Effect of secondary dopants on electrochemical and spectroelectrochemical properties of polyaniline

Polyaniline (PANI) was doped with poly(styrene sulfonic acid) (PSS) via doping-dedoping-redoping procedure. Incorporation of PSS in PANI resulted modifications in electrochemical and electrochromic properties, morphology and polymer structure of the polymer film as evidenced by the results of cyclic voltammetry, in situ UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis and conductivity measurements. PANI doped with PSS was found to have a cross-link/branched structure with a minimum degradation product. The absence of degradation products improves the electrochemical, electrochromic properties and thermal stability of the PANI layer for electrochromic applications.     

Sequentially adsorbed electrostatic multilayers of polyaniline and azo polyelectrolytes

In this study, multilayer films composed of alternate polyaniline (PANI) and azo-polyelectrolyte (PNACN, PPAPE, PNANT or PNATZ) layers were fabricated through the electrostatic layer-by-layer self-assembly scheme. In the electrostatic adsorption process, PANI was used as the polycation and the azo polyelectrolytes were used as the polyanion. The multilayer growth was monitored by UV-vis spectroscopy and optical ellipsometry. The photoresponsive and electrochromic properties of the multilayer films were studied by UV-vis spectroscopy and electrochemical measurement. Results show that the multilayer films exhibit linear increases in both the absorbance and film thickness with the increase of the deposition cycles. The thickness contributed by each individual layer depends on the pH of the PANI and azo-polyelectrolyte dipping solutions. The multilayer films can show photoinduced dichroic properties contributed by the azo-polyelectrolyte layers, but the ability to form surface-relief-grating (SRG) upon Ar⁺ laser irradiation is relatively weak. The multilayer films possess the characteristic absorption bands related to the azo chromophores and PANI. As the location of the PANI bands depends on its oxidation states, the multilayer films can show sensitive electrochromic variation. For instance, the PANI/PNACN multilayer films can undergo a transition from transparent yellow-green through deep green to opaque black when the potential changes from −0.1 to 0.8 V. It is demonstrated that using the azo polyelectrolytes with different hues, enriched spectrum of the colors can be obtained by the electrochemical transitions. The multilayer films containing both photoresponsive and electroactive components can be expected for applications in optics, photonic devices and others.     

Comparison of pristine and polyaniline‐grafted MWCNTs as conductive sensor elements for phase change materials: Thermal conductivity trend analysis

Phase change materials (PCMs) function based on latent heat stored on or released from a substance over a slim temperature range. Multiwalled carbon nanotubes (MWCNTs) and polyaniline are important elements in sensor devices. In this work, pristine and polyaniline‐grafted MWCNTs (PANI‐g‐MWCNTs) were applied as conductive carbon‐based fillers to make PCMs based on paraffin. The attachment of PANI to the surface of MWCNTs was proved by Fourier transform Infrared analysis. Dispersion of MWCNTs in paraffin was studied by wide‐angle X‐ray scattering. Heating and solidification of PCM nanocomposites were investigated by differential scanning calorimetry, while variation in nanostructure of PCMs during heating/solidification process was evaluated by rheological measurements. It was found that after 30 min of sonication, the samples filled with 1 wt % MWCNTs have melting and solidification temperatures of 29 and 42 °C, respectively. It was also found that PANI attachment to MWCNTs significantly changes thermal conductivity behavior of PCM nanocomposites. The developed MWCNTs‐based sensor elements responded sharply at low MWCNTs content, and experienced an almost steady trend in conductivity at higher contents, while PANI‐g‐MWCNTs sensor followed an inverse trend. This contradictory behavior brought insight for understanding the response of PCMs against thermal fluctuations. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45389.     

Dispersion of multiwalled carbon nanotubes in polyacrylonitrile‐co‐starch copolymer matrix for enhancement of electrical,thermal, and gas barrier properties

Nanomaterials gained great importance on account of their wide range of applications in many areas. Carbon nanotubes (CNTs) exhibit exceptional electrical, thermal, gas barrier, and tensile properties and can therefore be used for the development of a new generation of composite materials. Functionalized multiwalled carbon nanotubes (MWCNTs) reinforced Polyacrylonitrile‐co‐starch nanocomposites were prepared by in situ polymerization technique. The structural property of PAN‐co‐starch/MWCNT nanocomposites was studied by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The conductivity, tensile strength, and thermal properties of nanocomposites were measured as a function of MWCNT concentrations. The thermal stability, conductivity, and tensile strength of PAN‐co‐starch/MWCNT nanocomposites were improved with increasing concentration of MWCNTs. Oxygen barrier property of PAN‐co‐starch/MWCNT nanocomposites was calculated and it was found that, the property was reduced substantially with increase of MWCNTs proportion. The synthesized PAN‐co‐starch/MWCNT nanocomposites may used for electrostatically dissipative materials, aerospace or sporting goods, and electronic materials. © 2013 Society of Plastics Engineers     

