Novel conducting polyaniline blends with cyanoresin

Novel conducting polyaniline (PANI)/cyanoresin (Cyan) blends were prepared by the addition of Cyan/dimethylformamide solutions to aniline monomer/dopant solutions and the in situ chemical oxidative polymerization of aniline with ammonium persulfate as an oxidant in aqueous p‐toluene sulfonic acid solutions. The PANI/Cyan blends were prepared with various compositions (5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, and 70:30), and blend films of PANI/Cyan were obtained with a casting method. The conductivity of the PANI/Cyan blend films was 10^?7 to 10^?2 S/cm, which was measured by a four‐probe technique. The tensile strength of the blend films was maintained with an increasing amount of PANI (up to 50 wt %), and this was attributed to intermolecular interactions such as hydrogen bonding between PANI and Cyan and a reinforcing effect through blending. This hypothesis was corroborated by Fourier transform infrared spectroscopy. Field emission scanning electron microscopy and thermogravimetric analysis were also used to investigate the morphology and thermal properties of the conducting PANI/Cyan blend films, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1035–1042, 2005     

Shrinking rate of conducting grains in HCl–protonated polyaniline,polypyrrole, and polypyrrole/polyaniline blends with their thermal aging

The dc electrical conductivity (σ) of HCl‐protonated polyaniline, polypyrrole, and their blends was measured from 80 to 300 K for thermal aging times between approximately 0 and 600 h. The thermal aging took place at 70°C under room atmosphere. The change of σ with the temperature (T) and the decrease of σ with the thermal aging time (t) are consistent with a granular metal type structure, in which conductive grains are randomly distributed into an insulating matrix. Aging makes the grains shrink in a corrosion‐like process. From σ = σ(T) measurements the ratio s/d, where s is the average separation between the grains and d their diameter, as well as the rate d(s/d)/dt of their decrease with t were calculated. These revealed that the conductive grains consist of a shell, in which aging proceeds at a decreasing rate, and a central core, which is consumed at a much slower rate. Our measurements not only permitted the estimation of the shell thickness, which lies between 0 and 5 Å, but also gave quantitative information about the quality of the shells and the cores from their aging rates. The shells are consumed with an average rate of d(s/d)/dt = 6.6 × 10^?4 (h^?1), which is about 5 times greater than the more durable cores. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 117–122, 2005     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Study of polyaniline polyacrylamide composites by positron annihilation technique

Polyaniline doped with nonoxidizing Bronsted acids is recognized as a conducting material, as its electrical conductivity changes with percentage of doping. In the present work, different percentages of doped polyaniline were blended with polyacrylamide and their electrical conductivities as well as the positron annihilation lifetimes were measured. Analysis of data yielded three lifetime components. It was observed that the value of the short lifetime component remained constant for doping concentration, whereas that of the intermediate component τ₂ decreased. The relative intensity pertaining to τ₂, however, increased with the increase in doped PANI concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 930–933, 2003     

Conducting polymer blends prepared from polyaniline with n-dodecylbenzenesulfonic acid zinc salt as the secondary dopant

A red-shift of the UV–vis spectra of n-dodecylbenzenesulfonic acid doped polyaniline (PANI (DBSA)_0.5), resulting from the secondary doping of polyaniline backbones, was found in the presence of n-dodecylbenzenesulfonic acid zinc salt (Zn(DBS)₂). It is proved to behave as steric hindrance spacers to induce the extension of the conjugation length through the straightening effect on the polyaniline backbones and the obtained mixtures (PANI(DBSA)_0.5 plus Zn(DBS)₂) can be used as master batch materials (MB-13) for blending with regular polypropylene polymer (PP). The thermal degradation accompanied with loss of conductivity for MB-13 can be delayed to over 250°C when enough Zn(DBS)₂ was secondarily doped on PANI(DBSA)_0.5., which allow the performance of its blending with other nonconducting/regular polymers possible. Below 80 rpm, increasing shear rates would induce higher viscosity difference between the MB-13 and PP matrix, resulting in elongation of MB-13 in the PP matrix and higher conductivities of the polyblends. The deviation from the Taylor equation, which is used to estimate the degree of elongation for a polyblend, started when shear rate is over 80 rpm. The leakage of Zn(DBS)₂ out of MB-13 can be confirmed by comparing the DSC thermograms and X-ray diffraction patterns with that of neat PP. Gradual deformation for the conductive fillers (MB-13) and a well-defined and expanded layered structure can be found when processing time is below 15 min with 60 rpm shear rate. The layers started to shrink back after 15 min of procession with the loss of the Zn(DBS)₂ from MB-13 in the PP matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical and structural analysis of conductive polyaniline/polyimide blends

Conducting films of dodecylbenzenesulfonic (DBSA)‐doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X‐ray diffraction technique, thermal analysis, a UV‐vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA‐doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI–camphorsulfonic acid/polyamic acid (PANI–CSA/PAA). A well‐defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2169–2178, 1999     

Reactive processing and evaluation of butadiene–styrene copolymer/polyaniline conductive blends

Blending is an important way to obtain materials based on intrinsically conductive polymers and conventional plastics and rubber materials. Much research has been carried out to determine the best performance of materials be used for electrostatic dissipation and electromagnetic interference shielding. Mechanical mixing, codissolution, and in situ polymerization have been used to prepare these materials. The method used depends on the host polymer and its thermal stability and acid attack resistance. Homogeneity and miscibility are properties that should be controlled during blend preparation. In this study, we prepared a conductive thermoplastic elastomer material based on butadiene–styrene copolymer (SBR) and polyaniline (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and poly(styrene sulfonic acid) (PSS). PSS also acted as compatibilizer between PANI and SBR. PANI was doped by reactive processing with DBSA and PSS to produce the conductive complex PANI–DBSA–PSS. This complex was mixed with 90, 70, and 50% (w/w) SBR in a counterrotatory internal mixer. Conductivity tests, swelling studies, thermal analysis, and mechanical property and reflectivity testing were done, and the results show a strong dependence on PANI concentration and the ratio between PANI–DBSA and PSS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 681–685, 2006     

Dielectric behavior of PVDF/POMA blends that have a low doped POMA content

The real (ε′) and imaginary (ε″) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o‐methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA–TSA were determined in the frequency interval between 10² and 3 × 10⁶ Hz and in the temperature range from ?120 up to 120°C. It was observed that the values of ε′ and ε″ had a greater increase with the POMA–TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA–TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell–Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA–TSA in the blends. A strong decrease was observed in POMA–TSA conductivity in the blend, which was bigger the lower the POMA–TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 752–758, 2003     

Dependence of the electrical conductivity and elastomeric properties on sample preparation of blends of polyaniline and natural rubber

Blend films (free‐standing) containing 20% in volume of polyaniline (PANI) in 80% of natural rubber (NR) were fabricated by casting in three different ways: (1) adding PANI‐EB (emeraldine base) dissolved in N‐methyl‐2‐pyrrolidone (NMP) to the latex (NRL), (2) adding PANI‐EB dissolved in m‐cresol to NR dissolved in xylol (NRD), (3) overlaying the surface of a pure NR cast film with a PANI layer grown by in situ polymerization (NRO). All the films were immersed into HCl solution to achieve the primary doping (protonation) of PANI before the characterization. The main goal here was to investigate the elastomeric and electrical conductivity properties for each blend, which may be applied as pressure and deformation sensors in the future. The characterization was carried out by optical microscopy, dc conductivity, vibrational spectroscopy (infrared absorption and Raman scattering), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile stress–strain curves. The results suggest that the NRL blend is the most suitable in terms of mechanical and electrical properties required for applications in pressure and deformation sensors: a gain of conductivity without losing the elastomeric property of the rubber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1498–1503, 2005     

X-ray photoelectron spectroscopy of conducting polyaniline and polyaniline–polystyrene blends

Conductive polyaniline solutions were chemically prepared using bis (2-ethylhexyl) hydrogen phosphate (DiOHP) as the dopant chemical species. The codissolution method leads to conductive polyaniline–polystyrene (PANI–PSt) composites with good mechanical properties. The electronic structure of both conducting PANI films and PANI–PSt blends was investigated by X-ray photoelectron spectroscopy, which allowed one to quantify the proportion of benzenoid amine, quinoid imine, and protonated units. Blending polyaniline with PSt does not involve important modifications in the polymer electronic structure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1209–1214, 1998     

Selective recognition of chloroacetic acids by imprinted polyaniline film

A novel conductive imprinted polyaniline (PAN) film is prepared by adding template during the PAN film preparation. Monochloroacetic acid (MCA) and trichloroacetic acid (TCA) were used as templates. The conductivity of imprinted PAN films was measured by the four‐point probe method. The conductivity changes of imprinted PAN films were compared to reference PAN reflecting the MCA and TCA specific sites on the surface of PAN films. The conductivities were linearly dependent on the template concentrations, and linear calibration curves were obtained in the range 1–30 and 1–40 ppm of the MCA and TCA, respectively. Excellent method reproducibility (standard deviation 0.04 S/cm⁻¹) was observed for the determination of 15 ppm MCA. The effect of various factors on preparation, properties, and recognition effects of the imprinted PAN films was investigated. The best electrical and mechanical properties were obtained with 7 × 10⁻⁴ mmol MCA as a template and doping agent. The measurements are carried out under room temperature, and the maximum conductivities are reached after about 10 and 20 min for reference and imprinted PAN film, respectively. Selectivity experiments were carried out with standard MCA, TCA, and five analogs (dichloro‐, dibromo‐, and monobromoacetic acid) in water. The results exhibited a good selectivity for the templates compared to structurally related compounds. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of polyaniline powder synthesized on microstructured aluminium

Aluminium surfaces were microstructured in 0.1 M HNO₃ by potentiodynamic anodic activation to potentials generating pitting. This surface was then used as an electrode to prepare polyaniline powder. The number of pits is responsible for the amount of powder produced. Emeraldine salt powder was successfully prepared from 0.4 M aniline in 0.5 M H₂SO₄ solution. Other acid solutions for deposition are not convenient because powders are electrochemically inactive (e.g., in 1 M HNO₃) or the electrode is covered by a film (e.g., in 0.5 M H₂C₂O₄).     

Electrochromic properties of chemically prepared polyaniline

The electrochromic properties in non-aqueous medium of chemically prepared polyaniline films proved not to depend on the oxidizing agent used for the synthesis and were very similar to the properties of electrochemically prepared films. These properties were studied by measuring the optical contrast changes at fixed wavelengths in the uv/visible region during cyclic voltammetric scans and by applying 7 × 10³–8 × 10³ redox potential steps.     

Physical properties of PVA/PSSNa blends

Blends of conductive polymers with conventional nonconductive ones have, together, the virtues of good electroconductivity and good mechanical properties, whose prospect for electronic industrial application is very good. We prepared poly(vinyl alcohol) (PVA)–sodium polystyrene–sulfonate (PSSNa) blends through aqueous solution casting; the films are flexible and transparent, with electroconductivity that could reach 10^?5 S/cm. The dependence of the electroconductivity on the weight fraction of PSSNa was found to follow the percolation theory. A general discussion is given on the factors that could influence the percolation threshold and the exponent. The films are stable in a 30% KOH solution and keep their conductivity after 10 days' exposure. Some mechanical properties are measured and the best mixing ratio is obtained for future use. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 79–87, 2003     

pH electrodes constructed from polyaniline/zeolite and polypyrrole/zeolite conductive blends

A new type of solid state electrodes sensitive to pH changes is described, in which the chemical‐sensitive layer consists of Pt microparticles deposited on a conducting polymer (polyaniline, polypyrrole) blend containing 22.7% w/w zeolite. These sensors are stable in aqueous electrolyte solutions of low pH value at temperatures up to 45°C with response time in seconds. At 25°C, sensor sensitivity was ?310 ± 40 mV/pH and ?1300 ± 100 mV/pH for polyaniline and polypyrrole blends, respectively. Interferences appear to be acceptably small. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1853–1856, 2006     

复合氧化剂在合成导电聚苯胺中的应用

以苯胺为单体,采用(NH4)2S2O8和抗坏血酸组成的复合氧化剂,在硫酸水溶液中,用化学氧化法直接合成导电聚苯胺。系统地研究了复合氧化剂配比、硫酸的浓度、氧化剂浓度等因素对苯胺聚合反应的影响。结果表明,该方法聚合反应的最佳条件为:在10~25℃的温度范围内,不加氮气保护条件下,苯胺1.0 mol/L,H2SO41 mol/L,(NH4)2S2O81 mol/L,(NH4)2S2O8/抗坏血酸(C6H8O6)的配比为10∶1,合成了电导率达1.33 S/cm、产率达82.17%的聚苯胺。通过红外光谱和X衍射研究了通过不同氧化剂聚合得到聚苯胺的结构变化,结果表明,复合氧化剂氧化聚合得到的聚苯胺结晶比通过过硫酸胺作氧化剂聚合得到的聚苯胺结晶好,并且相应基团在红外光谱上发生红移。     

