Polyaniline hollow microspheres constructed with their own self‐assembled nanofibers

Polyaniline (PANI) hollow microspheres constructed with their own nanofibers were prepared by inversed microemulsion polymerization associated with a template‐free method in the presence of β‐naphthalene sulfonic acid (β‐NSA) as the dopant. The hollow microspheres were 4.0–6.0 μm in outer diameter and 150–250 nm in shell thickness; they consisted of the nanofibers (20–30 nm in diameter and 150–250 nm in length). We propose that the coordination effect of the reversed emulsion and the dopant or dopant/aniline micelle might have been a driving force in the formation of the special microstructures/nanostructures, where the reversed microemulsion acted as a soft template in the formation of the microspheres and where NSA or the aniline/NSA micelle was regarded as a soft template in the formation of the nanofibers. The molar ratio of water to the aniline/NSA salt and ultrasonic irradiation were critical in the control of the formation yield and the diameter of the uniform microspheres. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3050–3054, 2006     

Facile fabrication of polyaniline/polypyrrole copolymer nanofibers with a rough surface and their electrorheological activities

Hierarchical polyaniline/polypyrrole (PANI/PPy) copolymer nanofiber was prepared via a two‐step method and adopted as dispersing materials for electrorheological (ER) fluids. The first step was used to synthesize PANI nanofibers by a rapid mixing method. Subsequently, the PANI/PPy copolymer nanofibers with a rough surface were obtained using an in situ polymerization method continuously. The morphology of the resultant PANI/PPy copolymer nanofibers can be controlled by varying the amount of Py monomer in the secondary in situ polymerization method. The rough surface of PANI/PPy copolymer nanofibers were confirmed by scanning electron microscopy and transmission electron microscopy. The diameter of PANI/PPy nanofiber is within the range 100–200 nm. The obtained PANI/PPy copolymer particles all exhibit amorphous structure through X‐ray diffraction measurement. We also demonstrated that the hierarchical PANI/PPy copolymer nanofibers exhibited characteristic ER behaviors, which were investigated using a Haake rotational rheometer at various electric field strengths. The ER efficiency e for PANI‐1mLPPy and PANI‐2mLPPy ER fluids at shear rate 0.1 s⁻¹ is 36.6 and 28.5 under electric field strength E = 3 kV/mm, respectively. Low leaking current density is observed even at high electric field strength and wide plateau region appeared, which show a strong ER activity for the PANI/PPy composite nanofibers. The results also indicate that the PANI/PPy composite particles have distinctly enhanced ER effect compared with the pure PANI and PPy particles under electric stimuli. The significantly improved ER property of PANI/PPy‐based ER fluid is ascribed to the enhanced interfacial polarization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46289.     

Poloxamer and gelatin gel guided polyaniline nanofibers: synthesis and characterization

A rapid polymerization technique was successfully employed to synthesize interconnected polyaniline (PANI) nanofibers using chemical oxidative polymerization inside a soft template. The thermoreversible hydrogels of Lutrol F 127 and gelatin were used as templates where the interstices present in the hydrogel were responsible for the formation of PANI nanofibers with a diameter in the range ca 70?75 nm and ca 50?55 nm respectively and several micrometers in length. The doped emeraldine salt of PANI was confirmed by Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy. The crystallinity of as‐synthesized PANI nanofibers for both cases was verified by an X‐ray diffraction study while thermogravimetric analysis was performed to compare the relative stability of the synthesized PANI nanofibers. The electrical conductivities of polymerized PANI are of the order of 10^?3 S cm^?1 and are compared with those of template fabricated PANI. The Lutrol F 127 gel guided PANI nanofibers showed a rectifying property while the gelatin gel guided PANI provided a simple ohmic nature. © 2013 Society of Chemical Industry     

Synthesis and characterization of hollow polyaniline microtubes and microbelts with nanostructured walls in sodium dodecyl sulfate micellar solutions