Carbon nanotubes/polyaniline nanocomposite coatings: Preparation,rheological behavior,and their application in paper surface treatment

Conventional cellulosic paper, rendered electro‐conductive, may hold considerable promise for diversified applications in such areas as electro‐magnetic interference shielding and energy storage. Here, an electro‐conductive cellulosic paper was prepared by surface application of multi‐walled carbon nanotubes (MWCNTs)/polyaniline (PANI) nanocomposites onto a conventional base paper. MWCNTs/PANI nanocomposites were prepared by in situ polymerization of aniline with different contents of MWCNTs and used as electro‐conductive filler for the fabrication of electro‐conductive surface‐coated paper. The achieved MWCNTs/PANI nanocomposites exhibited a core‐shell structure, as evidenced by TEM. Effects of feeding ratios of MWCNTs on the rheological behavior of nanocomposite coatings, as well as the mechanical properties and electrical conductivity of surface‐coated paper were studied. Results revealed that the rheological behavior of the nanocomposite coatings showed strong dependence on the MWCNTs content. Moreover, both the electro‐conductivity and mechanical properties of surface‐coated paper were improved as a function of surface application of MWCNTs/PANI nanocomposites, particularly, in presence of an optimum content of MWCNTs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46329.     

Antistatic packaging based on PTT/PTT-g-MA/ABS/MWCNT nanocomposites: Effect of the chemical functionalization of MWCNTs

Polymer/carbon nanotube nanocomposites have attracted high interest for a wide spectrum of applications, including antistatic packaging used to protect electronic devices against electrostatic discharge. Polytrimethylene terephthalate (PTT)/maleic-anhydride-grafted PTT (PTT-g-MA)/acrylonitrile butadiene styrene (ABS) blend-based multiwall carbon nanotubes (MWCNTs) nanocomposites were prepared through extrusion. It was conducted chemical functionalization on the MWCNTs by oxidation using nitric acid to introduce functional groups. The effect of the amount (0.5 or 1.0 wt%) and functionalization of MWCNTs on the nanocomposites was investigated. Despite the poor barrier properties of PTT/PTT-g-MA/ABS/MWCNT nanocomposites due to the presence of voids confirmed by scanning electron microscopy (SEM), the nanocomposites with functionalized MWCNT (MWCNTf) showed excellent barrier properties, indicating that the functionalization process improved the interaction between the MWCNTs and the matrix. The addition of MWCNTs into PTT/PTT-g-MA/ABS blend decreased the electrical resistivity by eight orders of magnitude. The use of MWCNTf may still disrupt the electrical network pathway and slightly decreasing the electrical resistivity, but the nanocomposites present the desired properties required for antistatic packaging.     

Modified Carbon Anode by MWCNTs/PANI Used in Marine Sediment Microbial Fuel Cell and its Electrochemical Performance

Improving the performance of anode is a crucial step for increasing power output of marine sediment microbial fuel cells (SMFCs). A multi‐walled carbon nanotube/polyaniline (MWCNTs/PANI) modified anode was prepared by the way of electrochemical deposition and its electrochemical performance is investigated in this paper. Result shows that the wettability of carbon felt becomes better and the number of bacteria (9.52 × 10¹² m⁻²) on anode biofilm is increased respectively, which is 9 times higher than that of the unmodified. The anti‐polarization ability of the modified anode increases significantly and its kinetic activity of electron transfer increases 4 times. Its exchange current density is 3.62 × 10⁻⁵ A cm⁻². The maximum power density of the modified SMFC reaches 527.0 mW m⁻², which is 4 times higher than that of the unmodified one. Finally, a novel molecular synergistic mechanisms for the enhanced SMFC is also presented, based on the higher bacteria number, the capacitive performance of PANI, the hydrogen bond interaction and higher conductivity of MWCNTs. This excellent electrochemical performance makes the MWCNTs/PANI composite be a potential choice for higher output SMFC.     

Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction

Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6‐tetramethyl‐1‐piperidinyloxy) modified multi‐walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs‐g‐TEMPO) were synthesized using the Cu(I)‐catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy. The PBS grafting on the sidewalls of MWCNTs was carried out in solution via peroxide‐induced formation of macroradicals and it was confirmed by EPR and attenuated total reflectance Fourier transform infrared analysis. Preliminary rheological and calorimetric analyses revealed that the grafting improves both the quality of stress transfer across the polymer ? nanotube interface and the degree of dispersion of the filler, which also exhibited a moderate nucleating action on the PBS. Overall, our results demonstrate that nitroxide radical coupling is an efficient and feasible ‘grafting to’ method to covalently bond polymer chains on MWCNTs with possible advantages in the final properties of the polymer nanocomposites. © 2015 Society of Chemical Industry     

Facile synthesis and morphology control of graphene oxide/polyaniline nanocomposites via in-situ polymerization process

This study reports the synthesis of graphene oxide (GO)/polyaniline (PANI) nanocomposites with controllable morphologies through in-situ polymerization of aniline monomers in the presence of GO sheets. Specific reaction parameters including solution acidity, aniline concentration, and reaction temperature are used to control the final shape of the composite product. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images are used to explore the morphology of the composite. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), FT–IR and UV–vis spectrophotometers are utilized to characterize the intermediates and the final products of the GO/PANI composites. Experiment results reveal that the polymerization operated in low acidity and low temperature conditions inclines to form GO/PANI nanotubes. On the other hand, the polymerization operated in high acidity inclines to form either nanospheres or aligned nanofiber arrays. These different morphologies are resulted from different polymerization routes and the formation mechanisms of these different shapes of nanocomposites are explored. Among the various nanocomposites, the GO/PANI nanospheres exhibit a highest electrochemical surface area. This study provides a facile and effective strategy to control the morphology of GO/PANI nanocomposites with characteristic electrochemical property.     

Synthesis of Silica Decorated MWCNTs for Field Emission Property

A novel route to nanocomposites containing surface modified multiwalled carbon nanotubes (MWCNTs) by silica thin film is reported. The effect of chemical oxidation on the surface of MWCNTs by using different acid-treatments is studied.The acidic processes are characterized by Raman spectroscopy, thermogravimetry analysis, scanning electron microscopy, and transmission electron microscopy. MWCNTs can be coated homogeneously with silica film by using tetraethoxysilane (TEOS)as a precursor in a sol-gel process. Varying the shell thickness of amorphous silica coating layers on MWCNTs exhibits excellent thermal stability, reliability, and lifetime of field emission properties, especially down to less than 10 nm.     

Polyaniline/Montmorillonite Nanocomposites Obtained by In Situ Intercalation and Oxidative Polymerization in Cationic Modified-Clay (Sodium, Copper and Iron)

Polyaniline/montmorillonite nanocomposites (PANI/M) were obtained by intercalation of aniline monomer into M modified with different cations and subsequent oxidative polymerization of the aniline. The modified-clay was prepared by ion exchange of sodium, copper and iron cations in the clay (Na–M, Cu–M and Fe–M respectively). Infrared spectroscopy confirms the electrostatic interaction between the oxidized PANI and the negatively charged surface of the clay. X-ray diffraction analysis provides structural information of the prepared materials. The nanocomposites were characterized by transmission electron microscopy and their thermal degradation was investigated by thermogravimetric analysis. The weight loss suggests that the PANI chains in the nanocomposites have higher thermal stability than pure PANI. The electrical conductivity of the nanocomposites increased between 12 and 24 times with respect to the pure M and this increase was dependent on the cation-modification. The electrochemical behavior of the polymers extracted from the nanocomposites was studied by cyclic voltammetry and a good electrochemical response was observed.     

