Impact of carbon nanotube additives on carbide-derived carbon-based electroactive polymer actuators

The effects of single-walled carbon nanotubes (SWCNTs) on the properties of carbide-derived carbon (CDC)-based electroactive polymer (EAP) actuators were studied. SWCNTs were used as an additive to increase the mesoporosity and electrical conductivity of the electrodes, and also to support the CDC matrix. EAP actuators with various ratios of SWCNTs to CDC in the electrodes were fabricated and their electromechanical and electrochemical characteristics were examined. The addition of SWCNTs to CDC-based electrodes significantly increased the bending strain and stress (bending force) of the actuators. The actuator assembled with electrodes containing SWCNTs and CDC in the ratio 50/50 (wt.%/wt.%) showed the highest strain output among the samples at lower frequencies (<0.1 Hz). The increase in maximum strain was more than twice that of pure CDC-based EAPs (0.85% vs. 0.35% at an applied voltage of ±2 V). Also, the high frequency (5–50 Hz) response of the combined SWCNT/CDC-based actuators was considerably improved.     

Synthesis and characterization of polypyrrole‐platinum composite for use as electrode material

Synthesis and characterization of polypyrrole (PPy) supported platinum by a simple method is reported in this study. The porous structure of PPy and its tendency for doping with acids prompted us to utilize this property to incorporate platinum by adsorption followed by reduction on the PPy matrix. Dispersed platinum electro catalyst on the conducting PPy support provides favorable reaction site for redox reactions in electrochemical devices such as hydrox fuel cell. The mesoporous matrix of PPy as revealed by FESEM could facilitate effective contact between the reactant gases and electro catalyst. The cauliflower like structure of the PPy matrix could enhance the electrochemical active surface area of the catalyst. The composite material is characterized by cyclic voltammetry (CV), polarization study, four probe technique, density and porosity study. The CV highlights the use of PPy‐Pt hybrid as a capacitor and the Tafel plot infers on the high exchange current density of the hybrid material. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Polypyrrole/carbon nanotube composites: Molecular modeling and experimental investigation as anti-corrosive coating

In this work we present a computational method based on molecular mechanics (MM) and dynamics (MD), to predict mechanical properties of polypyrrole (PPy)/polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (CNT-PABS) and PPy/carboxylic acid-functionalized single-walled carbon nanotubes (CNT-CA) composites. Furthermore, experiments were carried out to assess the anticorrosive features of the PPy film and CNT-PABS and CNT-CA PPy reinforced composite coatings. Computational bulk models of PPy/CNT-PABS and PPy/CNT-CA were implemented at atomistic scale and composite coatings were grown in situ onto carbon steel (OL 48-50) electrodes. PPy, PPy/CNT-PABS and PPy/CNT-CA computational models and films were investigated concerning mechanical properties by using computational tools. The obtained films were assessed experimentally as anticorrosive materials using potentiodynamic measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results clearly confirmed that the CNT-PABS and CNT-CA are properly dispersed in the composite coatings and have beneficial effect on mechanical integrity. Moreover, the anticorrosion protecting ability of the composite coatings is significantly higher than the one characteristic to pure PPy. The Young's moduli generally increased with increasing of CNT content and values ranged from 2.67 GPa in the case of pure PPy to 4.15–4.61 GPa in the case of PPy/CNT-PABS composite system.In agreement with earlier results from the literature for conducting polymer organic coatings, the higher conductivity of material leads to a more efficient anticorrosion protection capability, our results exhibited an enhance of conducting features even for very low mass of CNT-PABS or CNT-CA loaded in composites coatings therefore, an improvement of anticorrosion protecting ability.     

Self‐assembled polypyrrole film by interfacial polymerization for supercapacitor applications

A facile interfacial synthesis strategy is proposed to synthesize self‐assembled polypyrrole (PPy) free‐standing films for electrochemical capacitors with the assistance of surfactants. The chemical structure of the obtained samples is characterized by Fourier transform infrared. The morphologies of the samples are studied by scanning electron microscope. The results show that the prepared PPy films own highly porous structures using Tween80 as a surfactant, while the synthesized PPy films have vesicular structures by adding Span80 as a surfactant. Furthermore, lowering polymerization temperature makes PPy films have smaller and more pores or vesicles. The PPy films prepared at 0°C with Tween80 as a surfactant possess a high specific capacitance of 261 F g^?1 at 25 mV s^?1 as well as retain 75% of the initial specific capacitance value after 1000 cycles. The good electrochemical properties can be attributed to the highly porous structural advantage of the PPy films caused by Tween80. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41615.     