Doped polyaniline in its emeraldine salt form (PANI‐ES) were successfully prepared by in situ chemical oxidative polymerization using various concentrations of sodium dodecyl sulfate (SDS) micellar solutions. Structural analysis using field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy showed that the morphologies of fabricated PANI‐ES contain hollow tube‐like and belt‐like structures with thickness in the range of 100–200 nm, diameters in the range of 1–5 μm, and lengths up to several tens and hundreds of micrometers. The changes of morphology from particle‐like into microtube‐like or microbelt‐like structure with nanostructured walls are strongly dependent on the concentration of SDS. The conductivities of fabricated PANI‐ES with 0.1 M SDS content at room temperature are 80% higher than those of PANI‐ES without SDS, perhaps because SDS may serve as a dopant or the formation of one‐dimensional structure to improve the conductivity of PANI‐ES. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

One‐step synthesis of polyaniline nanofibers decorated with silver

Polyaniline (PANI)/silver (Ag) nanocomposites containing PANI nanofibers decorated with well‐dispersed Ag nanoparticles were obtained with interfacial polymerization. It was interesting that silver nitride affected not only the diameter and crystallinity of the PANI nanofibers but also their room‐temperature conductivity. The conductivity increased with increasing Ag loading up to 10 (molar ratio of aniline to silver nitride), but the conductivity moderately decreased with further increasing Ag loading. Scanning electron microscopy and X‐ray diffraction analysis results indicate that the diameter of the PANI nanofibers became smaller and smaller, and their crystallinity got better and better with increasing Ag loading. However, Fourier transform infrared analysis proved that the balance of oxidized and reduced units of PANI became big with increasing Ag loading, which may have resulted in the decreasing conductivity of PANI. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Facile Synthesis of Polyaniline Nanofibers in the Presence of Polyethylene Glycol

Polyaniline (PANI) nanofibers were synthesized in the presence of Polyethylene glycol. The morphologies of polyaniline nanostructures were characterized by scanning electron microscopy and transmission electron microscopy. The PANI nanofibers have diameters in the range of 20–50 nm and lengths up to several micrometers. The properties of the as-prepared products were characterized by thermogravimetric analysis, Fourier-transform infrared spectroscopy and ultraviolet-visible absorption spectrum. CV experiment shows the obtained PANI nanofibers has good electrochemical activity.     

In situ fabrication of polyaniline‐silver nanocomposites using soft template of sodium alginate

Polyaniline (PANI)‐Ag nanocomposites were synthesized by in situ chemical polymerization approach using ammonium persulfate and silver nitrate as oxidant. Characterizations of nanocomposites were done by ultraviolet–visible ( UV–vis), Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM). UV–vis, XRD and FTIR analysis established the formation of PANI/Ag nanocomposites and face‐centered‐cubic phase of silver. PANInanofibers were of average diameter ～ 30 nm and several micrometers in length. Morphological analysis showed that the spherical‐shaped silver nanoparticles decorate the surface of PANI nanofibers. Silver nanoparticles of average diameter ～ 5–10 nm were observed on the TEM images for the PANI‐Ag nanocomposites. Such type of PANI‐Ag nanocomposites can be used as bistable switches as well as memory devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Template‐free electrochemical synthesis and electrochemical supercapacitors application of polyaniline nanobuds

One‐step and template‐free synthesis of polyaniline nanobuds (PANI NBs), synthesized using anodic electrochemical polymerization method, is reported at room temperature onto a conducting indium‐tin‐oxide glass substrate. The PANI NBs are characterized for their structural, morphological, and electrochromic properties. Scanning electron microscopy image reveals NBs type architecture, perpendicular to the substrate surface. These NBs are broader at their bottoms and narrower at the tops. Individual NB has confirmed 30 nm top diameter and 100–200 nm length. Electrochemical supercapacitive behavior of the PANI NBs electrode is investigated by measuring cyclic voltammetry curves. Moderate specific capacitance of 128 F/g is achieved in the potential range of ?0.2 to 1.0 V at 10 mV/s sweep rate in 0.5 M H₂SO₄ electrolyte. Influence of inner and outer charges on a resultant specific capacitance is also investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of polyaniline nanofiber and copolymerization with acrylate through in situ emulsion polymerization

