Synthesis and characterization of polymer–nanoclay conductive nanocomposites

Polymer–clay nanocomposites based on poly(3,4‐ethylenedioxythiophene)/polystyrene sulfonate (PEDOT) : PSS and nanoclay montmorillonite were synthesized and characterized. The doping of PEDOT with polystyrene sulfonate made it water dispersible (PEDOT–PSS). Sodium dodecyl benzene sulfonate (SDBS) and ionic liquid were used to increase the interlayer spacing and the conductivity of the nanocomposites, respectively. The nanocomposite was characterized by various techniques, such as X‐ray diffraction (XRD), TEM, surface resistivity, and thermogravimetric measurement analysis. Interlayer spacing increased as a result of the addition of SDBS, and this was confirmed by the 2θ shift observed via XRD analysis. The surface morphology of the conductive coated clay was examined by TEM analysis. Good electrical surface conductivity, interlayer spacing, and polymer coating were observed for the material prepared using the surfactant and conductive ionic liquid. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A PSS‐Free PEDOT Conductive Film Supported by a Hierarchical Nanoporous Layer Glass

The importance of transparent conductive film is increasing due to its use in applications such as touch‐panel devices. Although indium tin oxide is widely used because of its high conductivity and transparency, conductive polymers are being studied as alternative materials that avoid the use of rare metals and the brittleness associated with existing systems. Polyethylene dioxythiophene (PEDOT)/polyethylene sulfonic acid (PSS) is drawing a lot of attention due to its well‐balanced conductivity, transparency, film formability, and chemical stability. The nonconductive PSS reportedly covers the conductive PEDOT. The PSS shell provides carrier and film‐formability to PEDOT but is also a barrier that hinders electrical conductivity. Therefore, the PEDOT film formability is explored supported by a substrate without the addition of PSS. The “hierarchical nanoporous layer glass” holds the PSS‐free PEDOT with its nanopores to form a homogeneous, transparent film. The PSS‐free PEDOT film thus achieves transparency of over 85% and resistivity of below 500 Ω sq^?1.     

A focus on polystyrene tacticity in synthesized conductive PEDOT:PSS thin films

Poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) is a transparent conductive material and a good candidate for being employed as substitute for indium tin oxide (ITO) in reducing the production costs of organic solar cells. To enhance the performance of organic devices, an improving in the conductivity of PEDOT:PSS is crucial and using the solvent additive rises the electrical conductivity by the optimization of the film morphology. The studies have only focused on the relationship between the electrical conductivity of thin films and the crystallinity of PEDOT, and it is also found that the high conductivity is observed in the highly crystalline samples. This study focused on the effect of tacticity of PS on the conductivity of PEDOT:PSS films. First, atactic and isotactic polystyrenes were sulfonated and the complexes of PEDOT:PSS were synthesized. The N-methylpyrrolidone (NMP), as a secondary dopant, was then added to the complexes and conductivity enhancement was investigated in various annealing times. The obtained films were characterized by atomic force microscopy, X-ray diffraction, four point probe resistivity measurement system, UV–visible spectroscopy, FT-IR, and cyclic voltammetry. The electrical conductivity of PEDOT:iPSS films synthesized by the isotactic polystyrene was ~ 0.68 S/cm and by adding 5 wt% NMP into PEDOT:PSS solution, the conductivity of the annealed thin layers increased more than 10-folds (~ 7.73 S/cm) at an appropriate temperature.     

Effects of solvents on thermoelectric performance of PANi/PEDOT/PSS composite films

Organic thermoelectric materials based on conducting polymers, especially for polyaniline (PANi) and poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), have attracted great concern due to their tunable electron transport properties by controlling doping level. Here, the solvent effects of deionized H₂O and NH₃·H₂O were investigated on the electrical conductivity and Seebeck coefficient of PANi/PEDOT/PSS composite films. The introduction of PEDOT/PSS can not only effectively improve the quality of pure PANi film, but also enhance the electrical conductivity of PANi film. The different volumes of deionized H₂O as dilution have a great influence on the electrical conductivity of PANi/PEDOT/PSS composite thin film with a maximum electrical conductivity value of 63.5 S cm^?1, which is much higher than pure PANi and pristine PEDOT/PSS. The introduction of NH₃·H₂O shows a positive effect on Seebeck coefficient with a large decline on electrical conductivity of PANi/PEDOT/PSS. The Raman spectroscopy, scanning electron microscopy (SEM), and UV-vis spectroscopy were used to obtain the morphology and structure information of PANi/PEDOT/PSS.     