Investigation by EQCM of the electrosynthesis and the properties of polypyrrole films doped with sulphate ions and/or a Keggin-type heteropolyanion, SiMo12O40

The first part of this paper describes in detail the electrochemical synthesis of polypyrrole (PPy) films monitored by electrochemical quartz crystal microbalance (EQCM). These films are either doped only with a Keggin-type heteropolyanion (HPA), SiMo₁₂O₄₀⁴⁻, or co-doped with such polyanions and sulphate ions. It is evidenced that this HPA catalyses the electropolymerisation of the pyrrole since it is able to oxide pyrrole monomer, and on the other hand, that HPAs are definitively entrapped into the polypyrrole film as shown by their electrochemical response. All the PPy film is electroactive. When the co-doped film is obtained by potentiodynamic method, its anion composition is not homogeneous in depth, there is a concentration gradient of the doping anions. In the second part of this paper, the morphology of the films is shown as well as their electrochemical characterisations that were carried out by EQCM in order to focus on the charge compensation process that occurs during SiMo₁₂ reduction and re-oxidation. In a wide domain of potentials, only the HPA response is observed, the polymer remains in its conducting form. The SiMo₁₂O₄₀⁴⁻ doped PPy films are cationic films. When several types of cations are present in the medium, the influence of the pH on the nature of the cations implied in the charge compensation that occurs during SiMo₁₂ reduction and re-oxidation is important. When the PPy film is co-doped, it is possible to obtain a mixed PPy film. Another important finding is the stability of trapped SiMo₁₂ ions in contact with solutions of pH higher than 4, on the contrary to what occurs when they are in solution.     

Electrosynthesis of pyrrole 3-carboxylic acid copolymer films and nanotubes with tunable degree of functionalization for biomedical applications

Tailoring polypyrrole (PPy), an electroactive polymer, with functional groups to which a variety of bioactive molecules can be tethered is highly attractive for building biological structures on conducting surfaces for a range of biomedical applications. In this respect, we investigate the effects of three independent electrosynthesis parameters, namely the applied potential, the composition of the comonomer solution and the film thickness on the incorporation of carboxylic acid-functionalized pyrrole units (Py-COOH) into polypyrrole/Py-COOH copolymer films. FT-IR, XPS and fluorescence microscopy results show that a larger Py-COOH content is inserted in films electrosynthesized at low potential, that the surface functionality of the copolymer films increases with the molar percentage of Py-COOH in the comonomer solution, and that Py-COOH units are preferentially incorporated in the earlier stage of the electrosynthesis process. The method is further adapted for preparing functionalized PPy copolymer nanotubes with potential application in drug delivery. Specifically, functionalized copolymer nanotubes are electrosynthesized through the template method in polycarbonate membrane. Carboxylic acid groups available at the outer surface of these nanostructures are then derivatized to covalently immobilize poly(ethylene glycol) chains, a protein-repellent polymer, so as to enhance the antifouling properties of these promising delivery vehicles.     

Direct-Ink-Writing of Electroactive Polymers for Sensing and Energy Storage Applications

Considering the high levels of materials used in the fields of electronics and energy storage systems, it is increasingly necessary to take into consideration environmental impact. Thus, it is important to develop devices based on environmentally friendlier materials and/or processes, such as additive manufacturing techniques. In this work, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared by direct-ink-writing (DIW) by varying solvent evaporation temperature and fill density percentage. Different morphologies for both polymers are obtained, including dense films and porous membranes, as well as different electroactive β-phase content, thermal and mechanical properties. The dielectric constant and piezoelectric d₃₃ coefficient for dense films reaches up to 16 at 1 kHz and 4 pC N⁻¹, respectively for PVDF-HFP with a fill density of 80 and a solvent evaporation temperature of 50 °C. Porous structures are developed for battery separator membranes in lithium-ion batteries, with a highest ionic conductivity value of 3.8 mS cm⁻¹ for the PVDF-HFP sample prepared with a fill density of 100 and a solvent evaporation temperature of 25 °C, the sample showing an excellent cycling performance. It is demonstrated that electroactive films and membranes can be prepared by direct-ink writing suitable for sensors/actuators and energy storage systems.     

