Effect of amino-capped aniline trimer on corrosion protection and physical properties for electroactive epoxy thermosets

A series of electroactive epoxy thermosets (EETs) containing conjugated segments of electroactive amino-capped aniline trimer (ACAT) unit were successfully prepared and characterized. Furthermore, the redox behavior of as-prepared EET materials was identified by the electrochemical cyclic voltammetry studies. Higher concentration of ACAT component in as-prepare corresponding EETs was found to lead to an remarkably enhanced corrosion protection effect on cold-rolled steel (CRS) electrode based on sequential electrochemical corrosion measurements in 5 wt% NaCl supporting electrolyte. Mechanism for the enhancement of corrosion protection of EET coatings on CRS electrode might be attributed to the redox catalytic capabilities of ACAT units existed in EETs, leading to the formation of passive metal oxide layers, as further evidenced by SEM and ESCA studies. Effect of material composition on thermal stability and mechanical strength of EETs were also investigated by TGA, DSC and DMA, respectively.     

Advanced anticorrosive coatings prepared from electroactive polyimide-TiO2 hybrid nanocomposite materials

In this study, we present the first preparation and corrosion protection studies of a series of electroactive polyimide-TiO₂ (EPTs) hybrid nanocomposite materials containing conjugated segments of electroactive amino-capped aniline trimer (ATs) and TiO₂ nanoparticles of ∼10 nm in diameter. Redox behavior of as-prepared EPTs hybrid materials was identified by electrochemical cyclic voltammetry (CV) studies. Higher concentration of TiO₂ component in as-prepare corresponding EPTs was found to reveal better corrosion protection effect on cold-rolled steel (CRS) electrode based on sequential electrochemical corrosion measurements in 5 wt.% NaCl electrolyte. Enhancement of corrosion protection of EPTs coatings on CRS electrode could be interpreted by following three possible reasons: (1) Electroactive polyimide (EPI) could act as a physical barrier coating. (2) The redox catalytic capabilities of ATs units existed in EPTs may induce the formation of passive metal oxide layers on CRS electrode. (3) The well-dispersed TiO₂ nanoparticles in EPTs matrix could act as effective hinder to enhance the oxygen barrier property of EPTs.     

Synthesis and anticorrosive properties of electroactive polyimide/SiO2 composites

In this study, a series of electroactive polyimide/SiO₂ (EPIS) composite materials containing conjugated segments of electroactive amino‐capped aniline trimer (AT) unit were successfully prepared. First of all, the amino‐modified silica (AMS) particles of ∼100 nm in diameter were synthesized by performing the conventional base‐catalyzed sol–gel reactions. Subsequently, the AMS nanoparticles were blending into the polymerization reactions between AT and 4,4′‐(4,4′‐isopropylidenediphenoxy)‐bis(phthalic anhydride), leading to the formation of EPIS composites. The as‐prepared EPIS materials in the form of coating on cold‐rolled steel (CRS) electrode were found to be much superior in corrosion protection over those of non‐electroactive polyimide and EPI materials based on a series of electrochemical corrosion measurements in saline. The significant enhancement in corrosion protection of EPIS coatings on CRS electrodes might probably be attributed to the redox catalytic property of organic EPI inducing the formation of passive metal oxide layer and the barrier property of well‐dispersed AMS nanoparticles existed in EPI matrix. POLYM. COMPOS., 35:617–625, 2014. © 2013 Society of Plastics Engineers     

Advanced anticorrosive materials prepared from amine-capped aniline trimer-based electroactive polyimide-clay nanocomposite materials with synergistic effects of redox catalytic capability and gas barrier properties

