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1.
Conductive composites consisted of epoxy resin and polyanilines (PANIs) doped with dodecylbenzenesulfonic acid ( 1 ), dodecylsulfonic acid (2), di(2‐ethylhexyl)sulfosuccinic acid (3), and HCl were synthesized by use of Ntert‐butyl‐5‐methylisoxazolium perchlorate (5) under various reaction conditions. It was found that the composites with PANI doped with acid 2 (PANI‐2) prepared by curing with 10 mol % of reagent 5 at 80 °C for 12 h showed high electroconductivity along with the low conducting percolation threshold (3 wt % of PANI‐2). Furthermore, the composite with even ?10 wt % of PANI‐2 exhibited ?10?1 S/cm of electroconductivity. The UV–vis and IR measurements indicated that the conductive emeraldine salt form of PANI‐2 in the composite was maintained after the curing reaction. The thermal stability was studied by TGA and DSC measurements, and then, the Td10 and Tg of the composite with 5 and 10 wt % of PANI‐2 were found to be similar to those with the cured epoxy resin itself. In addition, the similar investigation with an oxetane resin instead of the epoxy resin was also carried out. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 718–726, 2006  相似文献   

2.
Polyaniline (PANI) in an emeraldine‐base form, synthesized by chemical oxidation polymerization, was doped with camphor sulfonic acid (CSA). The conducting complex (PANI–CSA) and a matrix, polyamide‐66, polyamide‐11, or polyamide‐1010, were dissolved in a mixed solvent, and the blend solution was dropped onto glass and dried for the preparation of PANI/polyamide composite films. The conductivity of the films ranged from 10?7 to 100 S/cm when the weight fraction of PANI–CSA in the matrices changed from 0.01 to 0.09, and the percolation threshold was about 2 wt %. The morphology of the composite films before and after etching was studied with scanning electron microscopy, and the thermal properties of the composite films were monitored with differential scanning calorimetry. The results indicated that the morphology of the blend systems was in a globular form. The addition of PANI–CSA to the films resulted in a decrease in the melting temperature of the composite films and also affected the crystallinity of the blend systems. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2531–2538, 2002  相似文献   

3.
Polyaniline (PANI) doped with p‐toluene sulfonic acid was synthesized by chemical polymerization method using (NH4)2S2O8 as an oxidizing agent. This is a single step polymerization process for the direct synthesis of the conducting emeraldine salt (ES) phase, without the need of doping, dedoping, and redoping of the polymer. Presence of a free carrier tail at higher wavelength, characteristic of extended coil conformation along with a sharp polaronic peak is observed in the UV–vis spectrum of doped PANI in m‐cresol solvent. FT‐IR studies show the characteristic peaks of ES phase along with a sharp peak at 1120 cm?1 representing vibration band of the dopant ion. Clumps of small fibers resulting in a sponge‐like structure was observed under scanning electron microscope. Thermal studies revealed a three‐step decomposition pattern. Conductivity is found to increase with an increase in the temperature showing “thermal activation behavior.” Decrease in resistance with increasing humidity is observed in a broad range of humidity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2161–2169, 2005  相似文献   

4.
Single‐walled carbon nanotubes (SWNTs)/polyaniline (PANI) composite films with enhanced thermoelectric properties were prepared by combining in situ polymerization and solution processing. Conductive atomic force microscopy and X‐ray diffraction measurements confirmed that solution processing and strong π–π interactions between the PANI and SWNTs induced the PANI molecules to form a highly ordered structure. The improved degree of order of the PANI molecular arrangement increased the carrier mobility and thereby enhanced the electrical transport properties of PANI. The maximum in‐plane electrical conductivity and power factor of the SWNTs/PANI composite films reached 1.44×103 S cm?1 and 217 μW m?1 K?2, respectively, at room temperature. Furthermore, a thermoelectric generator fabricated with the SWNTs/PANI composite films showed good electric generation ability and stability. A high power density of 10.4 μW cm?2 K?1 was obtained, which is superior to most reported results obtained in organic thermoelectric modules.  相似文献   

