TEMPO-oxidized cellulose nanofibril/poly(vinyl alcohol) composite drawn fibers

PVA/TOCN composite fiber with a weight ratio of 100:1 was prepared from a mixture of aqueous poly(vinyl alcohol) (PVA) solution and 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-oxidized cellulose nanofibril (TOCN) dispersion using spinning, drawing, and drying processes. The as-spun PVA/TOCN composite fiber was further drawn, up to a draw ratio of 20 by heating at up to 230 °C. The maximum tensile modulus of the PVA/TOCN composite drawn fiber reached 57 GPa, remarkably higher than that of commercial PVA drawn fibers. Moreover, the PVA/TOCN composite drawn fiber had storage modulus higher than that of the PVA drawn fiber at each temperature in the range from 28 to 239 °C. Structural analyses showed that amorphous PVA regions in the composite drawn fiber were more oriented than those in neat PVA fiber after the addition of the small amount of TOCN used. These results indicate that TOCN elements were individually dispersed in the PVA matrix without aggregation and formed hydrogen bonds with amorphous PVA molecules in the composite drawn fiber.     

Preparation of cellulose-based conductive hydrogels with ionic liquid

Conductive hydrogel composed of microcrystalline cellulose (MCC) and polypyrrole (PPy) was prepared in ionic liquid; and the resulting hydrogel was characterized with FT-IR, SEM, XRD and TGA. By doping with TsONa, the MCC/PPy composite hydrogels showed relatively high electrical conductivity, up to 7.83 × 10⁻³ S/cm, measured using a four-probe method. The swelling kinetics of the composite hydrogels indicated that the swelling process was mainly influenced by the cellulose content; and the equilibrium swelling ratio decreased as the increasing of MCC content in the hydrogels. In addition, the MCC/PPy composite hydrogels exhibited significantly enhanced mechanical property in contrast to MCC hydrogel.     

Fabrication and electroanalytical characterization of label-free DNA sensor based on direct electropolymerization of pyrrole on p-type porous silicon substrates

Label-free DNA sensors based on porous silicon (PS) substrate were fabricated and electrochemically characterized. p-type silicon wafer was electrochemically anodized in an ethanolic hydrofluoric (HF) solution to construct a PS layer on which polypyrrole (PPy) film was directly electropolymerized. To achieve direct electropolymerization of PPy on PS substrate without pre-deposition of any metallic thin-film underlayer, a low resistivity wafer (0.01–0.02 Ω cm) was used. The rough surface of the PS layer allowed for a strong adsorption of the PPy film. Intrinsic negative charge of the DNA backbone was exploited to electrostatically adsorb 26 base pairs of probe DNA (pDNA) into the PPy film by applying positive bias. The pDNA was designed to hybridize with the target DNA (tDNA) which is the insertion element (Iel) gene of Salmonella enterica serovar Enteritidis. Dependence of peak current (i _p ) around 0.2 V vs Ag/AgCl on tDNA concentration and incubation time were shown from the cyclic voltammograms of PS/PPy + pDNA + tDNA substrates in a 0.01 M potassium perchlorate solution. Plot of i _p vs incubation time showed a reduction in current density (J) by ca. 29 μA cm⁻² every hour. Sensitivity obtained from a plot of i _p vs tDNA concentration was −166.6 μA cm⁻² μM⁻¹. Scanning electron microscopy (SEM) image of the cross-section of a PS/PPy + pDNA + tDNA multilayered film showed successful direct electropolymerization of PPy for a nano-PS DNA biosensor.     

Electrochemically synthesized graphene/polypyrrole composites and their use in supercapacitor

Composite films consisting of polypyrrole (PPy) and graphene oxide (GO) were electrochemically synthesized by electrooxidation of 0.1 M pyrrole in aqueous solution containing appropriate amounts of GO. Simultaneous chronoamperometric growth profiles and frequency changes on a quartz crystal microbalance showed that the anionic GO was incorporated in the growing GO/PPy composite to maintain its electrical neutrality. Subsequently, the GO was reduced electrochemically to form a reduced GO/PPy (RGO/PPy) composite by cyclic voltammetry. Specific capacitances estimated from galvanostatic discharge curves in 1 M H₂SO₄ at a current density of 1 A g^?1 indicated that values for the RGO/PPy composite were larger than those of a pristine PPy film and the GO/PPy composite. In the case of 6 mg mL^?1 GO for the preparation of GO/PPy, a high specific capacitance of 424 F g^?1 obtained at the electrochemically prepared RGO/PPy composite indicated its potential for use as an electrode material for supercapacitors.     

