Conductive polymers as a new type of thermoelectric material

Thermoelectric properties were investigated for the films of electrically conductive doped polyanilines. The thermoelectric performance, evaluated by thermoelectric figure-of-merit (ZT = T (S² σ) / κ), of various protonic acid-doped polyaniline bulk films was found to depend on the electrical conductivity σ of the film. Thus, the higher the electrical conductivity, the higher the figure-of-merit is, because the thermal conductivity κ of polyaniline films does not depend on the electrical conductivity. Among the conductive bulk films of polyaniline, the highest figure-of-merit (ZT = 1 × 10⁻⁴) was observed for (±)-10-camphorsulfonic acid (CSA)-doped polyaniline in an emeraldine form (σ - 188 S cm⁻¹) at room temperature. The multilayered film, composed of electrically insulating emeraldine base layers and electrically conducting CSA-doped emeraldine salt layers, exhibited 6 times higher ZT at 300 K than that of a bulk film of CAS-doped polyaniline, showing the highest ZT value of 1.1 × 10⁻² at 423 K. Stretching of the CAS-doped polyaniline film also increased the figure-of-merit of doped polyaniline films along the direction of the stretching.     

Electrical conductivity enhancement of polyaniline by refluxing

The room temperature electrical conductivity of polyaniline (PANI) was found to increase remarkably after it was heated in tetrahydrofuran (THF) with refluxing for a certain period and then doped with methanesulfonic acid (MSA). The enhanced electrical conductivity of PANI was attributed to a partially cross‐linked network generated via the formation of new chemical bonds between adjacent PANI chain segments during thermal treating, which may shorten the inter‐chain distance and facilitate inter‐chain transition of charge carriers in doped PANI. During the refluxing, the moderate dissolving power for PANI as well as a much lower boiling point of THF were considered to have a unique effect on the formation of such partially cross‐linked network in PANI. As a comparison, PANI treated in poor solvents like methanol (or ethanol) and PANI treated in dimethyl formamide (DMF), which is a better solvent than THF but has higher boiling point, did not show an obviously increased electrical conductivity. Study on X‐ray diffraction (XRD) analysis of PANI after refluxing showed that crystallinity decreased gradually with the increase of cross‐linking degree, but the inter‐chain cross‐linking probably occurred first in crystalline region and then in the amorphous region. Electrical conductivity of PANI decreased after it was refluxed with THF for an extended period due to the decreased crystallinity and doping in PANI. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyaniline/silicon dioxide composites and preparation of conductive films

The focus of this study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop‐by‐drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/SiO₂ composite films were measured according to the standard four‐point‐probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/SiO₂ composites were also investigated by spectroscopic methods including UV‐Vis, FT‐IR, and Photoluminescence. UV‐Vis and FT‐IR studies showed that SiO₂ particles affect the quinoid units along the polymer backbone and indicate strong interactions between the SiO₂ particles and the quinoidal sites of PANI (doping effect). The photoluminescence properties of PANI and PANI/SiO₂ composites were studied and the PANI/SiO₂ composites showed increased intensity as compared to neat PANI. The increase of conductivity of PANI/SiO₂ composite may be partially due to the doping or impurity effect of SiO₂ where the silicon dioxides compete with chloride ions. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well dispersed and isolated in composite films. Copyright © 2009 John Wiley & Sons, Ltd.     

Lithium‐Salt‐Containing High‐Molecular‐Weight Polystyrene‐block‐Polyethylene Oxide Block Copolymer Films

Ionic conductivity in relation to the morphology of lithium‐doped high‐molecular‐weight polystyrene‐block‐polyethylene oxide (PS‐b‐PEO) diblock copolymer films was investigated as solid‐state membranes for lithium‐ion batteries. The tendency of the polyethylene (PEO) block to crystallize was highly suppressed by increasing both the salt‐doping level and the temperature. The PEO crystallites completely vanished at a salt‐doping ratio of Li/EO>0.08, at which the PEO segments were hindered from entering the crystalline unit of the PEO chain. A kinetically trapped lamella morphology of PS‐b‐PEO was observed, due to PEO crystallization. The increase in the lamella spacing with increasing salt concentration was attributed to the conformation of the PEO chain rather than the volume contribution of the salt or the previously reported increase in the effective interaction parameter. Upon loading the salt, the PEO chains changed from a compact/highly folded conformation to an amorphous/expanded‐like conformation. The ionic conductivity was enhanced by amorphization of PEO and thereby the mobility of the PEO blocks increased upon increasing the salt‐doping level.     