Mechanical,thermal, and conductivity performances of novel thermoplastic natural rubber/graphene nanoplates/polyaniline composites

Conventional polymer blending has a shortcoming in conductivity characteristic. This research addresses the preparation of conductive thermoplastic natural rubber (TPNR) blends with graphene nanoplates (GNPs)/polyaniline (PANI) through melt blending using an internal mixer. The effect of PANI content (10, 20, 30, and 40 wt %) on the mechanical and thermal properties, thermal and electrical conductivities, and morphology observation of the TPNR/GNPs/PANI nanocomposites was investigated. The results showed that the tensile and impact properties as well as thermal conductivity of nanocomposite had improved with the incorporation of 3 wt % of GNPs and 20 wt % of PANI as compared to neat TPNR and reduced with further increase of the PANI content. It was observed that the GNPs and PANI acted as a critical component to improve the thermal stability and electrical conductivity of the TPNR/GNPs/PANI nanocomposites. The most improved conductivity of 5.22 E-5 S/cm was observed at 3 wt % GNPs and 40 wt % PANI. Variable-pressure scanning electron microscopy micrograph revealed the good interaction and distribution of GNPs and PANI within TPNR matrix at PANI loadings lower than 30 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48873.     

In situ polymerization,thermal, damping,and mechanical properties of multiwalled carbon nanotubes/polyisobutylene‐based polyurethane nanocomposites

Despite the development of strong, durable, and cost efficient polyisobutylene‐based polyurethane (PIB‐based PU) materials has yet to be achieved. The well dispersion and maximum interfacial interaction between the nanofiller and the PIB‐based PU at low loading have been scarcely studied. Here, the preparation of PIB‐based PU nanocomposites with Multiwalled carbon nanotubes (MWCNTs) using a simple in situ polymerization method is reported. The thermogravimetric analysis tests show that MWCNTs significantly improved the thermal stability of MWCNTs/PIB‐based PU nanocomposites. Compare to the pure PIB‐based PU the onset temperature of degradation for the nanocomposite was about 20°C higher at 0.7 wt% MWCNTs loading. Efficient load transfer is found between the nanofiller MWCNTs and PIB‐based PU and the mechanical properties of the MWCNTs/PIB‐based PU nanocomposite with well dispersion are improved. A 63% improvement of Young's modulus and slightly increased of tensile strength are achieved by addition of only 0.7 wt% of MWCNTs. The experimentally determined Young's modulus is in well agreement with the theoretical simulation. It is worth noting that the PIB‐based PU and MWCNTs/PIB‐based PU nanocomposites exhibit excellent damping properties (tan δ > 0.3) from −45°C to 8°C. POLYM. COMPOS., 36:198–203, 2015. © 2014 Society of Plastics Engineers     

Synthesis,characterization, and thermal aging behavior of HCl‐doped polyaniline/TRGO nanocomposites

In this article polyaniline (PANI) nanocomposites containing thermally reduced graphene oxide (TRGO) were synthesized and characterized before and after thermal aging. The nanocomposites were prepared through in situ oxidative polymerization of aniline in the presence of TRGO nanoplatelets. FTIR and Raman spectroscopies, XRD, FESEM, and electrical conductivity measurements were used to characterize synthesized materials. PANI/TRGO nanocomposites showed considerably higher electrical conductivity when compared to pure PANI, which was associated with the higher electrical conductivity of TRGO and increased crystallinity of PANI in the presence of TRGO. Pure PANI and PANI/TRGO nanocomposites were thermally aged at 70, 80, 90, and 100 °C. The results showed that the characteristic time of thermal aging process is higher for PANI/TRGO nanocomposites and increases with TRGO loading, which indicates better stability of conductivity during thermal aging process. On the other hand, the characteristic time of thermal aging reduced with aging temperature and a fast decrease was observed from 80 to 90 °C. Improved resistance over thermal aging can be attributed to the barrier effect of TRGO nanoplatelets to the dopant molecules, which retards conductivity degradation in the thermal aging process. Furthermore, TRGO increases PANI crystallinity and it can also prevent crystallinity reduction during thermal aging process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44635.     

Optical,electrical, and electrochemical properties of graphene based water soluble polyaniline composites

Polyaniline (PANI) is one of the most common polymers known for its conducting properties. However, poor water solubility limits its applications. In this work, PANI has been functionalized with sulfonic acid groups to produce sulfonated PANI (SPANI) offering excellent solubility in water. To compensate for the decrease of electrical conductivity due to functionalization, SPANI was combined with reduced graphene oxide (RGO) to form SPANI/RGO composites with interesting optical, thermal, and electrical properties. The composites have been characterized using X‐ray diffraction (XRD), field emission scanning electron microscopy, UV–vis absorption spectroscopy, Raman spectroscopy, Fourier‐transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermogravimetric analysis, cyclic voltammetry, and four probe electrical conductivity measurement. The SPANI/RGO composites show increased thermal stability, reduced optical band gap and improved electrochemical properties compared with the pure polymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42766.     

