十二烷基苯磺酸掺杂聚苯胺的制备及性能

用十二烷基苯磺酸（DBSA）的水溶液对化学合成的聚苯胺（PAn)进行掺杂,获得了导电的DBSA掺杂PAn(PAn-DBSA),通过对本征态聚苯胺（PAnEB)掺杂率的计算和电导率的测定,研究了DBSA用量及其溶液浓度对掺杂效果的影响,结果表明,当DBSA／PAnEB(摩尔比）小于0．1时,溶液浓度的影响很小,当DBSA／PAnEB大于0．2时,溶液浓度的影响非常大,而且,高浓度比低浓度对提高掺杂率和电导率更有利。热重分析表明,PAnEB,PAn-DBSA在空气中的热分解温度分别为350和250℃,表现出良好的热稳定性。     

Fabrication and properties of solution‐cast polyaniline/carboxymethylchitin blend films

Blend films consisting of polyaniline in emeraldine base form (PANI EB) dispersed in partially cross‐linked carboxymethylchitin (CM‐chitin) were prepared by solution casting, and characterized for their physical, thermal, and electrical properties. Homogeneous and mechanically robust blend films were obtained having PANI EB contents up to 50 wt % in the CM‐chitin matrix. FTIR spectra confirm intimate mixing of the two blend components. The thermal stability of the blend films increased with increase of PANI EB content, suggesting the formation of an intermolecular interaction, such as hydrogen bonding, between PANI EB and CM‐chitin chains. The addition of PANI EB into the pure CM‐chitin film resulted in a decrease in electrical conductivity of the films owing to disruption of ionic conduction of the CM‐chitin structure. After doping the blend films by immersion in HCl solution, the electrical conductivity of the HCl‐doped films increased with increase of the PANI EB content to a maximum value of the order of 10^?3 S/cm at 50 wt % PANI EB content. The electrical conductivity of the blend films was also dependent on the HCl concentration as well as on the type of acid dopant. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of polyaniline and studying its electrical conductivity

Polyaniline was prepared by chemical methods. Its electrical conductivity was measured. The electrical conductivity of polyaniline salt and polyaniline base were compared with composites prepared by the hot press of polyaniline base with KBr, Co(CH₃COO)₂, and picric acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1658–1665, 2000     

Studies of AC conductivity and dielectric relaxation behavior of CdO‐doped nanometric polyaniline

The Cadmium oxide doped in nanocrystalline polyaniline (CdO/PANI) composite were prepared with various weight percentages by in situ polymerization method using aniline, ammonium per sulfate, and CdO as starting materials. The frequency dependent conductivity and dielectric behavior of PANI/CdO composites have been studied. The formation of nano PANI and PANI/CdO composites with regards to the structural and microstructural properties of the materials were investigated by XRD, FTIR, and SEM techniques. The variation of σ_ac with frequency obeys Jonscher power law except a small deviation in the low frequency region and is due to dipole polarization effect. The σ_ac increases with increase in CdO concentration. Studies of dielectric properties at lower frequencies show that the relaxation behavior is superimposed by dipole polarization effect. The appearance of peak for each concentration in the loss tangent suggests the presence of relaxing dipoles in the PANI/CdO composite. On addition of CdO, the peak shifts toward higher frequency side indicating the speed up of the relaxation time. Analysis of frequency dependent dielectric suggests that the electronic and polymer segmental motions are strongly coupled. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on Fourier transform infrared spectroscopy,scanning electron microscope,and direct current conductivity of polyaniline doped zinc ferrite

In situ polymerization of aniline was carried out in the presence of zinc ferrite to synthesize polyaniline/ZnFe₂O₄ composites (PANI/ZnFe₂O₄) by chemical oxidation method. The composites have been synthesized with various compositions (10, 20, 30, 40, and 50 wt %) of zinc ferrite in PANI. From the Fourier transform infrared spectroscopy (FTIR) studies on polyaniline/ZnFe₂O₄ composites, the peak at 1140 cm⁻¹ is considered to be measure of the degree of electron delocalization. The surface morphology of these composites was studied with scanning electron micrograph (SEM). The dc conductivity has been studied in the temperature range from 40–160°C and supports the one‐dimensional variable range hopping (1DVRH) model proposed by Mott. The results obtained for these composites are of scientific and technological interest. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal dynamic processing of polyaniline with dodecylbenzene sulfonic acid

To attain an intrinsically conductive and processible polymer, polyaniline (PANI)/dodecylbenzene sulfonic acid (DBSA) blends of several compositions were processed at various elevated temperatures in a Brabender plastograph. The blends' temperatures during processing, as affected by the blends' composition and initial process temperature, were monitored. Accordingly, the process includes the following main stages: heating the blend, exothermic PANI-DBSA doping reaction accompanied by a paste to a solidlike transition, and plasticization of the resulting PANI/DBSA complex by the excess DBSA. Composition analysis of the process products sampled at the various stages showed that the initial blends, prior to their thermal processing, already consisted of partially doped PANI particles, having a core/shell structure; the core consists of PANI_base and the shell of PANI(DBSA)_0.32 complex. In addition, at the paste-to-solidlike transition, the doping reaction is completed; further mixing does not affect the complex composition, but results in conductivity reduction. The morphology of the blends sampled at the various processing stages was studied by electron microscopy. From the conductivity and processibility point of view, optimal PANI/DBSA blend composition and processing temperature were identified. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2199–2208, 1997     

过氧化钨酸-过氧化氢化学聚合法合成掺杂态聚苯胺

在过氧化钨酸-过氧化氢均相催化氧化体系中,在盐酸或对甲基苯磺酸的存在下合成出掺杂态聚苯胺(PANI/HCl和PANI/TSA)。反应终了后,加入碘化钾除去体系中剩余的过氧化氢。产物分离过程中,使用了抽滤法与甲苯-水共沸蒸馏法两种方法。与抽滤法相比,用共沸蒸馏法处理反应后的产物能得到高产率的掺杂态聚苯胺。使用傅立叶红外吸收光谱(FTIR)和紫外-可见光吸收光谱(UV-vis)研究了两种掺杂态聚苯胺的化学构造变化。使用四端子法测定了掺杂态聚苯胺的导电性能,其导电率能达到10-3S/cm数量级。     

微乳液法制备导电聚苯胺的研究

采用微乳液法制备了导电聚苯胺 ,并详细讨论了聚合温度和氧化剂用量对聚苯胺粒子的粒径、导电性能和分子结构等影响     

Effect of annealing on electrical conductivity and morphology of polyaniline films

We report structure–property relationships of polyaniline emeraldine base (EB) films that were produced by combining different processing steps in various sequences. The effect of annealing and doping processes on the surface structure of the films was investigated by atomic force microscopy (AFM), and the corresponding changes to the chemical structure of the EB films were monitored by Fourier transform infrared spectroscopy. AFM results indicate that after doping polyaniline (EB) films with HCl, the root mean square (rms) roughness of the surface of EB film increased ～ 46%. When the doped films were annealed at 180°C under a nitrogen atmosphere for 3 h, the rms roughness was essentially unchanged from that of the initial, undoped films. The electrical conductivity of the films also showed a significant dependence on the processing sequence. When the doped polyaniline (EB) films were annealed, no electrical conductivity was observed. When these films were redoped, only ～ 6% of the initial conductivity could be recovered. In another processing sequence in which the polyaniline (EB) films were first annealed and then doped, the electrical conductivity was only ～ 12% relative to the film that was doped immediately after being cast. From this work, a strategy to reduce the surface roughness of films made from electrically conducting polyaniline (EB) is proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3602–3610, 2001     

Electroanalytical studies on electrically conducting polyaniline:polyethyleneterephthalate composite films

Polyaniline (PANI):polyethyleneterephthalate (PET) composite was prepared by chemical polymerization of aniline diffused in the PET matrix. Thus prepared composite films were characterized by fourier‐transform infrared spectroscopy and scanning electron microscopy and their electrical properties and the thermo‐oxidative stability was studied by thermogravimetry and differential thermal analysis. The stability in terms of DC electrical conductivity retention was studied in an oxidative environment by two slightly different techniques viz. isothermal and cyclic techniques. DC electrical conductivity of composite films was found to be stable up to 90°C for most of the composites under ambient conditions. The composite films were employed as cathode material in secondary cells containing 1M ZnCl₂ solution. The studies were carried out on the charge/discharge cycles under a constant current load 140 mA. The composite films showed similar behavior in electrolyte solution and cell response is reversible. To determine the diffusion coefficient for the chloride ions diffusion into the composite films electrochemically, galvanostatic pulse method was used. The diffusion coefficient was estimated to be ～ 3.28 × 10^?12 cm² s^?1. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of thermal aging on electrical conductivity of the 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid‐doped polyaniline fiber

The thermal characteristics of inherently conductive polyaniline (PANi) fiber have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Fibers show five major weight losses at ∼100°C, 165°C, 215°C, 315°C, and 465°C, which are associated with the removal of moisture, residual solvent, decompositions of the sulfonic acid and degradation of PANi fiber, respectively. The 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPSA) that dopes the PANi (in fiber form) performs two‐stage decompositions. The conductivity of the drawn fibers aged at 50°C, 100°C, 150°C, and 190°C under vacuum for various periods of time decreases, particularly at temperatures higher than 100°C. The reduction in conductivity of the fiber aged at temperatures lower than 100°C is mainly due to the evaporation of the residual solvent (15–20% in the as‐spun fiber). Further decrease in conductivity of the fiber aged at temperatures higher than 100°C is caused by the decomposition of the dopant AMPSA. The temperature‐dependent conductivity of the fiber was measured at 15 K (−258.5°C) to 295 K (21.5°C). The conductivity of both aged and un‐aged fibers is all temperature activated, however, the conductivity of the un‐aged fibers is higher than that of the aged fibers. Although a negative temperature coefficient was observed in the temperature range from 240 K (–24.5°C) to 270 K (–3.5°C) for the un‐aged fibers, it was disappeared when the fibers were thermal aged at 100°C for 24 h in vacuum oven. These results indicate that the residual solvent trapped inside the fiber enhanced the electrical conductivity of the fibers and its “metallic” electrical conductivity at temperatures ∼263 K (–10°C). © 2001 John Wiley & Sons, Inc. † J Appl Polym Sci 79: 2503–2508, 2001     

Optical and conductivity studies of Pseudo‐doped chitin‐polyaniline blend

In this article, we report the preparation and characterization of self‐doped conducting chitin, polyaniline blends by solution blending method. The characterization of the blends was done by UV–vis absorption spectrum, FTIR, and conductivity studies. Conductivity of the self doped blends increases from less than ～10^?7 S/cm to 2.15 × 10^?5 S/cm, depending on the percentage of polyaniline in the blend. Spectroscopic analysis shows interaction between chitin and polyaniline and the electronic states are similar to those of the emeraldine and protonically doped forms of polyaniline. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhanced conductivity and fluorescence of polyaniline doped with Eu3+, Tb3+, and Y3+ ions

The doped polyaniline (PANI) with rare earth ions, which exhibits an increasing conductivity and strongly enhanced fluorescence emission, was prepared by dispersing PANI powder suspension in acetonitrile solution containing rare earth ions according to different mass ratios of rare earth ions to PANI at room temperature. The structure of the doped PANI was characterized by the spectra of FTIR, Raman, UV-vis, and XRD. Red-shifted change for the quinoid and benzenoid stretching vibration is observed in IR and Raman spectra after doping rare earth cations, and UV-vis absorption peak also presents a red-shift, indicating that the doped PANI possesses a better delocalization of electrons along the mainchain backbone. The experimental data show that the electrical and optical behaviors of PANI strongly depend on the species of rare earth cations and their concentration. It is found that enhancing fluorescence for the doped PANI is observed by comparing with emeraldine base (EB). Moreover, the conductivity of the protonated PANI samples doped with Eu³⁺, Tb³⁺, and Y³⁺ ions, increases from 2.1 × 10⁻⁴ to 3.33 S cm⁻¹, 1.50 × 10⁻¹ S cm⁻¹ and 2.26 × 10⁻¹ S cm⁻¹. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and electrical conductivity of polyaniline derivatives: Study with the metal ions Cu(II), Ni(II), and Co(II)

Poly(2-aminophenol), poly(3-aminophenol), poly(2-aminobenzyl alcohol), and poly(3-aminobenzyl alcohol) were synthesized by using ammonium persulphate as oxidizing reagent in HCl and HCl/CH₃CN mediums in the presence and absence of Cu(II), Ni(II), and Co(II) ions. The polymers were characterized by Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy, thermal analysis, and electrical conductivity measurements. The substituent in 2- and 3-positions decreases the yield regarding aniline. Poly(2-,3-aminobenzyl alcohol) are obtained in an intermediate redox state and polymerized as aniline. On the contrary, poly(aminophenols) are obtained as overoxidated structures. The presence of metal ion produces an important increase of the polymerization yield. The metal cations would act as oxidizing agents. The incorporation of these metal ions depends on the reaction medium. The metal ion increases the thermal stability. Poly(2-aminobenzyl alcohol)-copper ions also increases the electrical conductivity. The electrical conductivity is higher by acid doping than by the incorporation of metal ions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 330–337, 2001     

Acrylic acid‐doped polyaniline sensitive to ammonia vapors

Acrylic acid and HCl‐doped polyanilines were synthesized by chemical oxidative polymerization. The synthesized materials were used as sensors for ammonia. Comparison of the responses of the two polymers reveal that the acrylic acid‐doped polymer exhibits higher sensitivity and reversibility. Further, the resistance is observed to decrease on exposing the acrylic acid‐doped polyaniline to saturated ammonia vapors. A reversed trend is observed in the case of HCl‐doped polyaniline. The results are explained in terms of the differences in the chemical interactions of the two polymers with respect to ammonia vapors. The proposed mechanism is further supported by the X‐ray diffraction and FTIR analysis. The X‐ray diffractogram of acrylic acid‐doped polymer shows an enhancement in the crystallinity on exposure to ammonia vapors, while the HCl‐doped polymer exhibits a loss in crystallinity. The FTIR spectra shows a higher doping level in acrylic acid doped polymer as observed from the intense peak of the dopant ion at 1158 cm⁻¹, which is seen to be shifted to a lower wavenumber i.e. ∼1128 cm⁻¹ on exposing the polymer to ammonia vapors. On the other hand, in HCl‐doped polyaniline, the peak of the dopant ion ∼1120 cm⁻¹ is initially less intense, which is further suppressed on exposure to ammonia. Conductivity measurements show a large vapor‐induced increase in conductivity, in the case of ammonia‐exposed acrylic acid‐doped polyaniline, which results in the formation of a more crystalline‐conducting phase. Exactly the opposite results were obtained in the case of HCl‐doped polyaniline exposed to ammonia. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1994–1998, 2001     

A facile method for synthesis of polyaniline nanospheres and effect of doping on their electrical conductivity

The synthesis of polyaniline (PANI) nanospheres by a simple template-free method has been described. The polymerization of aniline in aqueous medium was accomplished using ammonium persulfate without any protonic acid. The UV-vis spectrum of PANI nanospheres displayed the characteristic absorption peak of π-π* transition of the benzenoid ring at 355 nm. The oxidation state of PANI nanospheres was identified with FT-IR spectroscopy by comparing the two bands at 1582 (ring stretching in quinoid unit) and 1498 cm(-1) (ring stretching in bezenoid unit). The X-ray diffraction patterns demonstrated the low crystalline nature of PANI nanospheres. The morphology of PANI nanospheres was spherical and the mean diameter of nanospheres was found in the range of 3-12 nm. The thermal behavior of PANI nanospheres was studied by thermogravimetric analysis. The effect of doping of HCl and H(2)SO(4) on PANI nanospheres was studied by measuring the current as a function of time of exposure. The high electrical conductivity of 6×10(-2) S cm(-1) was obtained for PANI nanospheres at their optimum doping state by 100 ppm HCl.     

Effect of drying conditions on microwave conductivity of polyaniline

Polyaniline was synthesized by using ammonium persulfate initiator in the presence of 1M HCl. It was dried under different drying conditions like room temperature drying (for 48 h), oven drying (at 50–60°C for 8 h under a vacuum), and vacuum drying (at room temperature for 16 h). The conductivities of these samples were measured at microwave frequencies. These samples were also pelletized and the measurements were repeated. The cavity perturbation technique was used for the study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2008–2012, 2002     

聚苯胺及其复合材料研究现状

对聚苯胺的结构、合成及其机理、质子酸掺杂 ,聚苯胺的应用 ,以及聚苯胺复合材料的研究现状进行了综合阐述 ,并详细介绍了有关煤基聚苯胺的研究情况。煤基聚苯胺和纯聚苯胺相比 ,电导率下降不大 ,而且成本降低、热稳定性增强 ;同时 ,煤基聚苯胺也为煤的非能源利用提供了新途径和新机遇 ,具有一定的推广价值。     

Electrical conductivity and mechanical properties of polyaniline/natural rubber composite fibers

Electrically conducting elastomer fibers based on natural rubber (NR) and up to 10% w/w polyaniline (PANI) in its emeraldine base (EB) form were fabricated by a wet spinning process. The resulting fibers at various PANI contents were doped by immersion in aqueous HCl solution, which converted the PANI to the electrically conductive emeraldine salt (ES) form. The morphology of the composite fibers was studied by scanning electron microscopy (SEM). PANI particles were inhomogeneously distributed in the NR matrix. The electrical conductivity of the fibers increased with the increasing PANI‐ES content and leveled off at a value of around 10^?3 S/cm at PANI‐ES concentration of 5% w/w. The fibers retained most of their elasticity upon doping, while the tenacity was somewhat reduced. Gratifyingly, the electrical conductivity of the new elastomer fibers was preserved upon elongational deformation, even if strains as large as 600% were applied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

不同酸掺杂聚苯胺的电化学聚合及性能

采用循环伏安（CV）法在镀金PET膜上分别聚合了硫酸（H2SO4）、十二烷基苯磺酸（DBSA）、硫酸-十二烷基苯磺酸掺杂的聚苯胺（PANI）膜,对比研究了掺杂酸种类对PANI结构和性能的影响。结果表明,SO42?、DBSA?可以随聚合过程进入PANI分子链;H2SO4掺杂的PANI具有较高的电导率,但是在空气中的稳定性较差;大分子的DBSA使PANI优先产生单螺旋的纤维,提高了PANI在平行分子链方向上的结晶度和在空气中的稳定性;相对于单一酸掺杂,复合酸掺杂的PANI在酸溶液中电扫描表现出优良的循环伏安特性,在保持较高电导率的同时,提高了PANI在空气中的稳定性。