Study of the anticorrosive properties of polypyrrole/polyaniline bilayer via electrochemical techniques

In this work, using electrochemical techniques the authors investigated the protective properties of a polypyrrole/polyaniline bilayer as a conductive polymer. A polypyrrole/polyaniline bilayer was deposited on carbon steel substrate by potentiostatic method. The electric capacitance and resistance of the films were monitored with the immersion time in a corrosive solution to investigate the water permeability of the films. Polypyrrole/polyaniline bilayer has a relatively low permeability and good catalytic behavior in passivation of carbon steel in longer periods. The results show that the bilayer has a better anticorrosive behavior compared to homopolymers (polypyrrole and polyaniline).     

Dispersion polymerization of aniline using hydroxypropylcellulose as stabilizer: role of rate of polymerization

Hydroxypropylcellulose (HPC) has been used as a steric stabilizer for preparing polyaniline dispersions using the route of oxidative dispersion polymerization of aniline. Using strongly acidic conditions (1 mol l^?1 HCl), low temperature of about 2 °C and a concentration of aniline as low as 0.5%, ammonium peroxodisulfate at 1.25% and hydroxypropylcellulose concentrations at 0.5–1 g d l^?1, unstable dispersions were obtained not only in water but also in aqueous alcohols (ethanol and methanol) up to at least 70 vol% alcohol. In contrast, dispersions that remained stable for at least 72 h were obtained when the alcohol concentration of the medium was as high as about 80 vol%. Kinetic studies of the polymerization systems suggested that success in the latter case was due to a lowering of the rate of polymerization. Transmission electron microscopy studies showed that dispersion particles prepared in 80 vol% alcohol media are spherical in shape and their diameter decreases with increasing stabilizer concentration. However, a change of morphology from spherical to aggregated needle‐shaped was observed when the rate was increased by increasing the aniline concentration from 0.5% to 0.75% g d l^?1 in the above recipe. The aggregated particles were found to be broken down to spherical nanoparticles when the as‐prepared dispersions were sonicated for about 30 min. The sonicated dispersion on drying showed the presence of fractal clusters of polyaniline particles in the dried film. The fractal dimension was determined to be 1.77 which agreed well with the theoretical value determined by computer simulation based on a diffusion limited cluster–cluster aggregation model in three dimensions. © 2001 Society of Chemical Industry     

Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

Polyaniline‐modified cellulose nanofibrils as reinforcement of a smart polyurethane

Segmented polyurethanes exhibiting shape memory properties were modified by the addition of polyaniline (PANI)‐coated cellulose nanofibrils (CNFs). The two‐phase structure of the polymer is responsible for the material's ability to ‘remember’ and autonomously recover its original shape after being deformed in response to an external thermal stimulus. PANI was grown on the surface of the CNFs via in situ polymerization. Modified nanocrystals were added to the segmented polyurethane in concentrations ranging from 0 to 15 wt%. The changes in the material properties associated with the percolation of the coated fibrils appear at higher concentrations than previously observed for non‐modified CNFs, which suggests that fibril agglomeration is occurring due to the PANI coating. The shape memory behavior of the composites is maintained at about the same level as that of the unfilled polyurethane only up to 4 wt% of fibrils. At higher concentrations, the rigidity of the nanofibrils as well as their interaction with the hard‐segment phase and the increasing difficulty of dispersing them in the polymer collaborate to produce early breakage of the specimens when stretched at temperatures above the melting point of the soft segments. Copyright © 2010 Society of Chemical Industry     

Preparation of activated rectangular polyaniline-based carbon tubes and their application in hydrogen adsorption

Porous materials, especially porous carbon materials, have the most potential as hydrogen adsorbents. In this research, a series of novel rectangular polyaniline tubes (RPTs) are synthesized using hollow carbon nanosphere (HCNS) templates. By changing mass ratios of ammonium persulfate to HCNSs, the sizes of RPTs can be controlled. Chemical activation with KOH gives rise to a large specific surface area (SSA), ranging from 1680 to 2415 m2 g⁻¹, and big pore volumes that range from 1.274 to 1.550 cm³g⁻¹. These observations demonstrate that activated rectangular polyaniline-based carbon tubes ARP-CTs are promising hydrogen adsorbents. Hydrogen uptake measurements show that the highest hydrogen adsorption reaches 5.2 wt% at 5 MPa/77 K and 0.62 wt% at 7.5 MPa/293 K respectively. Notably, the large pore volume can contribute 2.8 wt% to the total hydrogen storage which has approached 8.0 wt% at 5 MPa/77 K.     