Polypyrrole nanocoatings of poly(styrene-co-methacrylic acid) particles

In this study the properties of polypyrrole (PPy) nanocoating over poly(styrene-co-methacrylic acid) (PS-MAA) particles were investigated. Monodisperse PS-MAA templates were obtained by free surfactant emulsion polymerization. The addition of methacrylic acid into the monomer feed mixture reduced particle size, ionic charge and hydrophobicity of the template surface. Correlations between template sizes and compositions, PPy confinement (granularity, shell size, etc.) and electrical conductivity, σ, are discussed. After dissolving the PPy/PS-MAA composites in tetrahydrofurane, PPy void spheres are obtained proving the core-shell nature of the coated particles. Bare styrene templates show densely packed PPy coatings and electrical conductivities near 7 S cm⁻¹ at high PPy loadings; on the contrary, at the same PPy mass percentage, the richer methacrylic acid particles show low packed PPy grains and conductivities that fall to 0.8 S cm⁻¹. In core-shell particles the PPy mass per unit area, Γ, is the key parameter which determines the insulator-conductor transition for any particle size. The conductivity values of PPy/PS-MAA composites follow a percolation law: σ∝t(Γ−Γc), with a critical threshold Γ_c=(0.262 ± 0.002)×10⁻⁶ g cm⁻². The critical exponent obtained t = 1.98 ± 0.07 agrees with the predicted value t = 2.0 for three-dimensional lattices of random resistors.     

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.     

Characterization and corrosion protection properties of polypyrrole / montmorillonite electropolymerized onto aluminium alloy 1100

Films of Polypyrrole/Montmorillonite (PPy/MT) clays were electropolymerized potentiostatically on aluminium alloy 1100, using sodium dodecylbenzenesulfonate (SDBS) as a dopant. Two clay species were used: Na⁺-Montmorillonite (MT-Na) and modified-Montmorillonite (MT-M). The characterization of the PPy/MT films performed by XRD and TEM shows that the exfoliation method employed, as well the electrochemical polymerization method used in this work, allow nanocomposite materials to be obtained. The PPy/MT films were found to have less electrical conductivity than pure PPy. The corrosion protection of aluminium alloy 1100 covering PPy/MT was evaluated by electrochemical techniques in 0.05 mol L⁻¹ NaCl medium. The electrochemical parameters derived from the polarization curves, together with the EIS data, revealed that the corrosion resistance of PPy/clay coatings depends on the type and concentration of Montmorillonite employed. The best performance in the corrosion protection of the aluminum was achieved with PPy/MT films containing 1% of clay.     

Low-Cost,Highly Sensitive,and Flexible Piezoresistive Pressure Sensor Characterized by Low-Temperature Interfacial Polymerization of Polypyrrole on Latex Sponge

Piezoresistive pressure sensors based on sponge are widely concerned because of their wide strain range, convenient signal acquisition, and good compressibility, yet it is still a challenge to acquire sponge-based pressure sensors with low cost and excellent sensing performance. Herein, low-priced FeCl₃^.6H₂O and pyrrole (Py) are dispersed in deionized water to form FeCl₃^.6H₂O/Py solution. Commercial latex sponge is impregnated into this solution to prepare conductive polypyrrole/latex (PPy/latex) sponge through low-temperature interfacial polymerization. The surface of latex sponge is covered by the micro-wrinkled PPy, which endows the PPy/latex sponge with a certain electrical conductivity. The specific porous structure and high elasticity of the latex sponge are the basic conditions for PPy/latex sponge excellent piezoresistive behaviors. PPy/latex sponge based piezoresistive pressure sensor shows high sensitivity (0.084 kPa⁻¹ at below 3.12 kPa), wider sensing range (0–85.0%) and long durability over 3800 s (1800 cycles). At the same time, the ability of the PPy/latex sponge based piezoresistive pressure sensor to monitor human movement has been successfully evaluated in some application scenarios, such as bending fingers, grabbing objects, tiptoe rising, and crouching.     

Synthesis of ultra-thin polypyrrole nanosheets for chemical sensor applications

Ultra-thin polypyrrole nanosheets (UPNSs) are fabricated by organic crystal surface-induced polymerization (OCSP) of pyrrole in an aqueous suspension containing hydrated crystals of sodium decylsulfonate (C₁₀SO₃Na) below the Krafft temperature using FeCl₃ as an oxidant. The hydrated C₁₀SO₃Na crystals are used as templates through electrostatic binding of the cationic polypyrrole (PPy) chains oxidized by Fe(III) ions on the anionic C₁₀SO₃Na crystal surface. The resulting UPNSs have a single layer thickness of ∼21 nm, widths between 2 and 6 μm, and lengths greater than 10 μm. The UPNSs are composed of a single continuous PPy domain. Moreover, the UPNSs exhibit higher conductivity (30.6 Scm⁻¹) and longer conjugation lengths than the PPy nanoparticles (2.4 Scm⁻¹) prepared using emulsion polymerization. We systematically investigate the UPNSs as gas sensors for detecting and quantifying toxic gases such as HCl and NH₃. The UPNSs exhibit much higher gas sensitivity and faster response times compared with the PPy nanoparticles.     