Nanoscale measurements of conducting domains and current-voltage characteristics of chemically deposited polyaniline films

Spatial variations in electric conductivity and evolutions of band structures of polyaniline (PANI) films have been studied by use of a so-called current-sensing atomic force microscope (CS-AFM) or atomic force microscope current image tunneling spectroscopy (AFM-CITS). PANI films were deposited chemically onto indium-tin oxide- (ITO-) glass substrates, and their thickness and doping levels were controlled by polymerization and acid-doping conditions. The conducting uniformity of the PANI films depends on their doping level and thickness. Conducting domains were observed in fully doped PANI film, even when the bias voltage was reduced to as small as 30 mV. High current flowing regions gradually disappeared when conducting PANI films were partially dedoped. The point-contact current-voltage (I-V) characteristics of conducting tip-polymer/ITO systems were investigated on PANI films with different thickness and degree of doping. Various types of I-V curves representing metallic, semiconducting, and insulating states were obtained depending on the aggregation of polymer chains and doping level of the polymer film. The band gap energies (estimated from the I-V or dI/dV-V curves) of emeraldine base (EB) (undoped polyaniline) films are all higher than 3.8 eV, and a wide distribution of the band gap energies (0-1.1 eV and 0.75-1.8 eV for fully and partially doped PANI thin films, respectively) was found in a single polymer film.     

Electro‐ and photoconductive properties of the PVA/PAN‐I2 blends

The electrical conductivity of poly(vinylalcohol)/polyaniline‐iodine blend (PVA/PAN‐I₂) prepared by solution process was investigated. The FTIR spectroscopy revealed a structural change of both shape and intensity of the polyaniline (PAN) bands after doping with iodine, indicating the formation of a charge transfer complex. The J‐V curves for pure PAN; PAN‐I₂ and PVA/PAN‐I₂ film obey the ohm law at lower voltages, deviate from the linear response at higher voltages and finally display the breakdown behavior. The PVA/PAN‐I₂ exhibit photoconductivity by UV/visible irradiation as well as oscillations that may be attributed to a nonlinear behavior of the blend.     

高能球磨法固相掺杂制备樟脑磺酸掺杂聚苯胺

通过高能球磨方法引发樟脑磺酸(CSA)对本征态聚苯胺(PANI)的固相掺杂反应, 制备了樟脑磺酸掺杂聚苯胺(PANI-CSA)粉末. 采用SEM, XRD, FT-IR等分析方法对所得的PANI-CSA进行了形貌和结构表征, 采用四点探针法对电导率进行了测定. FT-IR图谱的变化反映了聚苯胺的质子化过程, 而XRD谱图表明, 聚苯胺分子链在外力诱导下形成了有利于电荷传导的取向排列. 系统地研究了球磨时间对掺杂率和电导率的影响规律. 结果表明, 固相掺杂具有较高的掺杂速率, 其电导率和掺杂率均随球磨时间先增大后减小, 其最高电导率可达到3.25 S/cm, 对应掺杂率为0.31.     

