Simultaneously depositing polyaniline onto bacterial cellulose nanofibers and graphene nanosheets toward electrically conductive nanocomposites

In this study, we report the construction of a ternary flexible nanocomposite of bacterial cellulose/graphene/polyaniline (BC/GE/PANI) via a facile two-step strategy. Bacterial cellulose/graphene (BC/GE) is first prepared by a novel in situ membrane-liquid-interface method, in which the three-dimensional continuous BC nanofibers can be maintained and the introduced GE can improve the mechanical properties mainly due to the uniform dispersion of GE in the BC matrix. To construct the effectively interconnected conductive paths between separated GE nanosheets, polyaniline (PANI) is simultaneously deposited on the surfaces of both BC nanofibers and GE nanosheets to obtain BC/GE/PANI with excellent electrical conductivity. It is found that the as-prepared BC/GE/PANI has an electrical conductivity of 1.7 ± 0.1 S cm⁻¹, which is higher than most of PANI-based composites. It is believed that the BC/GE/PANI nanocomposite possesses great potential for applications in electromagnetic shielding and flexible electrodes.     

Polymerization of aniline on bacterial cellulose and characterization of bacterial cellulose/polyaniline nanocomposite films

Bacterial cellulose/polyaniline nanocomposite film was prepared by the chemical oxidative polymerization of aniline with bacterial cellulose. Polyaniline conducting polymer nanocomposite films with bacterial cellulose fibers was prepared and characterized. In nanocomposite film, the bacterial cellulose was fully encapsulated with polyaniline by direct polymerization of the respective monomers using the oxidant and dopant. These bacterial cellulose/polyaniline nanocomposite films materials exhibited the inherent properties of both components. The deposition of a polyaniline on the bacterial cellulose surface was characterized by SEM. XPS revealed a higher doping level of the nanocomposite films doped with p-TSA dopant. From the cyclic voltammetry results, the polyaniline polymer was thermodynamically stable because redox peaks of electrochemical transitions in the voltagrams were maintained in bacterial cellulose/polyaniline nanocomposite films.     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

Effects of temperature and humidity on electrospun conductive nanofibers based on polyaniline blends

This study focuses and discusses the effects of temperature and humidity on electrospun conductive nanofibers, made with different polymer blends, deposited directly on interdigitated electrodes. The selected conductive polymers were based on blends of polyaniline emeraldine salt form and three different carrier hosting polymers: polyvinilpyrrolidone, polystyrene, and polyethylene oxide respectively. The obtained fibrous layers were investigated by the electrical measurements and morphological analysis (scanning electron microscopy). The study was made on the correlation between the electrical changes and morphological discrepancies due to temperature treatment. Moreover, this article reports the effects of relative humidity variations on electrical parameters. Since polyaniline is a well-known sensing material for different gases and volatile organic compounds, this study could be considered a supportive study for employing of the mentioned polymer blends as chemical interactive materials in gas sensor applications.     

Effects of dodecylamine and dodecanethiol on the conductive properties of nano-Ag films

Nano-Ag particles, with dodecylamine (DDA) and dodecanethiol (DDT) as the protective agent, were prepared and studied in order to investigate the effect of protective agent in the post heat-treatment of nano-Ag films. Results of electrical resistivity, micro-structural evolution and thermal analysis showed that the Ag-DDA films require a lower treatment temperature to convert into conductive materials compared to that of the Ag-DDT films. And the Ag-DDA films also have lower final electrical resistivity as well as more uniform and dense microstructure in comparison with the Ag-DDT films. Further study indicated that Ag-DDA films are thermodynamically unstable and the sinter of Ag-DDA particles could occur spontaneously even at room temperature. FT-IR, ¹H NMR and X-ray diffraction determinations revealed that both DDA and DDT molecules coordinate to the surface of nano-Ag particles through their head-groups. The bonding energy of Ag-S is higher than that of Ag-N and the alkyl chains ordering of chemisorbed DDT is also higher than that of chemisorbed DDA. It is implied that the post heat-treatment temperature and final resistivity of nano-Ag films are associated with the bonding energy and configuration of different capping molecules. Finally the conductive ink was prepared with well dispersed Ag-DDA nanoparticles and the ink-jet printed patterns on PI films show a sheet resistance of 166 mΩ/□ after heat-treating at 140 °C for 60 min.     