Electrically conductive poly(3,4‐ethylenedioxythiophene)–polystyrene sulfonic acid/polyacrylonitrile composite fibers prepared by wet spinning

Composite conductive fibers based on poly(3,4‐ethylenedioxythiophene) (PEDOT)–polystyrene sulfonic acid (PSS) blended with polyacrylonitrile (PAN) were prepared via a conventional wet‐spinning process. The influences of the PEDOT–PSS content on the electrical conductivity, thermal stability, and mechanical properties of the composite fibers were investigated. The fibers with 1.83 wt % PEDOT–PSS showed a conductivity of 5.0 S/cm. The breaking strength of the fibers was in the range 0.36–0.60 cN/dtex. The thermal stability of the PEDOT–PSS/PAN composite fibers was similar to but slightly lower than that of the pure PAN. The X‐ray diffraction results revealed that both the pure PAN and PEDOT–PSS/PAN composite fibers were amorphous in phase, and the crystallization of the latter was lower than that of the former. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of PEDOT:PSS (poly(3,4‐ethylenedioxythiophene))/poly(4‐styrene sulfonate))/ ngps (nanographitic platelets) nanocomposites as chemiresistive sensors for detection of nitroaromatics

Polymer nanocomposites (NCs) are a special class of materials having unique properties and wide application potential in electronics and other diverse areas. In this study, NCs consisting of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrene sulfonate) (PEDOT:PSS) matrix reinforced with graphite nanosheets were fabricated by solution method. The graphite used was functionalized before fabrication of NCs. The functionalized graphite was characterized by transmission electron microscopy (TEM) and Fourier transform Infrared spectroscopy (FTIR) technique. The NCs prepared were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and FTIR technique. The conductivity studies of the prepared NCs were carried out. The prepared NCs films were investigated for the detection of nitrobenzene vapors. The detection mechanism is based on measuring resistivity changes that occur in a NC due to the absorption of nitrobenzene vapors by PEDOT:PSS film. These sensors exhibited excellent response at room temperature when exposed to vapors of nitrobenzene. Sensitivity as high as 18.5% was observed for PEDOT:PSS/NGPs composite. The chemresistor exhibits a fast response (～1.14 min) and good recovery time (～1–2 min). The response of NC to the nitrobenzene vapors is reproducible. POLYM. ENG. SCI., 53:2045–2052, 2013. © 2013 Society of Plastics Engineers     

Effect of microstructure on the dielectric properties of poly(vinyl alcohol)–poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) composite films

Poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT–PSS) was blended with poly(vinyl alcohol) (PVA) to form 0, 10, 20, 30, 40, and 50 vol % PEDOT–PSS/PVA solutions, and their freestanding films were prepared with a simple and cost‐effective solution casting technique at 27 °C in the absence of additives. Field emission scanning electron microscopy images revealed changes in the cocontinuous network to a rodlike morphology in the composite films from 10 to 50 vol % PEDOT–PSS/PVA. The alternating‐current conductivity was found to obey Jonscher's power law. The obtained values of the dielectric constant at 27 °C were relatively high, and a maximum value of 6.7 × 10⁴ at 100 Hz for 40 vol % PEDOT–PSS'/PVA was observed. The dielectric loss attained a maximum value of about 10⁶ at 100 Hz for 40 vol % PEDOT–PSS/PVA. However, a decrease in the dielectric parameters was observed at 50 vol % PEDOT–PSS/PVA because of locally induced strain in the microstructure. The variations in polarization with respect to the applied electric field (P–E) were determined for 50, 100, and 500 Hz at 500 V for the freestanding composite films of lower concentrations up to 20 vol % PEDOT–PSS/PVA. In summary, the dielectric and P–E measurements confirmed that the electrical characteristics changed in accordance to the contribution from both resistive and capacitive sites in the PEDOT–PSS/PVA composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45079.     

Enhanced Thermoelectric Performance of PEDOT:PSS Films by Sequential Post‐Treatment with Formamide

This paper reports a series of sequential post‐treatments using a polar solvent formamide to enhance the thermoelectric performance of poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) anions (PEDOT:PSS). The electrical conductivity of PEDOT:PSS films significantly increases from 0.33 S cm^?1 for the pristine film to ≈2929 S cm^?1 for the treated film and meanwhile the Seebeck coefficient maintains as high as 17.4 µV K^?1, resulting in a power factor of 88.7 µW m^?1 K^?2. Formamide is a polar solvent with a high boiling point of 210 °C and high dielectric constant of 109, and PSS has a good solubility in it. Post‐treatment with formamide causes not only the phase segregation of PEDOT and PSS but also the removal of insulating PSS, therefore leading to the reorientation of PEDOT chains and enhancement in mobility without altering the doping level considerably. The cross‐plane thermal conductivity also reduces from 0.54 to 0.19 W m^?1 K^?1 after the post‐treatment, leading to a figure of merit (ZT) value of 0.04 at room temperature.     