The carbonization of colloidal polyaniline nanoparticles to nitrogen‐containing carbon analogues

The carbonization of nanostructures afforded by conducting polymers represents a new route to the preparation of functional nanostructured carbons. The exposure of colloidal polyaniline particles stabilized with poly(N‐vinylpyrrolidone) or silica nanoparticles at 650 °C in inert atmosphere led, in both cases, to nitrogen‐containing carbonaceous materials with specific surface areas of 200 and 205 m² g^?1, respectively, and conductivities of 8.3 × 10^?7 and 1.9 × 10^?10 S cm^?1, respectively. The latter material contained 77 wt% of silica. The original particulate nanostructure of the samples was preserved after carbonization. The carbon‐to‐nitrogen atomic ratio was 7.2 and 7.9; the nitrogen content in the carbonized polyaniline–poly(N‐vinylpyrrolidone) particles was 10.8 wt%. Thermogravimetric analysis in air revealed their stability to be up to 500 °C. This is comparable with commercial multi‐wall carbon nanotubes, which have similar areas of application. The nitrogen‐containing carbons are potentially useful as supports for catalysts and in applications where carbon of higher hydrophilicity would be of benefit. Copyright © 2010 Society of Chemical Industry     

Polyaniline doped with α, ω‐alkanedisulfonic acids: preparation and characterization

The use of α, ω‐alkanedisulfonic acid, HO₃S(CH₂)_nSO₃H (n = 1, 4, 6 and 12), as a dopant for polyaniline (PANi) was investigated. This series of disulfonic acids with varying chain lengths were synthesized and used in the doping of PANi. The doped polymers showed conductivity in the range 10^?2 to 10^?1 S cm^?1. Thermal studies showed that the doped polymers, depending on the chain length of α,ω‐alkanedisulfonic acid, were stable up to ca 300 °C and the thermal stability decreased with increasing dopant chain length. The thermal stability of α,ω‐alkanedisulfonic acid‐doped PANi was higher than that of alkanesulfonic acid‐doped PANi which typically degrades around 250 °C, suggesting a moderately broader processing window for α,ω‐alkanedisulfonic acid‐doped PANi for blending with other thermoplastics. Copyright © 2012 Society of Chemical Industry     

Chemical Synthesis and Characterization of Novel Antibacterial Polycyclic Polymer

Polyaniline (PAn) and poly(alkyl substituted anilines) were synthesized in aqueous media by chemical polymerization of alkyl substituted aniline in presence of ammonium peroxydisulphate as an oxidant. The products were investigated in terms of morphology, chemical structure, and mechanism of polymerization with scanning electron microscope (SEM), transmission electron microscopy (TEM), fourier transform infrared (FTIR), and UV–visible spectroscopy (UV–vis), respectively. Results indicated that physicochemical properties of poly(alkyl substituted anilines) depend on substituent groups bonded to N-position. In general, alkyl-substituted PAn have similar chemical and optical properties to parent PAn and it seems that the substituted PAn follow the same polymerization mechanism as reported for PAn. The prepared polymers were then tested for the antibacterial properties against Gram-negative bacteria: Escherichia coli (E. coli). The antibacterial properties were assessed by measuring the zones of inhibition. The antimicrobial results showed clearly that PAn and poly(alkyl substituted anilines) exhibited excellent antibacterial activity against the growth of E. coli microorganism.     

Enhancement of electrocatalytic properties of carbonized polyaniline nanoparticles upon a hydrothermal treatment in alkaline medium

The electrocatalytic activity of carbonized polyaniline nanostructures (Carb-nanoPANI) towards oxygen reduction reaction (ORR), estimated in 0.1 mol dm⁻³ KOH solution, was significantly improved upon a hydrothermal treatment in 1 mol dm⁻³ KOH solution. Namely, the onset of ORR was shifted by ∼70 mV to more positive potentials, and the number of electrons consumed per O₂ molecule was enhanced in comparison to the original material. The number of electrons involved in ORR depended on loading, and with a loading of 0.5 mg cm⁻², for the potentials lower than −0.5 V vs SCE, the number of electrons approached 4. For this material, high stability of electrochemical behavior and resistance to the poisoning by ethanol was evidenced by potentiodynamic cycling.