Polypyrrole/carbon nanotube composites: Molecular modeling and experimental investigation as anti-corrosive coating

In this work we present a computational method based on molecular mechanics (MM) and dynamics (MD), to predict mechanical properties of polypyrrole (PPy)/polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (CNT-PABS) and PPy/carboxylic acid-functionalized single-walled carbon nanotubes (CNT-CA) composites. Furthermore, experiments were carried out to assess the anticorrosive features of the PPy film and CNT-PABS and CNT-CA PPy reinforced composite coatings. Computational bulk models of PPy/CNT-PABS and PPy/CNT-CA were implemented at atomistic scale and composite coatings were grown in situ onto carbon steel (OL 48-50) electrodes. PPy, PPy/CNT-PABS and PPy/CNT-CA computational models and films were investigated concerning mechanical properties by using computational tools. The obtained films were assessed experimentally as anticorrosive materials using potentiodynamic measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results clearly confirmed that the CNT-PABS and CNT-CA are properly dispersed in the composite coatings and have beneficial effect on mechanical integrity. Moreover, the anticorrosion protecting ability of the composite coatings is significantly higher than the one characteristic to pure PPy. The Young's moduli generally increased with increasing of CNT content and values ranged from 2.67 GPa in the case of pure PPy to 4.15–4.61 GPa in the case of PPy/CNT-PABS composite system.In agreement with earlier results from the literature for conducting polymer organic coatings, the higher conductivity of material leads to a more efficient anticorrosion protection capability, our results exhibited an enhance of conducting features even for very low mass of CNT-PABS or CNT-CA loaded in composites coatings therefore, an improvement of anticorrosion protecting ability.     

Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

Hybrid nanostructure of polypyrrole and porous silicon prepared by galvanostatic technique

Nanostructured porous silicon (PS) layer is prepared in a lightly doped p-type substrate (with pores < 5 nm) and used as a working electrode to deposit conducting polypyrrole (PPy) by the electrochemical oxidative polymerization technique in an organic liquid phase. Three distinguishable stages of PPy deposition are observed and recorded under constant applied current: nucleation of polymer at the pore bottom, unidirectional growth of PPy inside the pores, and polymerization outside the PS surface. The hybrid nanostrucutre of PS/PPy shows a significant improvement of electrical conductivity as opposed to the unmodified PS layer. The improved conductivity is observed in spite of the formation of insulating layer of silicon oxides as detected by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) measurements. Systematic study of fabrication and characterization of this organic-inorganic heterosystem, quantification of the PPy in the PS matrix, and the mechanism of filling the nanopores with polymer are presented and thoroughly discussed.     

Manganese oxide embedded polypyrrole nanocomposites for electrochemical supercapacitor

MnO₂ embedded PPy nanocomposite (MnO₂/PPy) thin film electrodes were electrochemically synthesized over polished graphite susbtrates. Growing PPy polymer chains provides large surface area template that enables MnO₂ to form as nanoparticles embeded within polymer matrix. Co-deposition of MnO₂ and PPy has a complimentary action in which porous PPy matrix provides high active surface area for the MnO₂ nanoparticles and, on the other hand, MnO₂ nanoparticles nucleated over polymer chains contribute to enhanced conductivity and stability of the nanocomposite material by interlinking the PPy polymer chains. The MnO₂/PPy nanocomposite thin film electrodes show significant improvement in the redox performance as cyclic voltammetric studies have shown. Specific capacitance of the nanocomposite is remarkably high (∼620 F g⁻¹) in comparision to its constituents MnO₂ (∼225 F g⁻¹) and PPy (∼250 F g⁻¹). Photoelectron spectroscopy studies show that hydrated manganese oxide in the nanocomposite exists in the mixed Mn(II) to Mn(IV) oxidation states. Accordingly, chemical structures of MnO₂ and PPy constituents in the nanocomposite are not influenced by the co-deposition process. The MnO₂/PPy nanocomposite electrode material however shows significantly improved high specific capacitity, charge-discharge stability and the redox performance properties suitable for application in the high energy density supercapcitors.     