Effect of chain aggregation on the conductivity and ESR spectra of polyaniline

Solutions of polyaniline in m-cresol with and without camphorsulfonic acid (CSA), as well as films cast from these solutions were studied by ESR spectroscopy at 133–423 K and by optical spectroscopy in the range λ = 350–1100 nm. An analysis of the optical and ESR spectra shows that in the solutions and films without CSA polyaniline is fully doped but the conductivity of these films is low (∼10⁻⁸ S cm⁻¹; cf. 100 S cm⁻¹ for the films with CSA). Compared with the CSA-containing samples, the samples without CSA are characterized by broader ESR lines and higher contribution of the Curie spins to the magnetic susceptibility. These facts indicate a weak aggregation of polyaniline chains without CSA, which leads to low conductivity. A formula was proposed, which describes the temperature dependence of the polyaniline ESR linewidth and allows the interchain distance and the mobility of electrons moving along polymer chains to be determined. The conductivity of polyaniline films is affected by moderate heating (363–388 K) of the films and solutions from which the films were cast. It was found that the interchain distances correlate with the conductivity of the films and with the broadening of their ESR lines caused by the effect of O₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2701–2711, December, 2005.     

Photopyroelectric spectroscopy of polyaniline films

Photopyroelectric spectroscopy (PPES), in the 400 < λ < 900 nm wavelength range, was used to study thermal properties of differently doped polyaniline (PAN) films. The photopyroelectric intensity signal V_n(λ) and its phase F_n(λ) were independently measured, as well as the intensity V_n(f) and the phase F_n(f) (f being the chopping frequency) for a given λ of the saturation part of the PPES spectrum. Equations of both the intensity and the phase of the PPES signal, taking into account the thermal and the optical characteristics of the PAN films and the pyroelectric detector, were used to fit the experimental results. From the fittings we obtained, with great accuracy, the values of thermal conductivity k and thermal diffusivity coefficient α of PAN films of different doping degrees. It was observed that, in contrast with the strong doping‐dependence of the electrical conductivity, the thermal parameters of PAN films remained practically unchanged under doping. This apparent discrepancy is explained by the granular metal model of doped PAN. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1294–1300, 2000     

Thermal transporting properties of electrically conductive polyaniline films as organic thermoelectric materials

Thermal transporting properties of electrically conductive polyaniline films were first investigated in wide range of temperatures above room temperature as organic thermoelectric materials. Thermal conductivities of various protonic acid-doped polyaniline films were measured by combination of a laser flash method and a differential scanning calorimeter in relation with electrical conductivity and a kind of dopant. The thermal conductivities thus measured are in the range of conventional organic polymers, indicating that the doped polyaniline films have extremely low thermal conductivities among electrically conductive materials, and have correlation with neither electrical conductivity, nor a kind of dopant. Consequently the polyaniline film, which shows very high electrical conductivity, has comparable thermoelectric figure-of-merit (ZT) with feasible inorganic thermoelectric materials such as iron silicide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermoelectric power and conductivity of different types of polypyrrole

We have measured the thermoelectric power and conductivity as a function of temperature of a wide range of polypyrrole samples, including a film of soluble polypyrrole synthesized chemically, and wrinkled films synthesized using indium–tin oxide electrodes; other samples investigated include high‐conductivity polypyrrole films synthesized at different temperatures and current densities, films grown on nonconducting substrates, and polypyrrole gas sensors. The thermoelectric powers are remarkably similar and metal‐like for the medium and high conductivity samples but show nonzero extrapolations to zero temperature for wrinkled samples. The temperature dependence of conductivity tends to be greater for samples of lower conductivity. In contrast to polyaniline and polyacetylene, a crossover to metallic sign for the temperature dependence of conductivity at higher temperatures is not observed in any of our samples; the fluctuation‐induced tunnelling and variable‐range hopping expressions account for nearly all our conductivity data except for low‐temperature anomalies. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 953–960, 1999     

高导电聚苯胺薄膜的制备及其电磁屏蔽性能的研究

随着电器制品、电子器件的商用、军事用和科学应用的迅速增长 ,产生了亟待解决的电磁干扰 (也称作电磁环境污染 )问题 ,电磁干扰屏蔽日益受到关注 .本文从聚苯胺掺杂工艺角度出发 ,通过改变掺杂剂用量和溶剂种类 ,制备出高导电的聚苯胺薄膜 ,并对其电磁屏蔽特性进行了初步的测试与理论分析 ,将屏蔽效能的实测结果与理论计算值进行了比较     