Electrically conductive,melt-processed polyaniline/EVA blends

Mechanical blends of ethylene–vinyl acetate copolymer and polyaniline doped with dodecyl benzene sulfonic acid (PAni–DBSA) were prepared in a two-roll mill at 50°C and in a Haake internal mixer at 150°C. The effects of the blend composition and processing conditions on the electrical conductivity and mechanical properties were investigated. These blends exhibited high levels of electrical conductivity at a small amount of PAni complex. Blends prepared in a two-roll mill displayed conductivity values as high as 1 S/cm and a higher protonation degree than the pure PAni–DBSA, as indicated by X-ray photoelectron spectroscopy. Two different insulator–conductor transition points were observed in these blends. The mechanical performance decreased as the amount of PAni–DBSA increased, indicating blend incompatibility and a plasticizing effect of the DBSA. The morphology of the blends were studied by scanning electron microscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 114–123, 2001     

Preparation and properties of waterborne polyurethane/polyaniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid blends

A conductive poly(aniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid) [PANI‐D/H, yield: 32.2%, intrinsic viscosity ([η]): 1.39 dL/g, electrical conductivity: 7.3 S/cm] was synthesized by chemical oxidative polymerization from aniline‐dodecylbenzene sulfonic acid salt (A‐DS)/aniline‐hydrochloric acid salt (A‐HS) (6/4M ratio) in an aqueous system. Waterborne polyurethane (WBPU) dispersion obtained from isophorone diisocyanate/poly(tetramethylene oxide)glycol/dimethylol propionic acid/ethylene diamine/triethylene amine/water was used as a matrix polymer. The blend films of WBPU/PANI‐D/H with various weight ratios (99.9/0.1–25/75) were prepared by solution blending/casting. Effect of PANI‐D/H content on the mechanical property, dynamic mechanical property, hardness, electrical conductivity, and antistaticity of WBPU/PANI‐D/H blend films was investigated. The dynamic storage modulus and initial tensile modulus increased with increasing PANI‐D/H content up to 1 wt %, and then it was significantly decreased about the content. With increasing PANI‐D/H content, the glass transition temperature of soft segment (T_gs) and hard segment (T_gh) of WBPU/PANI‐D/H blend films were shifted a bit to lower the temperature. The tensile strength and hardness of WBPU/PANI‐D/H blend films increased a little with increasing PANI‐D/H content up to 0.5 wt %, and then it was dramatically decreased over the content. The elongation at break of WBPU/PANI‐D/H decreased with an increase in PANI‐D/H content. From these results, it was concluded that 0.5–1 wt % of PANI‐D/H was the critical concentration to reinforce those various properties of WBPU/PANI‐D/H blend films prepared in this study. The electrical conductivity of WBPU/ultrasonic treated PANI‐D/H (particle size: 0.7 μm) blend films prepared here increased from 4.0 × 10^?7 to 0.33 S/cm with increasing PANI‐D/H content from 0.1 to 75 wt %. The antistatic half‐life time (τ_1/2) of pure WBPU film was about 110 s. However, those of WBPU/ultrasonic treated PANI‐D/H blend films (τ_1/2: 8.2–0.1 s, and almost 0 s) were found to decrease exponentially with increasing PANI‐D/H content (0.1–9 wt %, and above 9 wt %). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 700–710, 2004     

Synthesis and characterization of polyacrylamide–polyaniline conductive blends

Conducting poly(acrylamide) films were synthesized by exposing the polyacrylamide films impregnated with ammonium peroxodisulphate, an oxidizing agent, to hydrochloric acid vapor and then to aniline vapor. The effects of varying the exposure time to aniline vapor and the resulting composite films of polyacrylamide–polyaniline were characterized by different methods. The mode of conduction has also been studied. The conductivity of the resulting composites reached up to 10⁻⁵ s/cm². © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 841–844, 1998     

Melt/solution processable conducting polyaniline: Elastomeric blends with EVA

Polyaniline (PANI) protonated with dopant, the sulfonic acid of 3‐pentadecylphenoxyacetic acid (SPDPAA; synthesized from an inexpensive naturally existing biomonomer, cardanol), was blended with an elastomeric polymer, the ethylene vinyl acetate (EVA) copolymer. Blending was performed either by emulsion polymerization of aniline into the EVA matrix or by the solution‐mixing method. Thin films were prepared by the conventional melt‐processing technique for an emulsion‐polymerized system and by the solution‐casting method for a solution‐mixed system. In the case of the emulsion‐polymerized system, the percolation threshold occurs at a very low weight percentage of PANI, and a maximum conductivity value of 0.85 S cm^?1 was obtained for 28.5 wt % of PANI. These elastomeric conducting blends were characterized by elemental analysis, FTIR and UV‐visible spectral analysis, conductivity measurements, SEM, XRD, tensile properties, TGA, and DSC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1438–1447, 2002; DOI 10.1002/app.10408