The mechanism of the oxidative polymerization of aniline and the formation of supramolecular polyaniline structures

Polyaniline is one of the most important conducting and responsive polymers. A molecular mechanism for the oxidation of aniline is proposed. This mechanism explains the specific features of aniline oligomerization and polymerization in various acidity ranges. The formation of polyaniline precipitates, colloids and thin films is reviewed and discussed on the basis of the chemistry of aniline oxidation. The generation of nanostructures, i.e. granules, nanotubes, nanowires and microspheres, is also considered. Oligomers containing phenazine constitutional units play an important role in self‐assembly to form templates. Polyaniline chains then grow from these templates and produce the various individual morphologies. Copyright © 2008 Society of Chemical Industry     

Exhaust hood for steam turbines-single-flow arrangement

In the past, increased attention was given to the development of an optimal shape for the inlet part of LP turbine casings in SKODA POWER. A double-flow design is typically used for high power output turbines. An optimized shape for the internal diffuser has been found, which transforms the kinetic energy of steam into increased pressure, thus effectively increasing the thermodynamic efficiency of the stage. Some conclusions have been drawn from laboratory experiments, others derived directly from on-site measurements at power plants. The conclusions from the development of double-flow turbines form the basis for the design of the single-flow turbine arrangement. Single-flow design is typically used for lower output turbines. There are still some limitations in applying this arrangement. The designer needs to resolve the bearing position and how to ensure access to them. Reinforcing the ribs and supports are used, therefore, to ensure the rigidity of the entire casing. The optimization of the single-flow diffuser shape is therefore the subject of the study presented below.     

Control of polyaniline conductivity and contact angles by partial protonation

Many studies require a specific value of conductivity when investigating conducting polymers. The conductivity of polyaniline can efficiently be controlled by partial protonation of the polyaniline base. Although this is a simple task in principle, practical guidelines are missing. In the present study, the changes in the conductivity of polyaniline base after immersion in aqueous solutions of various acids are reported. Polyaniline base has been reprotonated in aqueous solutions of picric, camphorsulfonic and phosphoric acids. The conductivity of partially reprotonated polyaniline varied between 10⁻⁹ and 10⁰ S cm⁻¹. The relation between the pH of a phosphoric acid solution, which was in equilibrium with polyaniline, and the conductivity σ is pH = 0.77 − 0.64 log(σ [S cm⁻¹]). The wettability, i.e. water contact angles, can similarly be set by partial protonation to between 78° for polyaniline base and 44° for polyaniline reprotonated in 1 mol L⁻¹ phosphoric acid. In solutions of picric acid, the transition from the non‐conducting to the conducting state occurs over a narrow range of acid concentrations, and the tuning of conductivity is consequently difficult. Phosphoric acid is well suited for the control of conductivity of polyaniline because of the moderate dependence of the conductivity on the acid concentration or pH. Copyright © 2007 Society of Chemical Industry     

Trace metals in Phragmites australis and Phalaris arundinacea growing in constructed and natural wetlands

Constructed wetlands with horizontal subsurface flow (HF CWs) designed for treatment of municipal sewage have been monitored extensively with respect to removal of organics, suspended solids, nitrogen, phosphorus and bacteria. However, the information on the removal of various metals and metalloids in these systems is very limited. During the period 2002-2004 aboveground and belowground biomass of Phragmites australis (common reed) and Phalaris arundinacea (reed canarygrass) were sampled in three HF CWs in the Czech Republic. Concentrations of monitored elements in both aboveground and belowground plant tissues were similar to those found in plants growing in natural stands. The concentrations were much lower as compared to those found in plants growing in wetlands receiving acid mine drainage waters, waters from smelters or highway runoff. Concentrations decrease in the order of roots>rhizomes>leaves>stems. The leaf:stem concentration ratios were quite similar for all monitored elements ranging between 1.0 and 1.9. The root:leaf concentration ratio varied widely between 1.5 (Cu) and 54 (Cr) with a mean value of 20.0. Belowground/aboveground plant tissue concentration ratios varied from 2.2 (Cu) to 32 (Cr) with the average value of 9.9.     

Polyaniline–silver composites prepared by the oxidation of aniline with silver nitrate in solutions of sulfonic acids

Aniline was oxidized with silver nitrate in aqueous solutions of sulfonic acids: camphorsulfonic, methanesulfonic, sulfamic, or toluenesulfonic acids. Polyaniline–silver composites were produced slowly in 4 weeks in good yield, except for the reaction, which took place in sulfamic acid solution, where the yield was low. Polyaniline in the emeraldine form was identified with UV–visible, FTIR, and Raman spectra. Thermogravimetric analysis was used to determine the silver content, which was close to the theoretical prediction of 68.9 wt.%. Transmission electron microscopy demonstrated the presence of silver nanoparticles of ca 50 nm average sizes as the dominating species, and hairy polyaniline nanorods having diameter 150–250 nm accompanied them. The highest conductivity of 880 S cm⁻¹ was found with the composite prepared in methanesulfonic acid solution. Its conductivity decreased with temperature increasing in the 70–315 K range, which is typical of metals such as silver. The conductivity of composites prepared in solutions of other acids was lower and increased with increasing temperature. Such dependence is typical of semiconductors, reflecting the dominating role of polyaniline in the conductivity behaviour. It is proposed that interfaces between the polyaniline matrix and dispersed silver nanoparticles play a dominating role in macroscopic level of conductivity.     