Very stable, highly electroactive polymers of zinc(II)-5,15-bisthienylphenyl porphyrin exhibiting charge-trapping effects

Two new thiophene-substituted porphyrins and their zinc complexes were synthesized and electropolymerized via thiophene units on different electrode surfaces. Electrochemical characterizations show that the resultant polythiophenemetalloporphyrin hybrid materials are highly electroactive and exhibit remarkable higher electrochemical stability. Interestingly, they exhibit a charge-trapping effect. A mechanism for the observed charge-trapping phenomenon was proposed and supported by using model compounds. The deposited polymer films on different electrode surfaces exhibit a homogeneous morphology and possess good processability (soluble in polar solvents such as DMSO or DMF). Besides electrochemical method, UV/vis, NMR, FTIR, TEM and SEM were employed to characterize the new hybrid material.     

Preparation of highly conducting and spin-probed polypyrroles using coupled electrochemical-chemical synthesis in the presence of nitroxyl radicals

Summary A new method for the synthesis of conducting polypyrroles (PPy), based on chemical and combined electrochemical-chemical oxidation of pyrrole monomers in the presence of nitroxyl radical (TEMPOL-2,2,6,6-tetramethyl-4-hydroxy-1-oxy-piperidyl) as oxidation agent (in its oxidation state) and redox mediator respectively is described. The PPy films obtained are extremely porous and the electrical conductivity () of the resulting PPy samples ranges from 1 to 100 S cm^–1. PPy prepared in aqueous solutions has a lower conductivity 1 S cm^–1 as compared to the PPy prepared in acetonitrile solutions with conductivity of about 100 S cm^–1. The PPy films are quite compact and thick films (1 mm) can be pealed off from the electrode surface and pressed as a disc for further studies. Only after partial reduction of polypyrrole film the spin-probed PPy was obtained. The concentration of nitroxyl radicals incorporated in the polymer matrix can be changed using various degrees of polymer reduction. The anisotropic broadening of the observed ESR lines indicates a low mobility of incorporated nitroxyl radicals in the PPy matrix. The electronic interaction between the nitroxyl groups and the paramagnetic centers of the polymer chains, polarons, causes an ESR line broadening of polaron signal both on air (1.1 mT) and in vacuum (0.7 mT) as compared to unmodified PPy (0.2 mT on air, 0.05 mT in vacuum).     

Effects of Hexagonal Boron Nitride Insulating Layers on the Driving Performance of Ionic Electroactive Polymer Actuators for Light-Weight Artificial Muscles

To improve the energy efficiency and driving performance of ionic electroactive polymer actuators, we propose inserting insulating layers of 170 nm hexagonal boron nitride (h-BN) particles between the ionic polymer membrane and electrodes. In experiments, actuators exhibited better capacitance (4.020 × 10⁻¹ F), displacement (6.01 mm), and curvature (35.59 m⁻¹) with such layers than without them. The excellent insulating properties and uniform morphology of the layers reduced the interfacial resistance, and the ion conductivity (0.071 S m⁻¹) within the ionic polymer improved significantly. Durability was enhanced because the h-BN layer is chemically and thermally stable and efficiently blocks heat diffusion and ion hydrate evaporation during operation. The results demonstrate a close relationship between the capacitance and driving performance of actuators. A gripper prepared from the proposed ionic electroactive polymer actuator can stably hold an object even under strong external vibration and fast or slow movement.     

Influence of conductive network composite structure on the electromechanical performance of ionic electroactive polymer actuators

The influence of the nanostructure of the conductive network composite (CNC) on the performance of ionic electroactive polymer (IEAP) actuators has been examined in detail. We have studied IEAP actuators consisting of CNCs with different volume densities of gold nanoparticles (AuNPs) and the polymer network. Varying the concentration of AuNPs in CNC thin films was used as a means to control the CNC–ion interfacial area and the electrical resistance of the CNC, with minimum effect on the mechanical properties of the actuator. Increasing the interfacial area and reducing the resistance, while maintaining porosity of the composite, provide means for generating motion of more ions into the CNC at a significantly shorter time, which results in generation of strain at a faster rate. We have demonstrated that cationic strain in actuators with denser CNCs is improved by more than 460%. Denser CNC structures have larger interfacial areas, which results in attraction/repulsion of more ions in a shorter time, thus generation of a larger mechanical strain at a faster rate. Also, time-dependent response to a square-wave voltage was improved by increasing the AuNP concentration in the CNC. Under 0.1 Hz frequency, the cationic strain was increased by 64% when the AuNP concentration was increased from 4 to 20 ppm.     