In this study, preparation and electrochemical corrosion protection studies of a series of polyimide-Clay nanocomposite (PCN) materials were first presented. Subsequently, the as-prepared PCN materials were characterized by FTIR, XRD and TEM studies. In-situ monitoring for redox behavior of as-prepared PCN materials was identified by UV-visible and CV studies.It should be noted that PCN coating was found to reveal advanced corrosion protection effect on cold-rolled steel (CRS) electrode as compared to that of neat non-electroactive polyimide coating based on series of electrochemical corrosion measurements in 5 wt% NaCl electrolyte. Enhancement of corrosion protection of PCN coatings on CRS electrode may be interpreted by following two possible reasons: (1) redox catalytic capabilities (i.e., electroactivity) of ACAT units existed in electroactive PCN may induce formation of passive metal oxide layers on CRS electrode, as evidenced by SEM and ESCA studies. (2) well-dispersed layered organophilic clay platelets embedded in electroactive PCN matrix could functioned as hinder with high aspect ratio to effectively enhance the oxygen barrier property of PCN, as evidenced by GPA.     

Electrochemical studies on aniline-pentamer-based electroactive polyimide coating: Corrosion protection and electrochromic properties

In this study, electrochemical investigations of corrosion protection and the electrochromic properties of an aniline-pentamer-based electroactive polyimide (AP-based EPI) coating prepared by oxidative coupling polymerization are presented. The in situ chemical oxidation of the reduced form of soluble, electroactive poly(amic acid) (EPAA) in N-methyl-2-pyrrolidone (NMP) was monitored by UV–Vis absorption spectra. Moreover, the electroactivity of the AP-based EPI was evaluated by performing electrochemical CV studies. Based on a series of electrochemical measurements in 3.5 wt% NaCl electrolyte, the AP-based EPI coating was found to exhibit enhanced corrosion protection effects on cold-rolled steel (CRS) electrodes as compared to the corresponding non-electroactive (NEPI) coating. A possible mechanism for the enhanced corrosion protection of EPI coatings on the CRS electrode has been proposed as follows: (1) EPI coatings may act as a physical barrier and (2) the redox catalytic properties of the aniline pentamer units in EPI may induce the formation of a passive metal oxide layer on the CRS electrode, as evidenced by SEM and ESCA studies. The electrochromic performance of EPI was investigated by measuring electrochromic photographs and UV absorption spectra.     

Comparatively electrochemical studies at different operational temperatures for the effect of nanoclay platelets on the anticorrosion efficiency of DBSA-doped polyaniline/Na-MMT clay nanocomposite coatings

In this paper, DBSA-doped polyaniline (PANI)/Na⁺-montmorillonite (MMT) clay nanocomposite (PCN) materials have been successfully prepared with dodecylbenzenesulfonic acid (DBSA) as emulsifier and dopant for the emulsion polymerization of aniline. The as-prepared DBSA-doped samples were subsequently characterized by FTIR spectroscopy, WAXRD patterns and TEM. It should be noted that the nanocomposite coating containing 1 wt.% of clay loading was found to exhibit an observable enhanced corrosion protection on cold-rolled steel (CRS) electrode at higher operational temperature of 50 °C, which was even better than that of uncoated and electrode-coated with PANI alone at room temperature of 30 °C based on the electrochemical parameter evaluations (e.g., E_corr, R_p, I_corr, R_corr and impedance). In this work, all electrochemical measurements were performed at a double-wall jacketed cell, covered with a glass plate, through which water was circulated from a thermostat to maintain a constant operational temperature of 30, 40 and 50 ± 0.5 °C. Moreover, a series of electrochemical parameters shown in Tafel, Nyquist and Bode plots were all used to evaluate PCN coatings at three different operational temperatures in 5 wt.% aqueous NaCl electrolyte. Effect of material composition on the molecular weight and optical properties of neat PANI and PCN materials, in the form of solution, were studied by gel permeation chromatography (GPC) and UV-vis spectra, respectively. Finally, electrical conductivity at three different operational temperatures of PANI and PCN powder-pressed pellets doped with different inorganic acids such as HCl, HNO₃ and H₂SO₄ was also investigated through the measurements of standard four-point-probe technique.     

Evaluating protection performance of zinc rich epoxy paints modified with polyaniline and polyaniline-clay nanocomposite

Cloisite 30B nano clay was delaminated in the presence of aniline monomers using supercritical CO₂ (ScCO₂) process. Rapid mixing polymerization of aniline monomers was done in supercritical CO₂ to produce exfoliated polyaniline clay (PAniC) nanocomposites with high barrier properties. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and XRD analysis have been used to characterize morphology and structure of the synthesized products. The synthesized products were added to a commercial zinc rich epoxy primer to improve its initial barrier properties. Barrier properties of unmodified and modified primers were then studied by determining water vapour transmission (WVT) rate of their free films, free corrosion potential (E_corr) and electrochemical impedance spectroscopy (EIS) measurements of carbon steel coated panels. Results showed that samples modified with PAniC nanocomposites had better barrier properties compared to PAni modified and original primers. The coating resistance of PAniC modified primer was at least one order of magnitude higher than other primers at the begining of immersion. After one year of immersion, the coating resistance of original, PAni modified and PAniC modified primers were found to be 267, 1610 and 5540 ohm, respectively.     

Amino‐capped aniline trimer/epoxy resin intercrosslinked networks

An amino‐capped aniline trimer (ACAT) in emeraldine base form was reacted with an epoxy resin to produce intercrosslinked networks. The quinoid structure of the ACAT was able to crosslink on curing and, thus, led to a very high glass‐transition temperature of the cured resin. The epoxy resin cured with the ACAT showed superior thermal properties over the resins cured with p‐phenylenediamine and 4,4′‐diamino diphenylamine. These findings were based on differential scanning calorimetry, IR, dynamic mechanical analysis, and thermogravimetric analysis data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 222–226, 2006     

Polyaniline/silver nanocomposites synthesized via UV–Vis‐assisted aniline polymerization with a reversed micellar microemulsion system

Polyaniline (PANI)/silver (Ag) nanocomposites were successfully synthesized within a sodium dodecyl sulfate reverse micro‐emulsion system and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, ultraviolet spectrometry, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and electrochemical methods. The results show that the core‐shell nanoparticles of less than 100 nm may be synthesized with PANI as shell formed around a core of nanoparticle. PANI/Ag nanocomposite prepared by this method has better thermal stability, higher conductivity, and electrochemical performance. The maximum conductivity (95.5 S/cm) was obtained when W₀ (water‐oil ratio) is 22. Cyclic voltammograms results show that PANI/Ag prepared by this method has a high response current and large capacitance. Polarization results show that E_corr (174.1 mV) and I_corr (50.6 μA/cm²) are better than the results for PANI and for PANI/Ag prepared by micro‐emulsion method. PANI/Ag nanocomposites prepared by the current method have potential applications in electrode materials, capacitors, conductive adhesives, and anticorrosion materials. POLYM. COMPOS. 37:1064–1071, 2016. © 2014 Society of Plastics Engineers     

Advanced antistatic/anticorrosion coatings prepared from polystyrene composites incorporating dodecylbenzenesulfonic acid‐doped SiO2@polyaniline core–shell microspheres

We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)‐doped SiO₂@polyaniline (SP) core–shell microspheres. First, aniline‐anchored SiO₂ (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base‐catalyzed sol–gel process with tetraethyl orthosilicate in the presence of N‐[3‐(trimethoxysilyl)propyl]aniline. SP core–shell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as‐prepared core–shell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as‐synthesized DBSA‐doped SP core–shell microspheres were then blended into PS using N‐methyl‐2‐pyrrolidone as solvent and then cast onto a cold–rolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 µm. The corrosion protection efficiency of the as‐prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as‐synthesized core–shell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP core–shell microspheres showed an electrical resistance of about 3.65 × 10⁹Ω cm^?2, which meets the requirements for antistatic applications. Copyright © 2012 Society of Chemical Industry     

Highly transparent and organosoluble polyimides derived from 2,2′‐disubstituted‐4,4′‐oxydianilines

Polypyrrole (PPy) and Polypyrrole‐ZnO (PPy‐ZnO) nanocomposites were electrodeposited on mild steel and its corrosion protection ability was studied by Tafel and Impedance techniques in 3.5% NaCl solution. Pure Polypyrrole film was not found to protect the mild steel perfectly but the coating with nano‐sized ZnO (PPy‐ZnO) has dramatically increased the corrosion resistance of mild steel. Electrochemical Impedance Spectroscopy (EIS) measurements indicated that the coating resistance (R_coat) and corrosion resistance (R_corr) values for the PPy‐ZnO nanocomposite coating was much higher than that of pure PPy coated electrode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electroactive PI sphere generated by electrospraying

In this study, electroactive polyimide microspheres (EPSs) based on conjugating segments of electroactive aminocapped aniline trimer as diamine and 4,4′‐(4,4′‐isopropylidenediphenoxy)‐bis(phthalic anhydride) as dianhydride were successfully prepared by electrospraying technology and characterized by time of flight mass spectroscopy, ¹H‐NMR, Fourier transform infrared spectroscopy and cyclic voltammetry. The prepared electroactive polyimide was then dissolved in a suitable organic solvent (N,N‐dimethylformamide; N‐methyl‐2‐pyrrolidone) followed by electrospraying treatment under four different operational parameters (i.e. solution concentration, applied voltage, feeding rate and deposition distance) to give EPSs of various diameters. Moreover, EPSs deposited on the Pt electrode were tested in a 1.0 mol L^?1 H₂SO₄ aqueous solution by cyclic voltammetry which showed an obvious redox peak similar to polyaniline. Copyright © 2011 Society of Chemical Industry     

Photoisomerization of electroactive polyimide/multiwalled carbon nanotube composites on the effect of electrochemical sensing for ascorbic acid

We present the first investigation of photoisomerization of the azo‐based electroactive polyimide (PI)/amino‐functionalized multiwalled carbon nanotube (MWCNT) composite electrode on the effect of electrochemical sensing for ascorbic acid (AA). First, MWCNTs were grafted with 4‐aminobenzoic acid in a medium of polyphosphoric acid/phosphorous pentoxide to obtain MWCNTs functionalized with 4‐aminobenzoyl groups (AF‐MWCNTs). Subsequently, photoactive and electroactive PI/AF‐MWCNT composites (PEPACCs) were prepared by introducing pendant conjugated oligoaniline (amino‐capped aniline trimer) in the main chain and azobenzene chromophores in the side chain, in the presence of AF‐MWCNTs. Photoactive and electroactive PI (PEPI) and PEPACCs were characterized by ¹H NMR spectra, UV?visible absorption spectra, cyclic voltammetry (CV) and transmission electron microscopy. The CV study shows that the PEPACCs have higher electroactivity than PEPI. The redox and reversible photoisomerization (i.e. cis ? trans) behavior of PEPACCs was analyzed by in situ monitoring through systematic studies of CV and UV?visible spectroscopy. The light of the UV lamp was 365 nm. It should be noted that the sensor constructed from a trans‐PEPACC‐modified carbon‐paste electrode (CPE) demonstrated a higher electrocatalytic activity by 2.75‐fold and 1.12‐fold towards the oxidation of AA compared with those constructed using a PEPI‐ and cis‐PEPACC‐modified CPE, respectively. The detection limit of the trans‐PEPACC‐modified electrode was 1.73‐fold and 1.70‐fold lower than that of PEPI‐ and cis‐PEPACC‐modified CPE. Moreover, the differential pulse voltammetry data showed that the trans‐PEPACC‐modified electrode had high electrochemical sensing ability for the determination of AA, dopamine and uric acid. © 2014 Society of Chemical Industry     

Effect of surface modified WO3 nanoparticle on the epoxy coatings for the adhesive and anticorrosion properties of mild steel

The effect of introducing WO₃ (tungsten oxide) nanoparticle in the epoxy coating was analyzed by electrochemical impedance spectroscopy and scanning electrochemical microscopy (SECM) methods in 3.5% NaCl. The (3-glycidyloxypropyl)trimethoxysilane was treated with the nanoparticle for the proper dispersion and chemical interaction of nanoparticle with the epoxy resin. The introduction of WO₃ nanoparticle in the epoxy coating enhances the charge transfer resistance (R_ct) as well as the film resistance (R_f). The observation of iron dissolution and oxygen consumption was done by applying the appropriate SECM tip potential in the WO₃-modified nanocomposite coated steel. The epoxy and epoxy–WO₃ nanocomposite-coated samples were used to study the adhesion and anticorrosion properties. The analysis by SEM/EDX displayed that the enriched W was detected in the nanocomposite coating of steel. The presence of the nano level corrosion product containing W was confirmed by focused ion beam-transmission electron microscope analysis. The high corrosion protection properties of the epoxy-based nanocomposite coating was due to the complex nanoscale layer formed and chemical interactions of epoxy resin with surface-modified nanoparticle in nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48323.     

Preparation,properties, and anticorrosion application of poly(methyl methacrylate)/montmorillonite nanocomposites coating on brass via solution polymerization

The aim of this study is to improve the anticorrosive property of 7Cu3Zn brass. The methyl‐methacrylate (MMA) monomer solution, modified with fluorine radical and silicone, was used as the polymer matrix to mix with the different percentages of modified montmorillonite (MMT) loading and to exfoliate the lamellar structure of MMT on a nanometer scale during the solution polymerization process, and then form a thin nanocomposites coating on brass as a protective layer. The structural characterization was examined using Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), and transmission electron microscope (TEM). The anticorrosive property of nanocomposites was evaluated using potentiodynamics polarization and electrochemical impedance spectra. The results show that the d‐spacing of MMT was increased, and both exfoliation and intercalation microstructure were observed. Moreover, with the MMT loading increase, the appearance of the intercalation microstructure was more remarkable as a result of silicate layers aggregation. The 1.0 wt %‐coated brass coupons presented the optimistic property of anticorrosion, whose oxygen permeability, corrosion current (i_corr), polarization resistance (R_p), and corrosion rate (R_corr) were 3.5 g/(m²°h), 6.86 nA/cm², 5.81 × 10⁵ Ω°cm², and 0.103 × 10^?3 mm/year, respectively. These results indicate that nanocomposites have potential for anticorrosion application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4135–4143, 2007     

Oxidative dissolution of pyrite in acidic media

The pyrite oxidative dissolution in air-saturated (AS), H₂O₂, and Fe³⁺ solutions at pH 2.5 and 25 °C was investigated by electrochemical and aqueous batch experiments. The corrosion current density (i _corr) increases from AS solution to Fe³⁺ and H₂O₂ solutions. For the same oxidant, i _corr increases when the concentration of the oxidant increases. Similar variation was observed for the corrosion potential (E _corr). Electrochemical impedance spectroscopy measurements have indicated that in AS and H₂O₂ solutions, the charge transfer is the rate determining step of pyrite oxidative dissolution. In the presence of Fe _(aq) ³⁺ , both the charge transfer process and mass transfer caused by the diffusion of oxidant or reaction products across the interface of electrode control the mineral oxidative dissolution. The corrosion current densities of oxidative dissolution measured by electrochemical methods are higher than those estimated from dissolution rates determined by aqueous bath experiments. The observed differences suggest that the mechanism of polarized electrode oxidation is different by the mechanism of pyrite oxidation under open circuit conditions.     

Electrochemical and XPS investigations of cobalt in KOH solutions

The electrochemical behaviour of cobalt in KOH solutions of different concentrations was studied. The effects of applied potential, temperature and the presence of aggressive Cl^– ions were investigated. Different electrochemical methods such as open-circuit potential measurements, polarisation techniques and electrochemical impedance spectroscopy (EIS) were used. The electrochemical behaviour of cobalt in naturally aerated KOH solutions is characterized by three different regions according to the alkali concentration. Corrosion behaviour was observed at high concentrations (0.3–1.0 M); passivation at lower concentrations (0.01–0.05 M), and at intermediate concentrations (0.1–0.2 M) corrosion followed by passivation was recorded. The corrosion parameters (i _corr, E _corr, and R _corr) under various conditions were calculated. Equivalent-circuit models for the electrode–electrolyte interface under different conditions were proposed. The experimental impedance data were fitted to theoretical data according to the proposed models. The relevance of the proposed models to the corrosion–passivation phenomena occurring at the electrode–solution interface was discussed. The electrochemical experimental results and discussions were supported by surface analytical techniques.     