Laminated alumina/zirconia ceramic composites prepared by electrophoretic deposition

The electrophoretic deposition of alumina and zirconia powders from isopropanolic suspension in the presence of monochloroacetic acid was studied in the constant-current regime. The different levels of electric current during deposition from 250 μA to 48 mA were used. The green density of the deposit depends on the current density and then on the particle velocity during deposition, reaching values from 58% to 61% according to the electric current used. It was found that the lower the green density of the green deposit, the larger the pores. The low green density led to low final fired density and subsequently to the low Vickers hardness HV5 ranging from 2000 to 1650 depending on electric current used. Based on these findings microlaminates having various thickness ratios to achieve different residual stress levels were prepared consisting of alternating layers of alumina and zirconia.     

External egg morphology of two stored-product anobiids, Stegobium paniceum and Lasioderma serricorne (Coleoptera: Anobiidae)

The external egg morphology of two stored-product pests, Stegobium paniceum and Lasioderma serricorne, is presented herein based on optical and scanning electron microscope micrographs. The diagnostic characteristics of the eggs of the pests, including the presence or absence of a micropyle, are described and discussed. Overall, several notable differences were observed between the eggs of these species in regard to their shape, size and surface structures.     

Double O,C,O-chelated diorganotin(IV) cation

The synthesis of double O,C,O-chelated diorganotin(IV) compound L₂SnBr₂ (1), where L is 2,6-(MeOCH₂)₂C₆H₃^?, the precursor for the synthesis of Sn ← O intramolecularly coordinated organotin(IV) cations is reported. Treatment of compound 1 with SnBr₄ yielded the double O,C,O-chelated diorganotin(IV) ionic pair [L₂SnBr]⁺ [SnBr₅·THF]^? (2). Both compounds 1 and 2 were characterized by ¹H, ¹³C, ¹¹⁹Sn NMR and molecular structure of compound 2 was established by X-ray diffraction.     

Assessment of photovoltaic potential in urban areas using open-source solar radiation tools

This study presents a methodology for the assessment of photovoltaic potential in urban areas using open-source solar radiation tools and a 3-D city model implemented in a geographic information system (GIS). The solar radiation tools are represented by the r.sun solar radiation model and PVGIS estimation utility. The applicability of the methodology has been demonstrated on a selected urban area of a small city in eastern Slovakia. The relevant attributes of buildings have been mapped and implemented in a GIS database. The selected urban area consists of various urban zones characterized by different morphology and functionality. The photovoltaic potential of buildings has been assessed using the PVGIS estimation utility. The analysis has shown a high photovoltaic potential that could cover about 2/3 of current electricity consumption in the city. However, this potential exhibits large spatial and temporal variations caused by global and local factors. This study has also shown that national assessments of photovoltaic potential can be improved by extrapolation of local assessments using spatial databases of urban areas.     

Polyaniline nanotubes: conditions of formation

The courses of aniline oxidation with ammonium peroxydisulfate in aqueous solutions of strong (sulfuric) and in weak (acetic) acids, followed by temperature and acidity changes, are different. In solutions of sulfuric acid, granular polyaniline (PANI) was produced; in solutions of acetic acid, PANI nanotubes were obtained. The external diameter of the nanotubes was 100–300 nm, the internal cavity 20–100 nm, and the length extended to several micrometres. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of the acid. PANI nanotubes were also produced when aniline was oxidized in the absence of any acid. The bulk conductivity of PANI prepared in solutions of acetic acid was 0.08–0.27 S cm^?1, depending on the acid concentration. Protonated PANI prepared in sulfuric and acetic acids were deprotonated with ammonium hydroxide to obtain PANI bases and the ammonium salt of the protonating acid. FTIR spectroscopy showed the differences in the molecular structure of the PANI bases. Irrespective of whether the polymerization was performed in solutions of sulfuric or acetic acid, PANI had hydrogen sulfate counter‐ions only. The PANI morphology is thus not controlled by the nature of counter‐ions. The acidity of the reaction medium determines the protonation of monomer, oligomer and polymer species. The chemistry of aniline oxidation is likely to be affected especially by the protonation of an intermediate in the pernigraniline form. It is proposed that, in the course of aniline oxidation, pH‐dependent self‐assembly of aniline oligomers predetermines the final PANI morphology. Copyright © 2005 Society of Chemical Industry