5.
Composites of multiwall carbon nanotubes (MWCNTs) and sulfonated polyaniline (SPAN) were prepared through the oxidative polymerization of a mixture of aniline, 2,5‐diaminobenzene sulfonic acid, and MWCNTs. Fe, Pd, or Fe–Pd alloy nanoparticles were embedded into the MWCNT–SPAN matrix by the reduction of Fe, Pd, or a mixture of Fe and Pd ions with γ radiation. Sulfonic acid groups and the emeraldine form of backbone units in SPAN served as the source for the reduction of the metal ions in the presence of γ radiation. The existence of metallic/alloy particles in the MWCNT–SPAN matrix was further ascertained through characterization by high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, and conductivity measurements. HRTEM pictures clearly revealed the existence of Fe, Pd, and Fe–Pd nanoparticles of various sizes in the MWCNT–SPAN matrices. There were changes in the electronic properties of the MWCNT–SPAN–M composites due to the interaction between the metal nanoparticles and MWCNT–SPAN. Metal‐nanoparticle‐loaded MWCNT–SPAN composites (MWCNT–SPAN–M; M = Fe, Pd, or Fe–Pd alloy) showed better thermal stability than the pristine polymers. The conductivity of the MWCNT–SPAN–M composites was approximately 1.5 S cm?1, which was much higher than that of SPAN (2.46 × 10?4 S cm?1). Metal/alloy‐nanoparticle‐embedded, MWCNT‐based composite materials are expected to find applications in molecular electronics and other fields. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3355–3364, 2006  相似文献   

6.
A novel method for preparing organosoluble and conducting polyaniline (PANI) is presented. It is demonstrated that Cu(II) is an excellent catalyst for the polymerization of aniline by air oxygen in aqueous emulsions. Reactions carried out at 0 °C or at room temperature yield PANIs of reasonably high molecular weights (number‐average molecular weight = 23,000–114,000 Da) in an emeraldine base form that are soluble in many organic solvents, such as tetrahydrofuran, dimethylformamide, N‐methylpyrrolidinone, chloroform, and acetone. Spectroscopic investigations (ultraviolet, Fourier transform infrared, and 1H NMR) have shown that PANI obtained by this procedure has the same structure as those prepared by the conventional persulfate oxidation method. The resulting PANIs show reasonable electronic conductivities (0.067–0.320 S cm?1) upon doping with p‐toluenesulfonic acid or dodecyl benzene sulfonic acid. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6025–6031, 2006  相似文献   

7.
Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004  相似文献   

8.
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005  相似文献   

9.
DC conductivity of conjugated polymer‐single‐walled carbon nanotube (SWNT) composite films has been measured for different SWNT concentrations. The composite was prepared by dispersing SWNTs in the poly (3‐octylthiophene), P3OT matrix already dissolved in xylene. The conductivity of the composite films showed a rapid increase as the SWNT concentration increases beyond a certain value. This behavior is explained in terms of percolating paths provided by the SWNTs in the volume of polymer matrix. To investigate the effect of length of nanotubes on the percolation conductivity, different SWNT samples were employed with similar diameter but varying tube lengths. It was found that the conductivity of the composite films is strongly dominated by the length of the nanotubes. Lower percolation limit and high conductivity value of composite films is observed for longer nanotubes. Furthermore, the conductivity is observed to be dependent on the size of the host polymer molecule also. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 89–95, 2010  相似文献   

10.
Polyaniline (PAni) films of different intrinsic oxidation states, including emeraldine salt, emeraldine base and leucoemeraldine base, were synthesized. Free‐standing membranes and thin film bilayers of aluminum–polyaniline were fabricated by magnetron sputter deposition of aluminum onto polyaniline films. Aluminum–polyaniline samples were analyzed by transmission electron microscopy (TEM) to investigate the microstructures of specimens, including cross‐sectional TEM micrographs of the metal‐polyaniline interfacial structure not previously reported in the literature. Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS) were employed to study the chemical bonding and interaction between deposited aluminum and polyaniline at the interface. Results indicated that the intrinsic oxidation state of the polyaniline influenced the chemistry of the aluminum–polyaniline interface. Distinct interaction between aluminum and polyaniline in the emeraldine salt‐form was observed. However, there was no evidence of direct interactions of the aluminum with emeraldine base and leucoemeraldine base polyaniline. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