Humic acid/polypyrrole on a paraffin‐impregnated graphite electrode and its use in arsenic extraction

A novel and simple electrode with rapid preparation was developed with humic acid (HA) and polypyrrole (PPy) films. The method for modified electrode preparation embraced the abrasive transfer technique on a paraffin‐impregnated graphite electrode (PIGE) followed by the electrochemical incorporation of a PPy polymeric film upon bare PIGE and PIGE/HA electrodes. Cyclic voltammetry, electrochemical impedance spectroscopy, and chronoamperometry were used for the study of the modified electrodes. Morphological characterization was performed by scanning electron microscopy. The obtained results demonstrated that the presence of HA did not affect the electrical properties of the system but indeed provoked changes in the polymer morphology, turning it more granular. Next, PIGE/HA/PPy was tested in arsenic solutions [As(V)] because arsenic contamination of water is an important worldwide environmental issue because of the sources of arsenic contamination of water come from both natural processes and anthropogenic activities. The modified electrode displayed good and reversible extraction properties toward the analyte in acid medium and was 18% more efficient than a previously reported PPy‐modified electrode (PIGE/PPy). From an environmental standpoint, this novel application of conductive polymer properties with the chelating capacity of humic substances constitutes a first step in the development of more efficient technologies for the removal of contaminants present in soil–water media. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Preparation of conducting composites of polypyrrole using supercritical carbon dioxide

Supercritical carbon dioxide, saturated with pyrrole, was brought into contact with oxidant‐impregnated films of poly(chlorotrifluoroethylene) (PCTFE), crosslinked poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and porous crosslinked polystyrene (PS) in order to form conducting composites via the in situ polymerization of pyrrole. The two nonporous hosts—PCTFE and crosslinked PDMS—did not form conducting composites with polypyrrole (PPy). On the other hand, the electrical conductivity of the PPy composites with carbon dioxide‐swollen PMMA and porous PS ranged from 1.0 × 10^?4 S/cm to 3.0 × 10^?5 S/cm. In these two cases, the level of pyrrole polymerized on the surface or in the pores of the host polymer was sufficient to attain the interconnected conducting polymer networks necessary for electrical conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1113–1116, 2003     

Interface porosity in multilayered all‐conducting polymer electrodes

Multilayered films made with at least two different electroactive polymers, in which the least conducting one acts as a dielectric and separates the layers made with the other, behave as efficient electrodes for electrochemical supercapacitors. In this work, we present a simple strategy to develop improved multilayered electrodes with structured interfaces by enhancing the porosity of the dielectric. This has been achieved by growing sodium chloride crystals onto a conducting polymer layer and, after generation of all required layers using the layer‐by‐layer electrodeposition technique, salt crystals have been eliminated by water etching. Results from morphological and topographical studies on single‐layered poly(3,4‐ethylenedioxythiophene) (PEDOT), poly(N‐methylpyrrole) (PNMPy), and poly(3,4‐ethylenedioxythiophene‐co‐N‐methylpyrrole) (COP), as well as electrochemical investigations on bi‐layered films with enhanced porosity at the interface between the two layers, have been used to design new four‐layered electrodes. These consist in two layers of PEDOT separated by two layers of nanosegregated COP with a porous interface in the middle. Although the properties of the new four‐layered electrodes improve due to the porous interface, the highest specific capacitance corresponds to the two‐layered electrode in which two PEDOT layers are separated by an ultra‐porous interface. POLYM. ENG. SCI., 59:1624–1635 2019. © 2019 Society of Plastics Engineers     

Remediation of chromium(VI) at polypyrrole-coated titanium

The application of conducting polypyrrole (PPy) and polyaniline (PAni) coated substrates in remediation of chromium, Cr(VI), is an area of considerable interest. Here, we discuss the implementation of PPy-coated titanium as a new material for the reduction of Cr(VI) to the less toxic trivalent state, Cr(III). An alkaline-peroxide based etching process was used to ensure the adhesion of the PPy coatings to the underlying titanium. The PPy films showed excellent resistance to acidic Cr(VI) solutions and remained adherent after continuous exposure to the solutions. In order to optimise the remediation process a number of experimental parameters were investigated, including the thickness of the PPy coating, the reduction potential used in pre-treatment of the PPy and the degree of solution agitation. The durability of the materials on exposure to the Cr(VI) test solutions made them suitable for repeated remediation experiments. Following several test-runs, the cleanup efficiency of the material was found to decrease slightly, however, increasing the exposure/experiment time resulted in significantly improved cleanup ability.