Glucose oxidase electrodes based on microstructured polypyrrole films

Highly sensitive glucose oxidase (GOD) electrodes were fabricated on the basis of microstructured polypyrrole (PPy) films. The microstructures of the PPy films had a morphology like cups and were arranged in a density of approximately 4000 units/cm². GOD was immobilized in microstructured PPy films coated on a Pt or stainless steel (SS; AISI 321) substrate electrode. The GOD/PPy/Pt electrode showed a linear response to glucose concentrations in the range of 0–17 mM at a potential of 0.4 V (vs a saturated calomel electrode). Its sensitivity was measured to be approximately 660 nA/(mM cm²) at 15°C, and the response time (t_95%) was approximately 20 s. In comparison, the sensitivity of the GOD/PPy/Pt electrode based on a flat PPy film was only approximately 330 nA/(mM cm²) under the same conditions. The sensitivity of the microstructured GOD/PPy/Pt electrode could be increased to as high as approximately 2400 nA/(mM cm²) at 37°C. The microstructured GOD/PPy/SS electrode had a sensitivity of approximately 550 nA/(mM cm²) and a t_95% value of approximately 30 s at 15°C and 0.4 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2550–2554, 2005     

Electrosynthesis of PAni/PPy coatings doped by phosphotungstate on mild steel and their corrosion resistances

Polyaniline/polypyrrole (PAni/PPy), polyaniline-phosphotungstate/polypyrrole (PAni-PW₁₂/PPy) and PAni/PPy-PW₁₂ have been successfully electrodeposited on mild steel (MS) by cyclic voltammetry in aqueous oxalic acid solutions. It was found that the incorporation of PW₁₂ enhanced the corrosion resistance of PAni/PPy coating. Moreover, in comparison to PAni-PW₁₂/PPy, PAni/PPy-PW₁₂ coating exhibited better corrosion resistance for mild steel. After immersion of 36 h in 0.1 M HCl, for instance, the polarization resistance of PAni/PPy-PW₁₂ coating reached 1695 Ω cm², more than those of both PAni/PPy and PAni-PW₁₂/PPy.     

PPy modified 1T-MoS2 hollow spheres with cohesive architecture as high-performance anode material for Li-ion batteries

A cohesive architecture of 1T-MoS₂ covered by PPy composite (1T-MoS₂@PPy) is successfully fabricated by a simple hydrothermal reaction followed by an in-situ polymerization route. The composite material consists of 1T-MoS₂ hollow microsphere and conductive PPy coating layer. The cohesive architecture enables the composite to show rapid shuttle of electrons/lithium ions and good ductility to buffer the volume changes during charging and discharging process when it is used as anode material. As expected, 1T-MoS₂@PPy composite exhibits a favorable discharge capacity up to 970.3 and 407.1 mAh g^?1 at 0.2 and 3 A g^?1, respectively. In addition, the composite also achieves impressive cycling performance of 717.1 mAh g^?1 at 1 A g^-1 after 500 cycles. This study provides a meaningful guidance in rational design of anode materials with cohesive architecture as well as high electrochemical performance.     

Fabrication of Tiron‐doped polypyrrole/MWCNT composite electrodes with high mass loading and enhanced performance for supercapacitors

In this study, the aromatic sulfonate compound Tiron with high charge to mass ratio is used as an anionic dopant for synthesis of polypyrrole (PPy). The fabricated PPy is investigated for electrochemical supercapacitor (ES) application. Testing results show that Tiron allows reduced PPy agglomeration, smaller particle size and improved charge storage properties of PPy. High capacitance and improved capacitive retention at high scan rates are achieved by the fabrication of PPy/multiwalled carbon nanotube (MWCNT) composite electrode using safranin (SAF) as a co‐dispersant. The Tiron‐doped PPy electrode shows the highest capacitance of 7.8 F cm^?2 with a mass of 27 mg cm^?2. The Tiron‐doped PPy/MWCNT composite electrode shows good capacitance retention with a capacitance of 1.0 F cm^?2 at the scan rate of 100 mV s^?1. Symmetric supercapacitor cells are fabricated using PPy based active materials. An energy density of 0.36 mWh cm^?2 is achieved. The energy/power density and capacitance retention of the Tiron‐doped PPy/MWCNT ES is significantly improved in comparison with PPy‐based ES, prepared without Tiron or MWCNT. The Tiron‐doped PPy/MWCNT symmetric supercapacitor presents good cycling performance with 91.4% capacitance retention after 1000 charge–discharge cycles. The PPy/MWCNT composites, prepared using Tiron and SAF co‐dispersant, are promising electrodes for ES. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42376.     