Capacitance properties of graphite oxide/poly(3,4‐ethylene dioxythiophene) composites

Poly(3,4‐ethylene dioxythiophene) (PEDOT) and graphite oxide (GO)/PEDOT composites (GPTs) doped with poly(sodium styrene sulfate) (PSS) were synthesized by in situ polymerization in aqueous media. The electrochemical capacitance performances of GO, PEDOT–PSS, and GPTs as electrode materials were investigated. The GPTs had a higher specific capacitance of 108 F/g than either composite constituent (11 F/g for GO and 87 F/g for PEDOT–PSS); this was attributable to its high electrical conductivity and the layer‐within/on‐layer composite structure. Such an increase demonstrated that the synergistic combination of GO and PEDOT–PSS had advantages over the sum of the individual components. On the basis of cycle‐life tests, the capacitance retention of about 78% for the GPTs compared with that of 66% for PEDOT–PSS after 1200 cycles suggested a high cycle stability of the GPTs and its potential as an electrode material for supercapacitor applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Transparent,conductive polymer blend coatings from latex-based dispersions

Flexible, transparent and conductive polymer blend coatings were prepared from aqueous dispersions of poly(3,4-ethylenedixoythiophene)/poly(styrenesulfonate) [PEDOT/PSS] gel particles (∼80 nm) and latex (∼300 nm). The stable dispersions were deposited as wet coatings onto poly(ethylene terephthalate) substrates and dried at 80 °C. Microstructure studies using tapping mode atomic force microscopy (TMAFM) indicate that a network-like microstructure formed during drying at 0.03 volume fraction PEDOT/PSS loading. In this network-like structure, the PEDOT/PSS phase was forced into the boundary regions between latex. In addition, migration of the PEDOT/PSS particles towards coating surface is likely during drying of the aqueous dispersions. The addition of a small amount of dimethyl sulfoxide (DMSO) in dispersions altered the distribution of the PEDOT/PSS phase. As PEDOT/PSS concentration increases to 0.15 volume fraction, the coating surface is dominated by the PEDOT/PSS phase. The effect of DMSO on microstructure becomes less apparent as PEDOT/PSS concentration increases. The conductivity of the polymer blend coatings increases in a percolation-like fashion with a threshold of ∼0.02 volume fraction PEDOT/PSS. The addition of DMSO in dispersions enhanced the coating conductivity beyond the threshold by more than two orders of magnitude. The highest conductivity, ∼3 S/cm, occurs at 0.20 volume fraction PEDOT/PSS concentration. The polymer blend coatings have good transparency with only a weak dependence of transparency on wavelength due to the small refractive index difference between filler and matrix.     

Study on the wet processable antimony tin oxide (ATO) transparent electrode for PLEDs

A polymer light emitting diodes (PLEDs) was fabricated using the wet processable antimony tin oxide (ATO) as the transparent electrode by spin coating method. PLED were fabricated with ATO (or ITO)/PEDOT:PSS/polymer/BaF₂/Ba/Al configurations. Electrical and optical properties of ATO transparent electrode were measured. Transmittance of ATO thin film was more than 90% in the visible region, sheet resistance was 30 Ω/□ and had a strong solvent resistance. The maximum brightness and maximum efficiency of PLED device using an ATO transparent electrode was 3637 cd/m² and 1.03 cd/A, respectively.     