11.
A series of linear‐dendritic hybrid polymers, containing pyrene units at the periphery of aliphatic polyester dendrons, were prepared for the purpose of dispersing shortened single‐walled carbon nanotubes (SWNTs) in tetrahydrofuran (THF). The prepared hybrids contained 1, 2, 4, 8, or 16 (G0 through G4) pyrene units and a linear segment composed of polystyrene. It was found that a minimum of four pyrene units was necessary to form a strong enough interaction with SWNTs to enable steric stabilization in solution, when using a linear polymer segment of 11.5 kDa. Increasing either the number of pyrene units per polymer chain or the length of the polymer segment to 18.0 kDa did not improve nanotube solubility, whereas decreasing the polymer length resulted in significantly less effective nanotube dissolution. The G4 dendron alone, without the linear polystyrene segment, was also found to impart solubility to the nanotubes in THF. Interactions between the series of linear‐dendritic hybrids and full‐length multiwalled carbon nanotubes were also investigated, and it was found that the polymers exhibited strong interactions with the multiwalled carbon nanotube surface, resulting in the formation of stable solutions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1016–1028, 2010  相似文献   

12.
This work is to make carbon nanotubes dispersible in both water and organic solvents without oxidation and cutting nanotube threads. Polystyrene‐singlewall carbon nanotube (PS‐SWNT) composites were prepared with three different methods: miniemulsion polymerization, conventional emulsion polymerization, and mixing SWNT with PS latex. The two factors, crosslinking and surface coverage of PS are important factors for the mechanical and electrical properties, including dispersion states of SWNT in various solvents. The PS‐SWNT composite prepared via a conventional emulsion polymerization showed SWNT bundles entirely covered with PS, whereas the PS‐SWNT composite prepared via a miniemulsion polymerization showed SWNT partially covered with crosslinked PS nanoparticles. The method of mixing SWNTs with PS latex did not show the well dispersed state of carbon nanotubes because PS was not crosslinked and was dissolved in a solvent, and nanotubes separated from PS precipitated. So the PS nanoparticle‐SWNT composite had lower electrical resistance, and higher mechanical strength than the other composites made by the latter two methods. As the amount of SWNT increases, the bare surface area of SWNT increases and the electrical conductivity increases in the composite made by the miniemulsion polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 573–584, 2006  相似文献   

13.
Uniform dispersion and strong interfacial interaction are two critical prerequisites for application of single‐walled carbon nanotubes (SWNTs) in polymer composites. To endow the composites with multifunctional feature, no damage on the chemical/electronic structure of SWNTs is also usually required. With these ends in view, two epoxide‐containing pyrene derivatives (EpPys) were designed, synthesized, and used as reactive noncovalent dispersants for developing multifunctional epoxy/SWNT composites. One having longer chain length between epoxide group and pyrene moiety, that is, EpPy‐16, shows higher dispersing efficiency and provides the nanotube dispersion with better stability, thus picking up for subsequent studies. Systematic characterization on SWNT/EpPy‐16 hybrid demonstrates that 13.2 wt % of EpPy‐16 is adsorbed on the SWNT surface through strong π‐stacking interaction, and intrinsic electronic structure of SWNTs is basically reserved. The solution‐based process adopted here preserves the good SWNT dispersing state in dispersion into the composites. Simultaneously, enhanced interfacial interaction is also realized by using EpPy‐16, which interacts noncovalently with SWNT but connects covalently to epoxy network. As a result, the composites acquire 37 and 22% increments in tensile strength and Young's modulus, respectively, relative to that of neat resin. A low‐electrical percolation threshold of 0.1 wt % SWNTs and improved thermal properties were also observed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

14.
We previously showed that in N,N‐dimethylformamide (DMF), poly(9‐anthracenylmethyl methacrylate) (PAMMA) and poly(2‐naphthylmethacrylate) selectively disperse semiconducting and metallic single‐walled carbon nanotubes (SWNTs), respectively. We have also proposed a new noncovalent polymer interaction based on photon induced dipole–dipole interaction to account for the metallicity‐based selectivity. In this article, we investigate two other polymethacrylates, that is, poly(benzyl methacrylate) (PBMA) and poly(methylmethacrylate)‐co‐(9‐anthracenylmethyl acrylate) (PMMA‐c‐PAMA) in the light of our previously proposed photon‐induced dipole–dipole interaction. We find that PBMA and PMM‐c‐PAMMA in DMF show no metallicity selectivity. The different selective behavior of the four polymers in DMF manifests the decisive influence of the side aromatic group in determining their metallicity selectivity. The nonpreferential energy transfer from PMMA‐c‐PAMA to SWNTs and the nonoverlap of PBMA fluorescence (in the ultraviolet range) with nanotube absorption account for their nonselectivity of specific nanotube species. Further, the parallel relationship between the diameters of extracted tube species and the affinity between polymers and solvents suggests the leading role of the polymeric conformation on the diameter selectivity. A sufficient (i.e., 2 weeks) standing time of the SWNTs solution after sonication, during which the polymers presumably optimize their conformation to the SWNTs, was found to be essential to the enrichment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

15.
While high shear alignment has been shown to improve the mechanical properties of single‐wall carbon nanotube (SWNT)‐polymer composites, this method does not allow for control over the electrical and dielectric properties of the composite and often results in degradation of these properties. Here, we report a novel method to actively align SWNTs in a polymer matrix, which permits control over the degree of alignment of the SWNTs without the side effects of shear alignment. In this process, SWNTs were aligned via AC field‐induced dipolar interactions among the nanotubes in a liquid matrix followed by immobilization by photopolymerization under continued application of the electric field. Alignment of SWNTs was controlled as a function of magnitude, frequency, and application time of the applied electric field. The degree of SWNT alignment was assessed using optical microscopy and polarized Raman spectroscopy, and the morphology of the aligned nanocomposites was investigated by high‐resolution scanning electron microscopy. The structure of the field induced aligned SWNTs was intrinsically different from that of shear aligned SWNTs. In the present work, SWNTs are not only aligned along the field, but also migrate laterally to form thick, aligned SWNT percolative columns between the electrodes. The actively aligned SWNTs amplify the electrical and dielectric properties of the composite. All of these properties of the aligned nanocomposites exhibited anisotropic characteristics, which were controllable by tuning the applied field parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1751–1762, 2006  相似文献   

16.
Grafting of aldehyde structures to single‐walled carbon nanotubes (SWNTs) has been carried out to endow the nanotubes with appropriate wettability. The results of Fourier transform infrared (FTIR) spectroscopy, ultraviolin‐visible‐near infrared (UV‐VIS‐NIR) spectroscopy, and Raman spectroscopy provide the supporting evidence of aldehyde structures covalently attached to SWNTs. The improved wettability of aldehyde‐functionalized SWNTs (f‐SWNTs) was demonstrated by their good dispersion in organic medium, namely, ethanol and phenolic resin. The prospective covalent bonding between aldehyde structures on the surfaces of f‐SWNTs and phenolic resin makes it possible to prepare an integrated composite with the enhanced‐interfacial adhesion. The f‐SWNT composites, therefore, show much higher average values of dσ/dWCNT and dE/dWCNT (i.e., tensile strength and Young's modulus per unit weight fraction) compared with the composites filled with pristine SWNTs or MWNTs. The respective maxima are 9680 MPa and 320 GPa. It is thus feasible for f‐SWNTs to prepare the moderately enhanced but lightweight phenolic composites. Furthermore, the incorporation of f‐SWNTs does not limit the application of phenolic resin as insulation material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6135–6144, 2009  相似文献   

