedure for preparing polymer nanoparticles of various morphologies via simple complexation technique. The nanoparticles observed in this study may find potential application in drug delivery, diagnostic imaging, nano reactors, catalysis and preparation of stimuli responsive materials.

Dispositivos flexíveis de monitoramento de pH e de deflexão mecânica à base de polianilina

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Analysis of the Al-PANI interfaces by complex impedance spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dielectric behavior of PVDF/POMA blends that have a low doped POMA content

The real (epsilon') and imaginary (epsilon) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o-methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA-TSA were determined in the frequency interval between 10(2) and 3 X 10(6) Hz and in the temperature range from -120 up to 120degreesC. It was observed that the values of epsilon' and epsilon had a greater increase with the POMA-TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA-TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell-Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA-TSA in the blends. A strong decrease was observed in POMA-TSA conductivity in the blend, which was bigger the lower the POMA-TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. (C) 2002 Wiley Periodicals, Inc.

A new route to obtain PVDF/PANI conducting blends

Electrically conductive poly(vinylidene fluoride)(PVDF) - polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF) and studied by electrical conductivity measurement, UV-Vis-NIR and FTIR spectroscopy. The samples were obtained as flexible films by pressing the powder at 180 degrees C for 5 min. The electrical conductivity showed a great dependence on the syntheses parameters. The higher value of the electrical conductivity was obtained for the oxidant/aniline molar ratio equal to 1 and p-toluenesulfonic acid-TSA/aniline ratio between 3 and 6. UV-Vis-NIR and FTIR spectra of the blend are similar to the doped PANI, indicating that the PANI is responsible for the high electrical conductivity of the blend. The electrical conductivity of blend proved to be stable as a function of temperature decreasing about one order at temperature of 100 degrees C. The route used to obtain the polymer blend showed to be a suitable alternative in order to obtain PVDF/PANI-TSA blends with high electrical conductivity. (c) 2006 Elsevier Ltd. All rights reserved.