Cold-sintered V2O5-PEDOT:PSS nanocomposites for negative temperature coefficient materials

A low temperature sintering method, namely cold sintering process, was used to prepare 97 vol%V₂O₅-3 vol% PEDOT:PSS (Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate ceramic-polymer nanocomposites. The density, phase purity, microstructure, elemental distribution and electrical properties of sintered tape-cast films were investigated. The composition with 97 vol%V₂O₅-3 vol% PEDOT:PSS ceramic-polymer nanocomposites can be densified (∼90%) after a cold sintering of 140 °C for 45 min under a uniaxial pressure of 300 MPa. The Transmission Electron Microscopy (TEM) microstructure shows that a ∼10 nm thick intergranular polymer of PEDOT:PSS has been distributed around the V₂O₅ grains after cold sintering. The resistivity decreases with temperature increasing, indicating a typical negative temperature coefficient (NTC) characteristic. The resistivity at 25 °C, temperature coefficient α at 25 °C, and B coefficient (material constant) are 6.34 Ωm, −2.4% K⁻¹ and 2153 K, respectively. The V₂O₅-PEDOT:PSS nanocomposite materials are suitable for new NTC devices, with properties that are comparable to traditional NTC materials that are sintered at much higher temperatures and with much more complexed process and compositions.     

Effect of solvent on electrical conductivity and gas sensitivity of PEDOT: PSS polymer composite films

Poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) was blended with polyethylene oxide (PEO) and polyvinyl alcohol (PVA) and composite film was cast. Additional solvents of dimethyl sulfoxide (DMSO) and ethylene glycol (EG) were mixed and their effects on electrical conductivity and structural changes were investigated. The electrical conductivity increased in response to the additional solvent, leading to an increase in the PEDOT ratio relative to the control. PEDOT:PSS/PEO composite film had a much higher electrical conductivity than PEDOT:PSS/PVA. When blended with PEO, the quinoid structure revealed by Raman spectroscopy increased relative to the PVA‐blended case, indicating higher electrical conductivity. The current–voltage response and gas sensitivity showed much better performance in PEDOT:PSS/PEO/DMSO composite film. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42628.     

Self‐assembly morphology evolution of the polyamide 6 (PA6) component in the PA6/polyethylene glycol system by in situ polymerization of ϵ‐caprolactam monomer

This paper describes the morphology evolution of polyamide 6 (PA6) components in the presence of polyethylene glycol (PEG) by self‐assembly via in situ anionic ring‐opening polymerization of ?‐caprolactam (CL) monomer and expands the study of morphology changes of PA6 in the PA6/PEG system. With a fixed mass ratio of [CL]/[PEG], it was found that by simply changing the reaction conditions the morphology of PA6 components could be changed from nano‐sized microspheres to regular 3D microsphere structured polyhedrons to 3D nano‐sized particle clusters to micro‐scale microspheres. The morphologies of the PA6 components were investigated by SEM and TEM analyses. The diameter range of the PA6 nano‐sized microspheres was controlled within 400 nm. The side length of an individual polyhedron could be effectively tuned from 10 µm to 100 µm. The diameter range of micrometer microspheres was about 5–8 µm. The results suggest that this strategy for self‐assembly can be applied to design materials with complex geometric structures. © 2018 Society of Chemical Industry     

High-performance indium-free flexible transparent ATO/Au/ATO tri-layer films by magnetron sputtering

Due to the scarcity of indium (In) in the earth and its potential harm to individuals, the development of In-free transparent conductive film is considered crucial. In this work, In-free SnO₂:Sb/Au/SnO₂:Sb (ATO/Au/ATO, SAS) tri-layer films with high transparency and conductivity were successfully prepared on polycarbonate (PC) substrates by RF and DC magnetron sputtering at room temperature. The influence of the Au layer thickness on microstructure, electrical and optical performances was systematically studied after fixing the ATO thickness to 50 nm. It was indicated by X-ray diffraction patterns that ATO is amorphous and Au is oriented along (111). The trend of increasing and then decreasing light transmission with Au layer thickness was observed in both experimental and simulation results. The improved figure of merit (FoM, 1.89 × 10^?2 Ω^?1) was achieved in SAS tri-layer film, the resistivity and average transmittance of which was lowered to 7.50 × 10^?5 Ω cm and 81.4%, respectively, when Au layer thickness is 11 nm. Moreover, the mechanism of the variation of optical and electrical properties at different Au layer thickness was proposed. Particularly, the SAS tri-layer films also exhibit superior flexibility, durability and adhesion. These results demonstrate SAS tri-layer films are promising alternative to ITO in flexible electronics applications.     