Positron beam studies on polyaniline and Ag-coated polyaniline

The effect of doping of the polyaniline emeraldine base (PEB), with Ni as well as Ni over layer coating has been investigated using variable low energy positron beam. Depth-resolved Doppler S-parameter measurements have been performed on undoped, Ni-doped polyaniline (PANI), and Ag (40 nm) film deposited PANI samples. Significant variation in S-parameter is observed for undoped and Ni-doped PANI. The size of the free volume hole has shifted to lower values upon doping with Ni as compared to that of undoped PANI, which is consistent with the conductivity measurements. For Ag-coated PANI systems, the S vs. E_p curves show distinct changes at the surface and interior regions. These results are discussed in the light of changes in free volume hole size distribution.     

Preparation, characterization, and property of polyaniline/Prussian blue micro-composites in a low-temperature hydrothermal process

Polyaniline/Prussian blue micro-composites have been synthesized by a low-temperature hydrothermal process. Prussian blue is obtained using the single iron-source precursor K₃[Fe(CN)₆] in acidic aqueous solution. The composite was characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transmission infrared spectroscopy (FT-IR), and X-ray diffractometer (XRD). The magnetic behavior of polyaniline/Prussian blue composites and the effect of the concentration of K₃[Fe(CN)₆] on the morphology of polyaniline/Prussian blue micro-composites have been investigated.     

Cobalt nanoparticles doped emaraldine salt of polyaniline: A promising room temperature magnetic semiconductor

Incorporation of magnetic nanoparticles in polymers with organic functional groups working as semiconducting substrate is of immense interest in the field of dilute magnetic semiconductors (DMS) and spintronics. In this article we report on synthesis and evaluation of dilutely doped (0-10 wt%) cobalt nanoparticles in emaraldine salt (ES) of polyaniline in the presence of dodecyl benzene sulfonic acid (DBSA) and p-toluene sulfonic acid (p-TSA) using a sonochemical-assisted-reduction approach as a possible DMS candidate. The X-ray diffraction pattern and high resolution transmission electron microscopy (HRTEM) image show the ES to be polycrystalline, in which 10 nm sized Co nanoparticles get embedded in its FCC structural form. From Fourier transform infrared (FT-IR) and UV-visible (UV-vis) spectroscopy studies, it is predicted that cobalt particles get electrostatically bound to the specific ion sites of ES, thereby modifying torsional degrees of freedom of the system. The applied field dependent magnetization study shows that the sample exhibits hysteresis loop with a minimal doping of 3 wt% of Co nanoparticles and increases with the amount of Co nanoparticles in ES due to dipolar interaction. The electron transport data show that with increase in Co wt% there is a gradual shift from ohmic to non-ohmic response to the sample bias, accompanied by opening of electrical hysteresis and an increased resistance. The non-linear response of higher doped systems has been attributed to the combination of direct and Fowler-Nordheim tunneling phenomena in these systems. Persistence of optical and transport properties of the polymer, with an introduction of magnetic moment in the system, envisages the system to be a fine magnetic semiconductor.     

EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

Nanocomposites (SiC-PANI) based on silicon carbide nanoparticles (SiC) encapsulated in conducting polyaniline (PANI) are synthesized by direct polymerization of PANI on the nanoparticle surfaces. The conductivity of PANI and the nanocomposites was modulated by several doping levels of camphor sulfonic acid (CSA). Electron paramagnetic resonance (EPR) investigations were carried out on representative SiC-PANI samples over the temperature range [100–300 K]. The features of the EPR spectra were analyzed taking into account the paramagnetic species such as polarons with spin S=1/2 involved in two main environments realized in the composites as well as their thermal activation. A critical temperature range 200–225 K was revealed through crossover changes in the thermal behavior of the EPR spectral parameters. Insights on the electronic transport properties and their thermal evolutions were inferred from polarons species probed by EPR and the electrical conductivity in doped nanocomposites.     

The effect of low frequency ultrasound on the production and properties of nanocrystalline cellulose suspensions and films

Suspension of nanocrystalline cellulose (NCC) produced from bleached cotton by controlled sulphuric acid hydrolysis was treated with low frequency ultrasound at 20 kHz and 60% amplitude for 0, 1, 2, 5 and 10 min and the effects of sonication on the properties of both the cellulose nanocrystals and their aqueous suspensions were investigated. Furthermore, a series of nanocellulose films were manufactured from the suspensions that were sonicated for different periods of time and tested. Laser diffraction analysis and transmission electron microscopy proved that sonication not only disintegrated the large NCC aggregates (D_v50 14.7 μm) to individual nanowhiskers with an average length and width of 171 ± 57 and 17 ± 4 nm, respectively, but also degraded the nanocrystals and yielded shorter and thinner particles (118 ± 45 and 13 ± 3 nm, respectively) at 10-min sonication. The ultrasound-assisted disintegration to nano-sized cellulose whiskers decreased the optical haze of suspensions from 98.4% to 52.8% with increasing time from 0 to 10 min, respectively. Sonication of the suspensions significantly contributed to the preparation of films with low haze (high transparency) and excellent tensile properties. With the increasing duration of sonication, the haze decreased and the tensile strength rose gradually. Irrespectively of sonication, however, all films had an outstanding oxygen transmission rate in a range of 5.5–6.9 cm³/m² day, and a poor thermal stability.     