Polyaniline (PANI) was prepared, respectively, by direct mixed oxidation method in different acids. Scanning electron microscopy showed that high quality of PANI nanofibers can be obtained easily in hydrochloric acid, sulfuric acid, and acetic acid, especially in the sulfuric acid; infrared and ultraviolet spectra characterization showed all products were the doped PANI. Then, using complex emulsifiers, PANI was dispersed in acrylate emulsion by supersonic dispersion assisted with mechanical stirred to obtain mixed pre‐emulsion, the result showed different PANI performed different dispersing stability in the pre‐emulsion. More importantly, PANI–polyacrylate copolymer was prepared through multi‐steps in situ emulsion polymerization using water‐soluble azo (VA‐044) as initiator. Experiment showed that good dispersing stability of PANI in the pre‐emulsion was premise to obtain the final stable copolymer emulsion. Further, the micro‐morphology and thermal property of the copolymer were studied by transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analyzer. The result proved that acrylate occurred in situ polymerization on surface of PANI nanofibers, the presence of PANI increased glass transition temperature (T_g) and thermal decomposed temperature of the copolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Oxidative solution polymerization of aniline hydrochloride onto electrospun nanofibers mats of polylactic acid: Preparation method and characterization

In this work, we present the preparation of polylactic acid (PLLA)/polyaniline (PANI) conductive composite nanofibers mats. They are prepared by bulk oxidative solution polymerization of PANI onto electrospun non‐woven fibers mats of PLLA. The PANI ratio in the composite is about 70%w/w. Scanning electron microscopy (SEM) shows that PLLA nanofibers are randomly oriented, beads free with diameters of 186 ± 85 nm, The PLLA/PANI composite nanofibers diameter values are 518 ± 128 nm with a good adherence between PANI and PLLA nanofibers. DSC and XRD measurements reveal an amorphous structure of the electrospun PLLA fibers due to the rapid evaporization of the solvent. FTIR and UV–vis spectra reflect good mutual interactions between PANI and PLLA chains. The DC‐conductivities ( ) far better than other published ones for similar composites prepared by bulk oxidative solution polymerization of PANI onto other electrospun nanofiber mats or with electrospun nanofibers from a solution mixture of PLLA and PANI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41618.     

Nanofiber organic semiconductors: The effects of nanosize on the electrical charge transport and optical properties of bulk polyanilines

The electrical transport, optical, and microstructural properties of bulk polyaniline (PANI) and nano‐PANIs were investigated. A field emission scanning electron microscopy (SEM) image of bulk PANI showed macroscopic and aggregated granular particles. A SEM image of the nanostructured PANI showed the formation of one‐dimensional nano/microstructures. The formation of nanofibers was observed from the transmission electron microscopy image. The electrical conductivities of the bulk and nanostructured PANIs increased with increasing temperature, which indicated semiconductor behavior. The electrical conductivities of the bulk and nanostructured PANIs at room temperature were found to be 2.12 × 10^?5 and 1.80 × 10^?2 S/cm, respectively. The electrical conductivity of the nanostructured PANI was about 850 times higher than that of the bulk PANI. The obtained band gaps of the bulk and nanostructured PANIs were determined from diffuse reflectance measurements and were found to be 3.27 and 2.41 eV, respectively. The refractive index of the PANI samples changed from 1.3 to 1.61. The obtained results indicate that the electrical and optical properties of the PANI were inherently dependent on the nanostructure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of water on inorganic acids doped polyaniline

Based on gravimetric measurements, the effect of water on thin films of inorganic acids doped polyaniline (PANI) was developed. The starting point was the fact that PANI coating on the electrode of quartz crystal microbalances (QCM) showed significant frequency shifts under exposure to liquid water. The changes in the frequency as a function of treatment time in water were quantitatively measured. These changes suggested that the mass decreases under water exposure were due to dopant ions release. The data have been collected using doped PANI films with HCl, H₂SO₄, and H₃PO₄. For PANI‐HCl upon immersion in water showed rapid mass loss followed by slow kinetically dopant ions release with time. However, PANI‐H₃PO₄ and PANI‐H₂SO₄ showed a slow kinetically release out of the film immediately upon immersion in water. The release process was well described by Fickian diffusion process. The diffusion coefficients (D) were determined and found to be dependent on the acid dopant utilized. They varied within the range of (1.68–14.7) × 10^‐14 cm²/s. This work presented an attempt to find a simple method based on the QCM for investigating the diffusion of dopant ions out of thin PANI films upon immersion in water and determining D. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and aggregation behavior of amphiphilic nanostructures composed of carbosilane dendrimer with peripheral poly(ethylene glycol) moieties

Dendritic amphiphiles as novel building blocks are very important for self‐assembling in the supramolecular chemistry area. In this work, a carbosilane dendrimer with hexamethylene as the branching unit (G1) was first synthesized as a hydrophobic core and then linked with poly(ethylene glycol) (PEG) units as the periphery by a hydrosilylation reaction to prepare an amphiphilic dendrimer (G1‐PEG) with a yield of 27%. The aggregation behavior of G1‐PEG in water was studied with surface tension, dynamic light scattering and transmission electron microscopy methods. The surface tension data showed that the critical aggregation concentration of such dendrimers in water is approximately 0.75 g L^?1. The results of dynamic light scattering and transmission electron microscopy indicated that the aggregate size of G1‐PEG dendrimers in water is related to the concentration. Small micelles of about 10 nm were found at high concentration, large vesicles of about 100 nm were observed at low concentration, and a mixture of micelles and vesicles was found at middle concentrations. The encapsulation of G1‐PEG to a fluorescence probe verified the existence of a hydrophobic microenvironment in the aggregates at high concentrations of the amphiphilic dendrimer. © 2014 Society of Chemical Industry     

Low Temperature Carbothermal Reduction Synthesis of ZrC Nanofibers via Cyclized Electrospun PVP/Zr(OPr)4 Hybrid

The fabrication capability of zirconium carbide (ZrC) nanofibers by a novel polymeric solution was examined using electrospinning method. The electrospinnable solution was prepared from the reaction of zirconium n‐propoxide (Zr(OPr)₄) with acetylacetone and acetic acid followed by the addition of polyvinylpyrrolidone (PVP) solution. By utilizing thermal and microstructural analyses such as differential scanning calorimetry–thermogravimetry (DSC–TG), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET), the effect of heat treatment type on the morphology and crystallinity of as‐spun PVP/Zr(OPr)₄ hybrid fibers was examined. The results showed that direct carbonization treatment of as‐spun fibers under argon atmosphere led to spherical ZrC aggregates in lack of fibrillar morphology, whereas carbonization coupled with cyclization could be recognized as the unique template to govern the morphology and crystallinity of ZrC nanofibers. Carbonization of the cyclized fibers at 1550°C in flowing argon atmosphere produced the thick, fragmented rosary‐like fibers with a diameter of 357 nm, while through a 100°C decrease in carbonization temperature to 1450°C, the thin, smooth, long, and uniform ZrC nanofibers with 176 nm diameter and a medium surface area of 23 m²/g were obtained.     

Synthesis of dendritic polyaniline nanofibers by using soft template of sodium alginate

Highly crystallized polyaniline (PANI) nanofibers were synthesized by oxidative polymerization of aniline in the presence of sodium alginate as a soft template in HCl and ammonium peroxydisulfate (APS) acting as an oxidizing agent. Sodium alginate, in presence of a protonic acid like HCl, formed hydrogen bonds with anilium ions or oligomers. The formed hydrogen bonds provide the driving force to form PANI nanofibers. The nanofibers were separated from the alginate gel by degelling with ammonium hydroxide and during degelling emeraldine salt was converted into emeraldine base form. The polymerized PANI was characterized using ultraviolet (UV)–visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and scanning electron microscopy (SEM). UV and FTIR spectra showed that the presence of sodium alginate had no effect on the electronic state and backbone structures of the resulting PANI products. It was evident from the XRD analysis that the obtained PANI nanofibers exhibit higher crystalline order. SEM micrographs showed that PANI nanofibers were just like a mat of interwoven twisted nanofibers. After magnification of the SEM image, it was found that most of the nanofibers were interconnected to form ramose structures rather than isolated nanofibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photoluminescence,FTIR, and electrical characterization of samarium(III) chloride‐doped polyaniline

The synthesized polyaniline (PANI) is doped with different concentrations of Samarium(III) chloride (SmCl₃). The electrical conductivity of doped PANI samples has been measured in the temperature range (300–400K). It has been found that dc conductivity increases with the increase of dopant concentration. Different parameters, based on the conductivity, such as pre‐exponential factor (σ₀) and activation energy (ΔE) have also been calculated. These parameters exhibit information about the nature and suitability of the dopant. Doped samples are characterized by FTIR and photoluminescence studies, which show the interaction of dopant with PANI. Two sharp peaks of different intensities from PL spectra at 388 and 604nm have appeared in doped PANI, which might be due to the effect of SmCl₃. It has been observed that SmCl₃ (dopant) shows noticeable changes in the electrical and spectroscopic properties of doped PANI. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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

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

Electrochemical synthesis and optical properties of helical polyaniline nanofibers

Helical polyaniline (PANI) nanofibers were facilely synthesized via a direct electrochemical method without using any template in the presence of (1S)-(+)-camphor-10-sulfonic acid (d-CSA) or (1R)-(−)-camphor-10-sulfonic acid (l-CSA) as the dopant. The helical morphologies of the PANI nanofibers prepared from potentiostatic deposition were confirmed with SEM and TEM. The helical PANI nanofibers induced by d-CSA and l-CSA exhibited mirror-imaged circular dichroism spectra in the UV-vis range, indicating the stereochemical selectivity of the electrochemical polymerization. The colors and optical activities of these nanofibers can be maintained on an indium-tin oxide (ITO) coated electrode with a dedoping/redoping treatment. The optical activities of the helical PANI nanofibers reversibly varied with different oxidized forms, which were easily controlled by the different potentials applied to the nanofibers.     

Synthesis of PANI‐CaO composite nanofibers with controllable diameter and electrical conductivity

We report the direct evidence of the control of diameter, surface morphology, and conductivity of polyaniline (PANI) nanofibers by systematically varying the addition of CaO in the range from 0.005 to 1.00 g. The possible incorporation of CaO in PANI was revealed by Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy. The diameter of PANI nanofibers was varied with the variation of CaO loadings. The low diameter, 30 nm was obtained for the highest loading of CaO (1.00 g). Field emission scanning electron microscopy analysis showed that the addition of CaO between the range of 0.005 and 1.00 g, always produces nanofibers with regular and uniform surface morphology and without secondary growth and agglomeration of primary nanoparticles. Conductivity measurements showed that the highest conductivity value of 6.329 S cm⁻¹ could be obtained by the addition of the lowest amount of CaO (0.005 g). Furthermore, we observed the decreasing trend of conductivity with the increasing of CaO loadings. POLYM. COMPOS., 36:359–366, 2015. © 2014 Society of Plastics Engineers     

聚苯胺纳米纤维的合成及表征

以D-樟脑磺酸为掺杂剂,十二烷基苯磺酸钠为软模板,过硫酸铵为氧化剂,在水溶液体系中通过苯胺原位聚合制备得到聚苯胺纳米纤维,对其进行了紫外和红外的表征,并使用SEM对其形貌进行了观测。进一步研究结果表明,樟脑磺酸的掺杂可促进聚苯胺纳米纤维的形成,并同时起到掺杂剂和软模板的双重作用;通过控制反应的时间,可调节产物的形貌结构。