Electrical and morphological properties of microinjection molded polypropylene/carbon nanocomposites

A series of different carbon (carbon black, carbon nanotubes, and graphite nanoplatelets) filled polypropylene nanocomposites were prepared by melt blending, then followed by compression molding or microinjection molding (µIM). Direct current electrical conductivity measurements and melt rheology tests were utilized to detect the percolated structure for compression molded polypropylene/carbon nanocomposites. For µIM, a rectangular mold insert which has a three‐step decrease in thickness along the flow direction was adopted to study the effect of abrupt changes in mold geometry on the electrical and morphological properties of subsequent micromoldings (µ‐moldings). Results indicated that the µ‐moldings exhibited a higher percolation threshold when compared with their compression molded counterparts. This is largely due to the severe shearing conditions that prevail in the µIM process. The morphology of µ‐moldings containing different carbon fillers was examined using scanning electron microscopy. The development of corresponding microstructure is found to be strongly dependent on the types of carbon fillers used in µIM, which is crucial to the enhancement of electrical conductivity for the resulting µ‐moldings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45462.     

High‐performance flexible epoxy/ZnO nanocomposites with enhanced mechanical and thermal properties

Flexible epoxy/ZnO nanocomposites were prepared using different loadings of ZnO nanoparticles (NPs) and nanotubes (NTs) via in situ curing of epoxy with polyoxyethylene diamines (ED₆₀₀). ZnO precursor was synthesized via precipitation method and ZnO NPs with an average size of 25 nm were used in the preparation of the nanocomposites. ZnO NTs with an average outer diameter, length of 200 nm and 2.4 µm respectively, were prepared by the wet method (hydrothermal method). The morphology, structure, and composition of the nanocomposites were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), and thermo‐gravimetric analysis (TGA). The effect of morphology and content of nano‐ZnO materials on the thermal and mechanical properties of flexible epoxy was studied. In addition, the hardness and indentation depth were calculated by means of nanoindentation. Results showed that the mechanical and thermal properties of flexible epoxy were enhanced by incorporation of ZnO nanostructure into the polymer matrix. POLYM. ENG. SCI., 57:932–946, 2017. © 2016 Society of Plastics Engineers     

Conductive poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonate) polymer glue as an ohmic and rectifying electrical contact for H‐terminated n‐Si and p‐Si wafers

An organic conductive glue based on a blend of poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and d ‐sorbitol was examined for laminating conductors to crystalline silicon. The PEDOT:PSS glue functions as a high‐work‐function solution processable conductor and exhibits an ohmic contact on p‐type silicon and a rectifying contact on n‐type silicon. Under illumination, the n‐Si/PEDOT:PSS:d ‐sorbitol junctions exhibit current–voltage characteristics suggesting minority carrier trap states, leading to charge recombination at the silicon/polymer interface. Conductive glue for laminating to crystalline silicon is desirable for making electrical contacts to flexible materials such as molecular semiconductors, graphene or transparent conductive oxides. These materials could eliminate the need for metal contacts to the front face of silicon solar cells. Conductive glue could prove especially useful for laminating to textured silicon or novel micro‐ or nanostructured silicon materials. © 2018 Society of Chemical Industry     

Preparation of polyaniline coated polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) microparticles and the further fabrication of hollow polyaniline microspheres

In this article, the microparticles of polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) (PS‐PSS) coated by polyaniline (PANI) were prepared and hollow PANI microspheres were further obtained by dissolving the core. First, surface‐sulfonated monodispersed PS was prepared by copolymerization of sodium 4‐styrenesulfonate (SSS) and styrene with dispersion polymerization method. Then aniline was polymerized on the surface of the surface‐sulfonated PS (PS‐PSS) by chemical oxidative polymerization. After purification, we prepared core‐shell (PS‐PSS)/PANI particles. Hollow PANI microspheres were prepared by dissolving the plastic PS core of the (PS‐PSS)/PANI particles in chloroform. The growth process of PANI on the surface of PS‐PSS particles was investigated and the hollow PANI microspheres were characterized. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Temperature dependence of electrical resistivity in carbon nanofiber/unsaturated polyester nanocomposites

This article described the temperature dependence of electrical resistivity for carbon nanofiber (CNF)/unsaturated polyester resin (UPR) nanocomposites prepared by a solvent evaporation method. It was found that the CNF/UPR nanocomposites had quite low electrical percolation threshold due to CNFs having a large aspect ratio and being well dispersed into the UPR matrix. A sharp decrease in the electrical resistivity was observed at about 1 wt% CNF content. The influence of CNF content on the electrical resistivity was investigated as a function of temperature in detail. The nanocomposites showed a positive temperature coefficient effect for the resistivity, and had a strong temperature dependence near the percolation threshold. When the number of thermal cycles was increased, the electrical resistivity decreased and had a weak temperature dependence, especially in the case of melting temperature. Moreover, the size influences of CNFs on the electrical properties of nanocomposites were analyzed and discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers