Improvement of the anticorrosion properties of polypyrrole by zinc phosphate pigment incorporation

A commercial zinc phosphate pigment was incorporated into polypyrrole (PPy) matrix during its electrochemical synthesis in order to improve the corrosion protection of polypyrrole on AISI 1010 steel. PPy/zinc phosphate composite films were synthesised in sodium salicylate medium with high current efficiency and containing 10% by weight of zinc and 4% by weight of phosphate. The influence of stirring and concentration of the electrolyte on the degree of pigment incorporation were investigated, as well as polymerisation time and applied current density. The morphology of the films was determined by scanning electron microscopy (SEM) and the distribution of pigment in the polymeric matrix was carried out by X-ray photoelectron spectroscopy (XPS). The PPy and PPy/zinc phosphate films were submitted to salt spray corrosion test, weight loss test and to electrochemical measurements like corrosion potential with time. In all tests, the composite films showed an enhancement in its protective action in comparison with PPy films.     

Synthesis of urethane acrylate based electromagnetic interference shielding materials

In this work, a new method, consists of synthesis of urethane acrylate (UA) followed by in situ polymerization of pyrrole using cerium (IV) as an oxidant and UV‐curing of the composites, for preparing polypyrrole–UA (PPy–UA) composite films was described. It appeared that dielectric constants of the composites increased with increasing the PPy content and decreased with increasing the frequency from 10^?2 to 10⁷, indicating an interfacial Maxwell–Wagner contribution to the permittivity. An incorporation of a small amount of PPy (15% Py) to UA matrix increased their dielectric constants more than 4 × 10⁴ (41,259) at 10^?2 Hz. So, the incorporation of PPy was very effective for enhancing the dielectric properties of UA matrix. Furthermore, the significant enhancement in dielectric properties (loss tangent and dielectric constant) contributes to the improvement in electromagnetic interference shielding efficiency. Composite films were characterized using Fourier transform infrared attenuated total reflectance (FTIR‐ATR) spectrophotometer and ¹H‐NMR. It was seen that PPy is blended with the UA matrix at the molecular level through H‐bonding interactions. A linear relationship was also observed between the characteristic groups' absorbances of PPy (from FTIR‐ATR) and dielectric constant values (from dielectric spectrometer). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

Deposition of zinc–zinc phosphate composite coatings on steel by cathodic electrochemical treatment

The present work aims at the development of an energy-efficient and eco-friendly approach for the deposition of zinc phosphate coatings on steel. The study describes the possibility of preparing zinc–zinc phosphate composite coatings by cathodic electrochemical treatment using dilute phosphoric acid as an electrolyte and zinc as an anode. The methodology enables the preparation of coatings with different proportions of zinc and zinc phosphate by suitably varying the applied current density, pH, and treatment time. Adhesion of the coating on mild steel and adhesion of paint film on the phosphate coating were found to be good. The surface morphology of the coatings exhibited platelet-type features and small white crystals (agglomerated at some places) which represented zinc and zinc phosphate, respectively. An increase in current density (from 20 to 50 mA/cm²) increased the size of the zinc crystals, and coatings prepared at 40 and 50 mA/cm² resembled that of electrodeposited zinc. Since the proportions of zinc and zinc phosphate could be varied with applied current density, pH, and treatment time, it would be possible to use this methodology to prepare coatings that would offer different degrees of corrosion protection.     

Fabrication of ZnO-functionalized polypyrrole microcomposite as a protective coating to enhance anticorrosion performance of low carbon mild steel

In the present work, PPy, ZnO, and polypyrrole/zinc oxide (PPy/ZnO) microcomposites (1, 2, and 5 wt%) were prepared and their properties have been tuned for anticorrosion applications on low carbon mild steel. The synthesized products: ZnO, PPy, and composites were characterized by various sophisticated analytical techniques such as XRD, FTIR, Raman, FESEM, EDX, UV–VIS, TGA, and BET. The band frequencies observed at 480 and 588 cm⁻¹ in FTIR spectrum correspond to stretching vibrations of Zn-O and N-H bonds, respectively, broadening of the bands in the composites indicate strong interactions between ZnO and PPy matrix. The potentiodynamic polarization study of PPy and PPy/ZnO composite was carried out in 3.5% NaCl solution to investigate the corrosion resistance efficiency. PPy/1 wt% ZnO (I_corr = 190 nA) composite coating on low carbon mild steel was observed to exhibit best corrosion protection property compared to PPy (121 μA), 2 and 5 wt% ZnO (242, 295 nA) composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48319.     

Improvement of anticorrosive performance of phosphate-based alkyd paints with suitable additives

The purpose of this investigation was focused on reducing the content of zinc phosphate in anticorrosive paints by means of the incorporation of low quantities of selected soluble corrosion inhibitors. The article describes the anticorrosive behavior of alkyd paints containing reduced levels of zinc phosphate, zinc oxide, and some soluble compounds used as additives (e.g., sodium polyphosphate, sodium phosphate, and sodium benzoate). Anticorrosive solventborne alkyd paints were formulated with a zinc phosphate content of 10% by volume (v/v) with respect to the total pigment concentration. In all cases, the PVC/CPVC (pigment volume concentration/critical pigment volume concentration) ratio was 0.8. Experimental paints, applied on sandblasted SAE 1010 panels, were evaluated by accelerated tests (salt spray cabinet) and electrochemical measurements (electrochemical impedance spectroscopy, EIS). The results show that the additions of small amounts of soluble corrosion inhibitors to low content zinc phosphate paint formulations enhance their performance in a very remarkable way. Perhaps, the most outstanding feature is that the employment of soluble additives allowed the reduction of the zinc phosphate content with concomitant savings.     

Anticorrosion efficiency of zinc-filled epoxy coatings containing conducting polymers and pigments

The dependence of the corrosion-inhibiting properties of zinc-filled organic coatings on the nature of the conducting polymers and conducting pigments added and on the pigment particles’ surface coating with conducting polymer layers were investigated. The following materials were selected to examine the corrosion-inhibiting properties of the conducting polymers: polyaniline phosphate (PANI), polypyrrole (PPy), natural graphite, and carbon nanotubes. Conducting pigment combinations for application in coating materials were formulated by applying pigment volume concentrations (PVC) of 0.3%, 0.5% and 1%, which were completed with Zn dust to obtain pigment volume concentrations/critical pigment volume concentrations (PVC/CPVC) = 0.64. Such conducting pigment/zinc dust combinations represented corrosion inhibitors to be used as ingredients in protective coatings. Solvent-based 2K epoxy resin based coating materials containing the corrosion inhibitors so formulated were prepared to examine their anticorrosion properties. The pigmented coatings were subjected to laboratory corrosion tests in simulated corrosion atmospheres and to standardized mechanical resistance tests. The protective coatings so obtained exhibited a higher efficiency than coating materials containing zinc dust alone. The coating material containing carbon nanotubes at PVC = 1% and the coating material containing graphite coated with polypyrrole (C/PPy) at PVC = 0.5% emerged as the best zinc-filled coating materials with respect to their corrosion-inhibiting efficiency. Treatment with the conducting polymers had a beneficial effect on the coating materials’ mechanical properties.     

Electrical actuation of ionic hydrogels based on polyvinyl alcohol grafted with poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid‐co‐acrylonitrile) chains

Novel electrically conducting composite materials consisting of poly(pyrrole) (PPy) nanoparticles dispersed in a poly(vinyl alcohol)‐g‐poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid‐co‐acrylonitrile) hydrogels were prepared within the polymer matrix by in situ polymerization of pyrrole. The conversion yield of pyrrole into PPy particles was determined gravimetrically while structural confirmation of the synthesized polymer was sought by Fourier Transform Infrared (FTIR) and UV‐visible spectroscopy. The morphology of PPy nanoparticles containing hydrogel matrix was investigated by Scanning Electron Microscopy (SEM) analysis. Electrical conductivity of nanocomposite hydrogels of different compositions was determined by LCR meter while electroactive behavior of nanocomposite hydrogels swollen in electrolyte solutions was investigated by effective bend angle measurements. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Influence of Process Parameters on the Conductivity and Surface Morphology of Polypyrrole Films