Synthesis of polyaniline nanoparticles and their application for the removal of Crystal Violet dye by ultrasonicated adsorption process based on Response Surface Methodology

The present study focuses the synthesis of polyaniline nanoparticles (PANP) by rapid mixing polymerization method. They were recognized by FTIR and SEM techniques. Moreover they were utilized for the removal of Crystal Violet (CV) dye by ultrasonicated adsorption process. It ensures a quick alternative method compared to other conventional processes, which led to enhancement of mass transfer by ultrasound waves. The effectiveness of the process was confirmed through the effect of certain conditions like sonication time, temperature, adsorbent dosage and CV concentrations. The validity of the process was estimated by various adsorption isotherms. Kinetics and thermodynamic studies was also conducted to authenticate the process. The optimum operating parameters (OOP) were evaluated by Response Surface Methodology (RSM) based on central composite design (CCD) for the removal of CV dye. Moreover analysis of variances (ANOVA) was employed to estimate the significance of experimental variables. The predicated removal efficiency was found to be 94.29% which prove to be effectiveness of the process.     

Preparation and characterization of nanocrystalline ZnO particles from a hydrothermal process

Rod-like ZnO nanoparticles were prepared by the hydrolysis of zinc acetate under heating in diethylene glycol (DEG). Structural characterization of the synthesized powders was investigated by XRD, FT-IR, electron paramagnetic resonance (EPR) and transmission electron microscopy (TEM). The size of the particles increased as the amount of H₂O added increased in the nano size range. The average crystallite size calculated from the XRD patterns varied from 6 to 64 nm corresponding to the amount of H₂O added. The ZnO nanopartilces possess the wurtzite type crystallographic structure. It was found that these ZnO nanoparticles had singly ionized oxygen vacancy defect () and superoxide ions from the EPR investigations. A strong near UV emission of the ZnO nanoparticles at about 380 nm was observed and its intensity decreased as the amount of H₂O increased. This emission of ZnO nanoparticles is found to be particles size dependent due to the confinement effect. A green emission at about 540 nm due to the recombination of electrons trapped at singly ionized oxygen vacancies defect () appeared when the amount of H₂O increased. The intensity of the green emission increases as the concentration of increases.     

Preparation and characterization of cobalt-based nanostructured materials

Nano-sized cobalt clusters passivated by alkane-thiol molecules were obtained by the action of concentrated thiol solutions on micrometric cobalt particles. Thiol molecules caused an erosive process on the metal grains with the consequent formation of nano-sized metal debris and cobalt thiolate as by-product. The final material microstructure was composed by cobalt clusters embedded into a continuum cobalt thiolate matrix. Depending on the thiol molecule length, the material texture ranged from rubbery to waxy. These new types of nanocomposite materials were found to be crystalline, thermally stable up to ca. 300 ^°C, intensely red colored, and high hydrophobic. In addition, they generated polymeric structures when dissolved in non-polar solvents. Received 27 September 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: giancaro@unina.it     

Synthesis and structural characterization of nanostructured copper

In this paper, we report on the preparation and characterization of nanocrystalline powder of copper by dc-magnetron sputtering. Liquid nitrogen cooled cold finger arrangement has been used to prepare nanocrystalline powder. The particle size, crystal structure, and morphology of the samples were characterized by in situ high temperature X-ray diffraction (XRD) and transmission electron microscope (TEM). Results of high temperature XRD showed that highly oriented (111) phase becomes randomly oriented at higher temperature with a systematic shift in peak positions toward lower 2θ values due to changes in lattice parameters. Temperature dependence of lattice constants under vacuum shows linear increase in their values. Diffraction patterns obtained from TEM are also in accordance with the XRD data.     