Phenol assisted deaggregation of polyaniline chains: simple route to high quality polyaniline film

High conducting polyaniline films were readily prepared by in situ chemical oxidative polymerization/deposition of aniline in the presence of a very small amount of organic additive such as phenol. The conductivity of a thin ( approximately 150 nm) polyaniline film synthesized in the presence of 0.01 wt % of phenol ( r-PANI) is an order of magnitude higher (as well as better conducting homogeneity) than that of a film (PANI) obtained from the conventional method without an additive. r-PANI also has better adhesion and electrochemical stability/reversibility, more transparency in the visible-light region, and faster/easier doping/dedoping response compared to PANI. The function of phenol molecule is to avoid the formation of the inter- and/or intrachain hydrogen bonding during the growth of the polyaniline chains. The deaggregation/reducing intrachain hydrogen bonding of polyaniline chains by phenol molecules was revealed with IR, SAXS, and SEM data. All these data supported that phenol does assist the deaggregation of polyaniline chains during the growth of polymer chains or nanorods.     

Structural and optoelectrical properties of nanocrystalline Gd-doped CdO films prepared by sol gel method

Gd-doped CdO thin films with various Gd concentrations have been prepared on glass and Si wafer substrates using sol gel technique. The films were characterised by X-ray fluorescence (XRF), X-ray diffraction (XRD), optical absorption spectroscopy, and dc-electrical measurements. XRF method was used to determine the %Gd content in the films while XRD was used to study the influence of Gd doping on the detailed crystalline structure. Experimental data indicate that Gd³⁺ doping with level of less than 2.4% slightly enlarge the CdO crystalline unit cell. The bandgap (E _g) of Gd-doped CdO suffers narrowing by about 13% due to a small (0.2%) doping level but with %Gd doping level larger than 2.4%, E _g becomes wider than that of undoped CdO. The electrical behaviours of the Gd-doped CdO films show that they are degenerate semiconductors. The 2% Gd-doped CdO film shows increase in its mobility by about 92%, conductivity by 320%, and carrier concentration by 127%, relative to undoped CdO film. From transparent-conducting-oxide point of view, the Gd doping of CdO by sol gel method is not effective. Finally, the absorption in the NIR spectral region was investigated to be due to the free electrons.     

Preparation and characterization of a conductive polyaniline/polysulfone film and evaluation of the effect of co-solvent

A novel conductive dense membrane composed of polyaniline (PANI) and polysulfone (PSU) was prepared. To improve the solubility of PANI in N-methyl pyrrolidone (NMP) and consequently increase the conductivity of the eventual film, a tertiary amine (1,3-dimethyl-2-imidazolidinone, DMI) was added to the solvent as a co-solvent. Different PANI solution concentrations in NMP/DMI were used to make blend films via solution blending with PSU solution in NMP in different ratio’s of PANI/PSU. The effect of the PSU fraction on the properties of the membrane has been investigated. The electrical conductivity, doping degree, crystallinity, miscibility of the polymers and shape stability were investigated. It was observed that an increase in the PSU fraction causes a decrease in the conductivity as well as less film deformation after doping. The conductivity and shape stability of the blend film were optimized by a change in PANI concentration in the casting solution and a change in the PSU fraction. The best conductivity was achieved using 3% PANI solution in NMP/DMI and the minimum percentage of PSU, allowing good shape stability after doping, was found to be 40%.     