17.
We designed and synthesized 4‐dodecyloxybenzenediazonium tetrafluoroborate ( 1 ), which preferentially reacts with metallic single‐walled carbon nanotubes (SWNTs) by kinetic control. We first determined the suitable experimental conditions for the preferential reaction of 1 with individually dissolved SWNTs by monitoring the decrease in absorbance for the metallic SWNT in the range of 400–650 nm in the absorption spectrum of the SWNTs. The reacted SWNTs were thoroughly rinsed with THF to obtain THF‐insoluble SWNTs. The Raman spectrum of the THF‐insoluble SWNTs showed a strong peak near 180 cm?1, which corresponds to a semiconducting breathing band. The metallic breathing bands (≈220 cm?1) and Breit–Wingner–Fano (BWF) modes (1520 cm?1) corresponding to the metallic SWNTs were much weaker than those of the pristine SWNTs. We also confirmed that metallic peaks in the range of 400–650 nm in the absorption spectrum of THF‐insoluble SWNTs that were individually dissolved in an aqueous micelle of sodium cholate were almost nondetectable. All the results indicate that the THF‐insoluble SWNTs are semiconducting.  相似文献   

18.
Crystallization of oligomers was applied for the preparation of single‐walled carbon nanotubes (SWNTs)/poly(p‐oxybenzoyl) (POB) crystals using SWNTs as a nucleating agent. Polymerization conditions were investigated to induce the crystallization of POB oligomers through SWNTs. SWNTs/POB plate‐like or lozenge‐shaped crystals were successfully prepared by direct polymerization of p‐hydroxybenzoic acid (HBA) in a mixed solvent of DMF/Py with TsCl in the presence of functionalized SWNTs. The size of the plate‐like crystals were ~200 nm to 3 μm. The crystals consisted of some layers, ~3 nm thick plates. Model reactions showed that esterification reactions proceed between functionalized SWNTs and HBA monomers in the polymerization system. The obtained crystals exhibited unique morphology and high crystallinity, producing a novel SWNT/POB hybrid. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1265–1277, 2008  相似文献   

19.
Single‐walled carbon nanotubes (SWNTs) possess extraordinary properties, but suffer from poor solubility and a lack of purity. Of the possible routes available to solubilize and purify nanotube samples, the use of noncovalent functionalization is ideal as carbon nanotube properties are not deleteriously affected. A multitude of different dispersants have been investigated thus far, but of particular interest is deoxyribonucleic acid (DNA), which has previously been demonstrated to effectively separate metallic and semiconducting carbon nanotubes. Here, we investigate the ability of synthetic nucleobase‐containing poly(acrylamide) polymers to produce stable nanotube dispersions in organic solvents. Polymers bearing different nucleobase and backbone structures, as well as block copolymers with different block sequences were investigated. Polymer:SWNT mass ratios and solvent compositions were optimized for the nucleobase‐functionalized polymers, and semiconducting and metallic SWNT populations were identified by a combination of UV‐Vis‐NIR absorption, Raman, and fluorescence spectroscopy. These results demonstrate the capacity for synthetic DNA analogues to disperse SWNTs in organic media. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2611–2617  相似文献   

20.
Poly(ethylene glycol) (PEG) was modified with aniline groups at both the end, and then PEG‐PANI rod‐coil block polymers have been synthesized by polymerization of the aniline with the aniline‐modified PEG. FTIR, NMR, and elemental analysis provided the chemical strucutre of the as‐prepared polymers. The achiral rod‐coil copolymer could form different superstructures by means of self‐assembly when adding diethyl ether into its THF solution and the length of PANI segments is a key factor to the superstructures. AFM measurements revealed that they form spring‐like helical superstructures from the short PANI‐containing copolymers while these form fibrous helical superstructures from the longer PANI‐containing copolymer. A possible mechanism of the helical superstructures is suggested in this article and the driving force is believed the π–π stacking of the rigid segment of the copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 12–20, 2008  相似文献   

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