Influence of electrochemical process parameters such as monomer and electrolyte concentrations, current density, pH of the electrolyte, and type of electrolyte have been studied during polymerization of polypyrrole (Ppy). The changes in the conductivity of synthesized Ppy film for different electrolytes were observed by chronopotentiograms recorded during the electrochemical polymerization and it was confirmed by measuring it using four probe techniques. It was found that the electrochemical process parameters have a considerable influence on the conductivity of the film. The Ppy film was synthesized on a platinum substrate by electrochemical polymerization with different electrolytes such as potassium nitrate, sodium nitrate, sulphuric acid, hydrochloric acid, potassium chloride, sodium chloride, oxalic acid, and sodium salicylate, under galvanostatic condition over a wide range of pH of the reaction medium and applied current density. The different concentration ratios of pyrrole and sodium nitrate were considered during synthesis of Ppy films. It has been observed that the polymerization potential increases with the pH and applied current density. One could synthesize Ppy film with very good surface morphology and conductivity with optimized process parameters. The characterization of synthesized Ppy film was done by electrochemical technique, electrical conductivity, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM).     

锌电解液中杂质离子的行为研究进展

在电沉积锌过程中,锌电解液中的杂质离子对电流效率、电能损耗和沉积锌的质量有很大影响.本文分别介绍了铜、钻、镍、铁、镉、铅和砷、锑、锗等杂质离子对锌电沉积过程的影响机理,综述了锌电沉积过程中杂质离子对电流效率、锌沉积层的质量和形貌等的影响的研究状况,为获得高质量的锌沉积层提供参考.     

Novel actuators based on polypyrrole/carbide-derived carbon hybrid materials

Polypyrrole (PPy) hybrid films incorporated with porous carbide-derived carbon (CDC) particles are synthesized through a novel one-step electrochemical synthesis process that provides a simple and efficient alternative for current tape-casting and inkjet printing technologies to make conducting polymer–CDC-based electroactive composites. The resulting porous, robust and electrically conductive hybrid layer was used to fabricate electroactive polymer actuators both as perpendicularly expanding actuators and as bending trilayer actuators. Raman and FTIR spectroscopy confirm successful incorporation of CDC in the PPy matrix. Cyclic voltammograms confirm slightly higher charging/discharging currents of the PPyCDC hybrid. This indicates the successful coupling of CDC in order to increase electric double-layer capacitance in the hybrid films. The maximum steady state electromechanical diametrical strain is 13% for hybrid material which is in the same order of magnitude as for PPy and 10× more than previously reported CDC films made with non-conducting polymer binders. Furthermore, the expanding actuators made from hybrid material are more efficient than non-modified PPy actuators, having doubled the amount of swelling per injected charge. This improvement is very important since the low energy efficiency is a major shortcoming for ionic electroactive polymers. The high pseudocapacitance makes these new hybrid materials also interesting for energy storage applications.     

磷酸锌微粉的合成及应用

结合制备磷酸锌微粉的研究工作概述了磷酸锌Zn3(PO4)2.nH2O微粉的合成原理、合成进展。阐明了磷酸锌用作防锈颜料应用机理、用途。提出了间接法合成磷酸锌无需粉碎,产品达到微细级标准的反应条件。     

Preparation and electrochemistry of nanostructured PPy/graphite nanosheets/rare earth ions composites for supercapacitor

Highly conductive PPy/graphite nanosheets/rare earth ions (PPy/nanoG/RE³⁺) composites were prepared via in‐situ polymerization with p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The microstructures of nanoG and PPy/nanoG/RE³⁺ were characterized by the SEM and TEM examinations. It was found that nanoG and PPy nanospheres formed the uniform composite with the PPy nanospheres embedded on the nanoG surface and/or filled between the nanoG. The effects of nanoG and RE³⁺ on the electrical conductivity and electrochemical performance of the composites were investigated. The results showed that the nanoG and RE³⁺ as the filler had effect on the conductivity and electrochemical performance of PPy/nanoG/RE³⁺ composites, which played an important role in forming a conducting network in PPy matrix. A specific capacitance of as high as 175 F/g at a current density of 1 A/g was achieved over the PPy/nanoG/Gd³⁺ composite. The capacitance of the PPy/nanoG/Gd³⁺ composite decreased only 5.1% after 800 charging/discharging cycles at a current density of 1 A/g. POLYM. ENG. SCI., 54:2731–2738, 2014. © 2013 Society of Plastics Engineers     

The effects of nickel and cobalt and their interaction with antimony on zinc electrowinning from industrial acid sulphate electrolyte

The effects of nickel and cobalt and their interaction with antimony on the electrowinning of zinc from industrial acid sulphate electrolyte were studied using X-ray diffraction, scanning electron microscopy and cyclic voltammetry. Concentrations of cobalt as high as 20 mgl^–1 had no effect on the zinc deposition current efficiency. The current efficiency decreased rapidly when the electrolyte contained >5 mgl^–1 nickel. Neither cobalt or nickel had an effect on the morphology of the 1-h zinc deposits. Nickel and cobalt caused characteristic changes in the cyclic voltammograms for zinc deposition. As a result this technique might provide a rapid means for evaluating the electrolyte prior to zinc electrowinning. The combined presence of cobalt and antimony in the zinc electrolyte was more deleterious to zinc electrowinning than was the combined presence of nickel and antimony. The presence of 0.08 mgl^–1 antimony in the electrolyte counteracted the effect of nickel both on the current efficiency for 1-h deposits and on the zinc deposition polarization curves.     

Diffusion-limited characteristics of mechanically induced currents in polypyrrole/Au-membrane composites

A mechanically induced current (MIC) in a polypyrrole/Au-coated membrane (PPy/Au-membrane) composite with various surface morphologies was investigated, and the electrolyte conditions were determined in an electrochemical cell. A MIC was induced on porous PPy/Au-membranes with a thin layer of PPy. Conversely, relatively small MICs were observed in non-highly porous films such as freestanding films and PPy/Au-membranes with thick PPy deposits. A MIC smaller by one order of magnitude was also observed in a Au-membrane without PPy. These results indicated that the MICs was due to a charging phenomenon in both the redox and the double layer capacitances. The MIC also varied with supporting electrolyte and their concentration. The MIC was strongly reduced in solutions with diluted electrolytes and with bulky cationic electrolytes, indicating that the number and the penetration speed of mobile ions limited the magnitude of the MIC. These characteristics indicated that the MIC was essentially a diffusion limited current. A two-electrode MIC cell was also configured to investigate a power generation film in a normal saline solution, which can possibly be utilized for biomedical applications.     

Comparison of the corrosion protection of mild steel by polypyrrole–phosphate and polypyrrole–tungstenate coatings

The electrodeposition of polypyrrole–phosphate (PPy–P) and polypyrrole–tungstenate (PPy–W) on mild steel (MS) were achieved in an oxalic acid medium with cyclic voltammetry techniques. Adherent and homogeneous PPy–P and PPy–W films were obtained. The corrosion behavior of mild steel with phosphate (PPy–P) and tungstenate (PPy–W) composite coatings in 3.5% NaCl solutions were investigated through a potentiodynamic polarization technique, open‐circuit potential–time curves, and electrochemical impedance spectroscopy (EIS). On the basis of a physical model for corrosion of mild steel composites, Zview (II) software was applied to the EIS to estimate the parameters of the proposed equivalent circuit. It was found that the PPy–W coatings could provide much better protection than the PPy–P and polypyrrole coatings. The effects of the phosphate and tungstenate process parameters on the morphology and structure of the passive films were investigated by scanning electron microscopy and electron dispersion X‐ray analyses. The results reveal that the PPy–P and PPy–W coated electrodes offered a noticeable enhancement in protection against corrosion processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Zinc hexacyanoferrate film as an effective protecting layer in two-step and one-step electropolymerization of pyrrole on zinc substrate

The two-step and one-step electrosynthesis processes of polypyrrole (PPy) films on the zinc substrate are described. The two-step process includes (i) the zinc surface pretreatment with hexacyanoferrate ion in the aqueous medium in order to form a zinc hexacyanoferrate (ZnHCF) film non-blocking passive layer on the surface and with the view to prevent its reactivity and (ii) electropolymerization of pyrrole on the ZnHCF|Zn-modified electrode in aqueous pyrrole solution. In this context, both the non-electrolytic and electrolytic procedures were adapted, and the effect of some experimental conditions such as supporting electrolyte, pH and temperature of the solution at the zinc surface pretreatment step as well as pyrrole concentration and electrochemical techniques at the polymerization step was investigated. By optimizing the experimental conditions in both steps, we have obtained a homogeneous and strongly adherent PPy films on the zinc substrate.The one-step process is based on the use of an aqueous medium containing Fe(CN)₆⁴⁻ and pyrrole. The ferrocyanide ion passivates the substrate by formation of ZnHCF film during the electropolymerization process of pyrrole and therefore makes it possible to obtain strongly adherent PPy films, with controlled thickness, either by cyclic voltammetry or by electrolysis at constant current or constant potential without any previously treatment of the zinc electrode surface. The polypyrrole films deposited on the zinc electrode were characterized by cyclic voltammetry and scanning electron microscopic (SEM) measurement.     

Polypyrrole as possible electrode materials for the aqueous-based rechargeable zinc batteries

Polypyrrole (PPy) thin film electrode was galvanostatically synthesized and characterized in 0.1 M HCl on graphite electrode as cathode materials for the aqueous-based rechargeable zinc batteries. The charge/discharge characteristics of PPy and zinc electrode in 0.1 M ammonium chloride and in the 0.1 M ammonium chloride with addition of 0.1 M sodium citrate were investigated. Electrochemical characteristic of possible Zn|PPy cell in chloride/citrate containing electrolyte was discussed and simulated.     

The effects of As(III) and As(V) on zinc electrowinning from industrial acid sulphate electrolyte

The effects of As(III) and As(V), with and without glue and glue+antimony additions, on the current effeciency and polarization behaviour of zinc deposition and on the morphology and preferred orientation of 1-h zinc deposits electrowon from industrial acid sulphate electrolyte have been determined. As(III) had no effect on the current efficiency and did not alter significantly either the zinc deposition polarization curve or the zinc deposit morphology and orientation. Increasing concentrations of As(V) resulted in a significant decrease in the current efficiency for zinc deposition from addition-free electrolyte and from electrolytes containing added glue and glue+antimony. As(V) also changed the zinc deposit morphology and orientation, and significantly altered the shape of the zinc deposition cyclic voltammogram.     

细乳液法制备MnO2/PPy复合材料及其电化学性能

以吡咯(Py)、高锰酸钾(KMnO₄)等为原料，撞击流-旋转填料床(IS-RPB)为乳化设备，通过细乳液法(W/O)制备了类球形花状结构的MnO₂/PPy复合材料。研究了对甲苯磺酸浓度、高锰酸钾浓度和反应时间对MnO₂/PPy复合材料比容量的影响，并对其电化学性能进行了考察。研究结果表明，细乳液法制备MnO₂/PPy复合材料适宜条件为对甲苯磺酸浓度0.84mol/L、高锰酸钾浓度0.094mol/L及反应时间3.5h。该条件下制备的MnO₂/PPy复合材料比表面积为177.1m²/g，比容量在0.5A/g时达到231.9F/g。同时，也表明MnO₂与PPy的协同作用有效提高了MnO₂/PPy的比容量和循环稳定性。