Synthesis of poly(o‐phenylenediamine) nanofiber with novel structure and properties

The poly(o‐phenylenediamine) (PoPD) was synthesized from the monomer o‐phenylenediamine in various organic solvent medium viz. dimethyl sulfoxide (DMSO), N,N‐dimethyl formamide (DMF) and methanol using ammonium per sulfate as a radical initiator. The structure just like polyaniline derivative with free ?NH functional groups of the synthesized polymers confirmed by various standard characterizations was explained from the proposed polymerization mechanism. All the synthesized polymers were completely soluble in common organic solvent like DMSO and DMF because of the presence of polar free ?NH functional groups in its structure. The formation of polymer nanofiber by reverse salting‐out process was confirmed, and the synthesized polymer in DMSO medium was the best polymer in terms of nano‐morphology as well as conducting properties. Interestingly, the average DC conductivity of undoped polymer film was recorded as 2.21 × 10^?6 Scm^?1 because of induced doping through self charge separation. Moreover, the conductivity of the polymer film was further increased to 1.16 × 10^?3 Scm^?1 after doping by sulfuric acid. Copyright © 2016 John Wiley & Sons, Ltd.     

Field‐induced bending deformation of various rubber films

The field‐induced bending deformation of various rubber films was measured. The deformation tended to increase with the increase in the conductivity of the films. In addition, the effect of doping with tetracyanoethylene (TCNE) was also studied. This doping significantly enhanced the bending deformation and conductivity when the film was made of acrylonitrile‐butadiene rubber. The tip of the film (5 × 30 mm², 0.28 mm thick) moved by 3 mm due to the bending deformation induced by the applied voltage (140 V). Such a rubber film may find applications as a polymer actuator. Copyright © 2007 John Wiley & Sons, Ltd.     

Structure and properties of plasma-polymerized thin films of polyaniline

Plasma polymerization of aniline and in-situ doping of polvaniline with iodine was carried out using radio frequency glow discharge. Thin films of polyaniline were deposited on platinum and glass. The infrared spectrum shows that the aromatic ring is retained under the plasma conditions. The electrical conductivity measurements indicate that the conductivity increases by more than seven orders of magnitude when the polyaniline is doped by iodine. The scanning electron microscopic studies reveal the formation of irregular pentagons on glass substrate while on platinum, polvaniline forms a fibrillar network. In both the cases a continuous film is obtained.     

Structure–electrical property study of anisotropic polyaniline films

The relationships of the structure and electrical properties of anisotropic HCl‐doped polyaniline (PANI) films cast from N,N′‐dimethylpropylene urea (DMPU) solutions and stretched to different draw ratios were studied. The anisotropic structure of the stretched PANI films was examined by X‐ray diffraction, near‐infrared wave‐guide coupling, and polarized infrared measurements. The PANI emeraldine base (EB) films cast from DMPU solutions had a single‐phase noncrystalline structure, and stretching of the films did not cause crystallization to occur. The transition moment angles of two weakly absorbing infrared bands were determined, and the Hermans' orientation functions for the PANI EB films were calculated. The PANI films were then doped with HCl, and the electrical properties were determined by impedance spectroscopy. With a specially designed test fixture, the in‐plane and through‐plane impedance was obtained. The conductivity along the stretch direction increased with orientation. The in‐plane conductivity was significantly higher than the through‐plane conductivity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 823–841, 2003     

Polyaniline thin film optical waveguides for integrated optics and VLSI prepared by vacuum evaporation technique

Polyaniline is emerging as an important polymer material which offers challenging opportunities for both fundamental research and new technological applications in waveguides. Metal doped polyaniline has been prepared initially in the form of powder by a solution growth technique. The emeraldine salt with doped metal was also prepared by solution growth technique. This powder was used for vacuum evaporation on optically flat glass substrate. The dark green doped (Fe, Al) polyaniline thin films were prepared by vacuum evaporation technique (10^?4 torr). Deposited waveguide thin films have been characterized structurally, using X‐ray diffraction (XRD), optically etc. Effective refractive index of the thin film waveguide was also calculated theoretically and experimentally. Waveguide parameters, namely refractive index, propagation loss and depth of vacuum deposited polyaniline thin films optical waveguide have been determined. The optical spectra and structure and waveguide parameters of vacuum deposited polyaniline thin films are strongly affected by the type of doping. It is possible to reduce the losses by addition of Fe to the vacuum deposited polyanine thin film and modify the effective refractive index (O_eff) according to particular requirements. Results are compared with the results in the literature. Copyright © 2002 John Wiley & Sons, Ltd.