Preparation,morphology, and conductivity of waterborne,nanostructured, cationic polyurethane/polypyrrole conductive coatings

To endow cellulose fiber papers with good conductivity and simultaneously retain the mechanical strength of the conductive paper, a kind of waterborne, nanostructured, cationic polyurethane (CPU)/polypyrrole (PPy) conductive coatings were developed to modify the paper surface. Fourier transform infrared spectroscopy, atomic force microscopy, and thermogravimetry–differential thermogravimetry demonstrated that the peak associated with hydrogen bonding between ? NH and C?O of CPU was shifted, and chemical bonds between CPU and PPy were formed. Good compatibility between CPU and PPy was simultaneously established. Transmission electron microscopy and atomic force microscopy also suggested that PPy was encased and embedded in the CPU colloidal particles in a uniform style, and the surface of the CPU/PPy film was covered with a smooth, coherent conductive layer. With increasing pyrrole (Py) content from 5 to 20 wt %, the particle size increased from 55.08 to 74.59 nm, and the dispersity index (DPI) decreased. In addition, the conductivity of CPU/PPy increased from 0.1 to 5.0 S/cm. When the Py content was greater than 20 wt %, apparent increases in the particle size and DPI were detected as was particle coagulation; this resulted in decreased conductivity. Compared with the uncoated paper, the paper coated with CPU/PPy dispersions displayed different surface morphologies. The surface of the paper was completely enwrapped by the CPU/PPy conductive films when the coating amount was 45.42 g/m². With increasing coating amounts from 10.35 to 67.86 g/m², the conductivity of the conductive coated paper increased from 2.78 × 10^?3 to 2.16 S/cm, the tensile strength increased from 35.3 to 60.4 N m/g, and the conductive coated paper displayed good conductivity stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41445.     

Mechanically strong high performance layered polypyrrole nano fibre/graphene film for flexible solid state supercapacitor

Paper like flexible electrode becomes one of the most important research objects recently in request of the fast expanding market of portable electronics. Flexible solid state supercapacitors are shortlisted as one of the most promising energy devices to power electronics with medium to high power density requirements. In this work, we developed a simple but effective way to produce a mechanically strong and electrochemically active RGO/polypyrrole (PPy) fibre paper. A well-bedded microstructure was created with interlaced polypyrrole fibres evenly distributed between the graphene layers. Such microstructure can create enormous amount of pores and therefore provides larger interfaces for charge carrier storage/release. The effects of polypyrrole fibres on the film’s morphologies, mechanical properties and electrochemical performance were discussed. A solid state supercapacitor was demonstrated using such paper electrodes and a gel type electrolyte – phosphate acid (H₃PO₄) infused polyvinyl alcohol (PVA). It showed a high capacitance (345 F g⁻¹) and an excellent cycling stability (9.4% drop after 1000 cycles).     

Facile synthesis of polypyrrole nanospheres and their carbonized products for potential application in high-performance supercapacitors

A facile method to prepare uniform polypyrrole (PPy) nanospheres is developed by using 3-chloroperbenzoic acid as oxidant, structure-induced reagent and dopant for polymerization of pyrrole without introducing extra acid, template and surfactant. The as-synthesized PPy nanospheres with an average diameter of 100–200 nm and conductivity about 10⁻² S cm⁻¹ are characterized by SEM, FTIR, UV–vis spectroscopy, XRD and elemental analysis in an effort to determine the identity of the nanospheres and the mechanism relevant to their formation and stabilization. Influences of experimental conditions on the morphology of the PPy nanospheres have been investigated. Via the high temperature pyrolyzation at 900 °C, the nitrogen-doped carbon nanospheres have been obtained from the PPy nanospheres precursors, which have a high conductivity of 10–100 S cm⁻¹, showing a good potential as the electrode materials for high-performance supercapacitors due to their excellent electrochemical performance.     

Polypyrrole electropolymerized on aluminum alloy 1100 doped with oxalate and tungstate anions

Polypyrrole films doped with oxalic acid and tungstate were potentiostatically electropolymerized on aluminum alloy 1100. Two statistical factorial designs (fractional and complete) were used to study the influence of the synthesis variables on the film performance against corrosion. Corrosion protection of the polypyrrole films doped with oxalate and tungstate anions (PPy/OXA/W) on the aluminum alloy was evaluated by potentiometric and electrochemical impedance spectroscopy (EIS) measurements in a 0.05 mol L⁻¹ NaCl solution. The results obtained showed that the best performance against corrosion was detected with the PPy/OXA/W film synthesized at 1.0 V, 1.5 C in 0.2 mol L⁻¹ pyrrole, 0.1 mol L⁻¹ oxalic acid and 0.05 mol L⁻¹ sodium tungstate solutions provide a protective effect against corrosion.     

Development of Polypyrrole Modified Screen-Printed Carbon Electrode Based Sensors for Determination of L-Tyrosine in Pharmaceutical Products

Good health, of vital importance in order to carry out our daily routine, consists of both physical and mental health. Tyrosine (Tyr) deficiency as well as its excess are issues that can affect mental health and can generate disorders such as depression, anxiety, or stress. Tyr is the amino acid (AA) responsible for maintaining good mental health, and for this reason, the present research presents the development of new electrochemical sensors modified with polypyrrole (PPy) doped with different doping agents such as potassium hexacyanoferrate (II) (FeCN), sodium nitroprusside (NP), and sodium dodecyl sulfate (SDS) for a selective and sensitive detection of Tyr. The development of the sensors was carried out by chronoamperometry (CA) and the electrochemical characterization was carried out by cyclic voltammetry (CV). The detection limits (LOD) obtained with each modified sensor were 8.2 × 10⁻⁸ M in the case of PPy /FeCN-SPCE, 4.3 × 10⁻⁷ M in the case of PPy/NP-SPCE, and of 3.51 × 10⁻⁷ M in the case of PPy/SDS-SPCE, thus demonstrating a good sensitivity of these sensors detecting L-Tyr. The validation of sensors was carried out through quantification of L-Tyr from three pharmaceutical products by the standard addition method with recoveries in the range 99.92–103.97%. Thus, the sensors present adequate selectivity and can be used in the pharmaceutical and medical fields.     

Coating optimization of yield pseudoplastic paste-based stereolithography 3D printing of alumina ceramic core

Yield pseudoplastic paste is prepared for self-supported stereolithography (SLA) 3D printing with critical shear stress of 290.7 Pa and viscosity of 28810 mPa·s under strain rate of 30 s^?1. Simulation analysis of paste coating is carried out based on established constitutive equation. Furthermore, corresponding stress field is analyzed under different layer thicknesses (25–100 μm) and blade speeds (1.5–4.5 mm/s). Then, flexural strength, porosity, surface roughness and microstructure of components, printed with different layer thicknesses and sintered at different temperatures, are systematically investigated. Finally, complex-shaped cores are fabricated with flexural strength of 38.56±1.45 MPa, porosity of 21.57±0.8% and surface roughness of R_a < 3 μm. The optimized parameters include layer thickness of 25–50 μm, blade speed of 3.5 mm/s, and sintering temperature of 1300 ^oC. Moreover, step-like undulating fracture morphology of the core is observed along printing layer, which shows that the coating process has an important influence on the mechanical properties of ceramic parts.     

Epoxy‐Polypyrrole‐Cotton Tertiary Composite with Electro‐Tunable Stiffness

In this work, a tertiary epoxy composite reinforced with polypyrrole (PPy) coated cotton fabric layers exhibiting electrical voltage induced thermally tunable stiffness is reported. The thin coating of PPy over cotton fabric is accomplished via oxidative vapor phase polymerization that allows creation of an active thin layer over the fibers without affecting their mechanical properties. Six such functional layers are stacked within an epoxy matrix to prepare the composite that shows in‐plane electrical insulator behavior (volume resistivity > 10⁹ Ω cm) but considerably reduced resistivity by an order of 10³ across the cross‐sections. The presence of conductive layers enables the composite to heat via Joule's effect when an electrical voltage is applied across two ends. This causes softening of matrix near the matrix‐reinforcement interface and thereby changing composite's stiffness. On application of variable voltage, a non‐linear decrease of 91% in composite stiffness is observed (6371.2 N m^?1 at 0 V to 566.4 N m^?1 at 63 V). A stable and tunable mechanical performance of the composite is further demonstrated by cyclic changes in stiffness due to voltage change with recovery up to 95% of original stiffness after 14 continuous cycles.