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.     

Optimal Sensor Networks for Area Monitoring Using Rotating and Beam Sensors

We consider the problem of monitoring the Euclidean plane using rotating sensors with detection sectors and beam sensors. We assume that intruders can appear anywhere at any time and move arbitrarily fast, and may have full knowledge of the sensor network. We require that such intruders be detected within a finite amount of time. We give an optimal network for this problem consisting of a combination of rotating sensors of angle 0 and beam sensors that uses the minimum number of both types of sensors. We show a trade-off between the density of beam sensors needed and the angle of the detection sector of the rotating sensors. Secondly, we give a family of sensor networks using only rotating sensors for the same problem, that demonstrate a trade-off between the detection time and the density of rotating sensors used. We show that the density of rotating sensors required in this case can be significantly reduced by increasing the angle of detection sectors. Finally, we show that our results on the infinite plane can be used to derive sensor networks that monitor some finite regions using a density of sensors that is asymptotically the same, or close to that of the infinite plane case.     

Regeneration of platinum-metal-based catalysts with carboxyphosphines as extractants

Separation of platinum-metal-based homogeneous catalysts was achieved by their conversion to complexes of functionalized phosphines of the general formulae R_3-n P[(CH₂) _x CO₂H)] _n , R = Me, Et, Ph,n = 1, 2, 3,x = 1, 2, and [(HO₂CCH₂)PCH₂]₂, followed by extraction of the complexes into aqueous phase. This approach to regeneration of platinum metals from reaction mixtures after carrying out homogeneously catalyzed reactions was demonstrated on 11 examples of various types of reactions with Ru, Rh, Pd, Os, Ir and Pt compounds as catalysts.     

Epoxy/poly(ɛ‐caprolactone) nanocomposites: Effect of transformations of structure on crystallization

The influence of morphology of the epoxy/poly(?‐caprolactone) (PCL) system and corresponding nanocomposites with organophilized layered silicate on PCL crystallization was studied by differential scanning calorimetry, scanning, and transmission electron microscopy. The results obtained indicate a significant affecting of nonisothermal PCL crystallization by phase morphology brought about by the reaction‐induced phase separation (RIPS) influenced either by various nanoclay contents or the epoxy/PCL ratio. Dispersed morphology of PCL matrix with epoxy globules induces crystallization at higher temperatures. The inverse dispersed morphology of epoxy matrix with PCL inclusions causes crystallization at lower temperature. The co‐continuous morphology induces crystallization in both steps. Rate of the second crystallization step is substantially higher than that in the first step. No nucleation effect has been found in the nanocomposites with the added nanofiller. Multicomponent samples show retarded crystallization, i.e., lower crystallinities and lower overall crystallization rate compared with neat PCL. The results obtained suggest that it is primarily morphological/interfacial effects that play a decisive role in the crystallization behavior of PCL in the epoxy/PCL/clay system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3197–3204, 2013     

Pyrolysis of brown coal under different process conditions

Pyrolysis tests were performed under laboratory conditions, simulating possible processes in the burning of brown coal mines. These tests focused on gaseous products of thermal decomposition of coal and how their concentrations changed depending on pyrolysis temperature. Results obtained can help to quantify the contributions of particular gases to overall explosiveness of a gaseous mixture and can explain the process of explosive gas release during conflagration.     

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.     

Physico-chemical properties of ethanol – Compilation of existing data

Physico-chemical properties of ethanol and aqueous solutions of ethanol are important for chemical engineering calculation, modelling and evaluation of processes during ethanol production and its use for food and non-food applications. The majority of these properties are possible to find in handbooks and tables as Yaws (1999): Chemical Properties Handbook; Miller and Yaws (1976): Correlation constants for liquids; Lide (2007–2008): CRC Handbook of Chemistry and Physics; Hole?ek (2007): Chemical-engineering tables; Critical Data Tables and other literature. Some of them are also accessible online. The goal of this paper is to present the formulas and developed algorithms for calculation of extended properties of ethanol collected from literature. Extended properties include density, vapor pressure, surface tension, viscosity, molar and specific heat capacity, enthalpy of vaporization, thermal conductivity and static relative permittivity (dielectric constant) of ethanol.     

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