Preparation and characterization of Pt-supported porous graphite nanofibers

In this work, porous graphite nanofibers (PGNFs) were manufactured as promising catalyst supporter by a physical activation method for direct methanol fuel cells, and Pt nanoparticles were loaded on the PGNFs in order to prepare electrode materials by a chemical reduction method. The pore structures of the Pt/PGNFs were analyzed by N₂ adsorption isotherms at 77 K. Electrocatalytic activities of final products were investigated by voltammetry and conductivity measurements in a 1.0 M CH₃OH/0.5 M H₂SO₄. As a result, electrocatalytic activities of Pt/PGNFs were increased in the presence of Pt particles on the PGNFs and with increasing the specific surface area of the carbons.     

Synthesis and characterization of conductive silver ink for electrode printing on cellulose film

Silver nanoparticles with size less than 50 nm were synthesized from silver nitrate, polyvinylpyrrolidone (PVP) and ethylene glycol, where these chemicals acted as metal precursor, stabilizer and reducing agent, respectively. Then a conductive silver ink was prepared with a suitable solvent by adding a viscosifier, hydroxyethyl-cellulose (HEC), and a surfactant, diethylene glycol (DEG). The combined effect of both viscosifier and surfactant on the physical property of the silver ink was analyzed by measuring the contact angle of the silver ink on a cellulose film. Moreover, the influences of PVP molecular weight and reaction temperature on the size of the silver nanoparticles were analyzed. Then the silver ink was coated on the cellulose film by spin coating and the effects of different solvents, sintering temperatures and solid contents on its electrical resistivity were examined. It was found that, with 50 % co-solvent of deionized water and DEG and solid content of around 50 %, the silver ink exhibited the lowest resistivity. This ink can be used for inkjet printing of conductive patterns on cellulose films.     

Phosphoric acid and pH sensors based on polyaniline films

Polyaniline (PANI)-chemically coated the electrode of quartz-crystal microbalance (QCM) has been developed for the determination of phosphoric acid (H₃PO₄) in the liquid phase. The sensing mechanism is based on the fact that the QCM devices produce a change in the oscillating frequency when the PANI coating the electrode of QCM interacts with different concentration of the acid. This was made during the subsequent redoping–dedoping processes of the PANI film in acid and ammonia solutions, respectively. Also, this was made during the successive redoping in different acid solutions. The QCM sensor demonstrated a rapid response to the acid with an excellent reversibility. A linear response of the sensor for different concentrations of H₃PO₄ was found in region of 1 M. The conductivity at different concentration of the acid was also determined. Finally, pH dependence on the electronic absorption of PANI phosphate film was studied which indicates that the film can be used as a sensor over a wider pH range of 3–12. This is in comparison to a PANI-sulphate film which shows limited pH absorption dependence (5–8).     

Nanometric laser trapping of microbubbles based on nanostructured substrates

Laser trapping near the surface of a nanostructured substrate is demonstrated. Stable microbubbles with radii of 1-20 μm have been created and manipulated with sub-micron precision by a focused laser beam in an immersion oil covering arrays of pairs of gold nanopillars deposited on a glass substrate. The threshold for bubble creation and trapping characteristics depended on near-field coupling of nanopillars. The nanometric laser tweezers showed giant trapping efficiency of Q ∼ 50 for the trapped microbubbles.     

Preparation and characterization of Ag nanoparticle-embedded polymer electrospun nanofibers

Poly (vinyl alcohol) (PVA) and poly (vinyl pyrrolidone) (PVP) nanofibers embedding Ag nanoparticles (5–18 nm) have been prepared successfully by electrospinning at room temperature. Scanning electron microscope (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Fourier transform IR spectra (FTIR), and Raman scattering were used to characterize the structure and properties of Ag nanoparticle-embedded PVA and PVP nanofibers before and after heat treatment at different temperature. The antibacterial activity of Ag nanoparticle-embedded PVP nanofibers after heat treatment was also tested, which indicated that the biological activity of yeast cells was effectively inhibited by these Ag nanoparticle-embedded PVP nanofibers.     

Large-area fibrous network of polyaniline formed on the surface of diatomite

Large-area fibrous network of polyaniline is obtained on the surface of diatomite by in situ polymerization of aniline without stirring. And it is characterized via Fourier-transform infrared spectroscopy, Raman spectroscopy, thermal analysis technology, four-probe technique and cyclic voltammetry, as well as specific surface, total pore volume, average pore size and pore size distribution. This composite contains 85% polyaniline, which conductivity is 5.08 S cm⁻¹ at 25 °C. It is more significant that its film electrode not only possesses good redox reversibility in the aqueous media ranging from pH 1.0 to 7.0, but also shows good electrochemical cycling stability in the aqueous media of pH 4.0. It will be a promising material for several applications due to increasing the operating pH window in the aqueous media and good conductivity.