Fabrication of a flower-like Cu(OH)2 nanoarchitecture and its composite with CNTs for use as a supercapacitor electrode

Fabrication of nanostructured electro-active materials with an ordered organization improved the overall performance of supercapacitor devices (SCDs). In this spirit, we developed Cu(OH)₂ nano-flakes that were statistically ordered to resemble flowers. To increase the specific capacitance and kinetics of the electroactive sample, we employed ultra-sonication to fabricate a Cu(OH)₂ nanocomposite with conductive and capacitive carbon nanotubes (CNTs). The textural and functional group analyses of the wet-chemically produced samples were completed using the XRD and FTIR techniques. I–V, FESEM, and EDX measurements Analyses of pure Cu(OH)₂ and its CNT-based nanocomposites were conducted to evaluate the materials' electrical conductivity, morphology, and chemistry, respectively. The electrochemical characteristics of the as-prepared material's electrodes were investigated, and the CNT-based nanocomposite electrode demonstrated an outstanding specific capacity (Csp) and a promising rate of performance. Our CNT-based nanocomposite had a Cs of 733 Fg^-1 at 1 Ag^-1 and dropped 8.7% after 4 × 10³ cycles. The higher electrochemical properties of the nanocomposite are governed by the nano-flakes-like architecture of the Cu (OH)₂ and the more conductive CNT matrix. According to the obtained findings, our manufactured Cu(OH)₂/CNT based electrode has great promise for practical applications in next-generation supercapacitor, which are known to be very efficient.     

Electrochemical behaviour of copper in neutral aerated chloride solution. I. Steady-state investigation

The electrochemical behaviour of a Cu rotating disc electrode in neutral aerated NaCl solution was investigated in the cathodic and anodic ranges and at the corrosion potential. In the cathodic range, where the reduction of oxygen takes place, reduction peaks allow the identification and quantitative evaluation of insoluble corrosion products (CuCl and Cu₂O). In the anodic range Cu is dissolved, most likely as CuCl ₂ ^– . A new mechanism for the anodic dissolution is proposed after comparing our data with previously published mechanisms. Corrosion currents were found to decrease with time and to be a function of the rotation rate of the electrode. Both the mixed kinetics of the anodic partial reaction and diffusion through a porous layer seem to be relevant in controllingl _corr.     

Influence of H+ and Cl− ions on inhibitive performance of poly(aniline) for iron corrosion in acid

The inhibition effect of poly(aniline) on pure iron corrosion in 1M HCl and with various H⁺ ions and Cl^? ions concentrations was investigated by the polarization and electrochemical impedance spectroscopy methods. The results showed that poly(aniline) suppressed both cathodic and anodic processes of iron dissolution in 1M HCl by its adsorption on the iron surface according to Langmuir's adsorption isotherm. The inhibition efficiency of poly(aniline) was found to increase with the inhibitor concentrations. Further, it was observed that, there was no significant variation in corrosion potential (E_corr) values in the presence of inhibitors suggesting that, this polymer behaved as mixed type inhibitor. Similar studies for the inhibitor at 500 ppm in various concentrations of H⁺ and Cl^? ions, have shown that the inhibition efficiency decreases with decrease in concentrations of H⁺ ions and Cl^? ions in aqueous solution. It reveals that, the adsorption of inhibitor on iron surface is by more cationic form of inhibitor and higher efficiency at higher H⁺ and Cl^? ions is due to enhanced adsorption of cat ionic form of inhibitor molecules. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007