聚苯胺/活性炭复合材料的共价键构筑及电容性能

导电聚苯胺(PANI)与活性炭(AC)构筑复合电极材料是当前制备高性能超级电容器电极材料的热点研究方向。其关键点之一是制备出炭与PANI两种材料均匀分散、且具有相当牢固强度连接界面的复合材料。为此,以AC为基材,对其进行功能化处理后,将苯胺在其表面原位聚合,获得具有界面共价键连接的PANI/AC复合材料(PANI–c–AC)复合材料。通过扫描电子显微镜、元素分析、傅里叶变换红外光谱、X射线衍射仪及电化学工作站等测试并研究其结构与电容性能。结果表明,具有界面共价键连接的PANI–c–AC复合材料比电容值(393.3 F/g)最高,既优于单一AC(111.8 F/g)与PANI(296.2 F/g),也优于无共价键连接的PANI–AC复合材料(360.5 F/g)。     

Thermal and electrical properties of carbon nanotubes based polysulfone nanocomposites

Carbon nanotubes (CNTs)-reinforced polysulfone (PSU) nanocomposites were prepared through solution mixing of PSU and different weight percent of multi-walled carbon nanotubes (MWCNTs). Thermal properties of nanocomposites were characterized using thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA studies revealed an increase in thermal stability of the PSU/MWCNTs nanocomposites, which is due to the hindrance of the nanodispered carbon nanotubes to the thermal transfer in nanocomposites and also due to higher thermal stability of CNTs. Morphological properties of nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM) and field emission scanning electron microscope (FESEM). The influence of CNTs loading on electrical properties of PSU/MWCNTs nanocomposites was studied by the measurement of AC and DC resistivity. Dielectric study of nanocomposites was carried out at different frequencies (10 Hz–1 MHz) by using LCR meter. An increase in dielectric constant and dielectric loss was observed with increase in CNTs content, which is due to the interfacial polarization between conducting CNTs and PSU.     

Polyaniline/silver nanocomposites synthesized via UV–Vis‐assisted aniline polymerization with a reversed micellar microemulsion system

Polyaniline (PANI)/silver (Ag) nanocomposites were successfully synthesized within a sodium dodecyl sulfate reverse micro‐emulsion system and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, ultraviolet spectrometry, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and electrochemical methods. The results show that the core‐shell nanoparticles of less than 100 nm may be synthesized with PANI as shell formed around a core of nanoparticle. PANI/Ag nanocomposite prepared by this method has better thermal stability, higher conductivity, and electrochemical performance. The maximum conductivity (95.5 S/cm) was obtained when W₀ (water‐oil ratio) is 22. Cyclic voltammograms results show that PANI/Ag prepared by this method has a high response current and large capacitance. Polarization results show that E_corr (174.1 mV) and I_corr (50.6 μA/cm²) are better than the results for PANI and for PANI/Ag prepared by micro‐emulsion method. PANI/Ag nanocomposites prepared by the current method have potential applications in electrode materials, capacitors, conductive adhesives, and anticorrosion materials. POLYM. COMPOS. 37:1064–1071, 2016. © 2014 Society of Plastics Engineers     

Amino functionalization of multiwalled carbon nanotubes by gamma ray irradiation and its epoxy composites

In this paper, γ‐ray radiation technique was utilized to simply functionalize multi‐walled carbon nanotube (MWCNT) with amino groups. The successful amino functionalization of MWCNTs (MWCNTs‐Am) was proven and the physicochemical properties of MWCNTs before and after radiation grafting modifications were characterized using FT‐IR, X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated that the γ‐ray radiation had the visible effects on the surface properties of MWCNTs. The effects of various functionalized MWCNTs on morphological, thermal, and mechanical properties of an epoxy‐based nanocomposite system were investigated. Utilizing in situ polymerization, 1 wt% loading of MWCNT was used to prepare epoxy‐based nanocomposites. Compared to the neat epoxy system, nanocomposites prepared with MWCNT‐Am showed 13.0% increase in tensile strength, 20.0% increase in tensile modulus, and 24.1% increase in thermal decomposition temperature. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Chemical surface coating of MWCNTs with riboflavin and its application for the production of poly(ester‐imide)/MWCNTs composites containing 4,4′‐thiobis(2‐tert‐butyl‐5‐methylphenol) linkages: Thermal and morphological properties

In this work, carboxylated multi‐walled carbon nanotubes (MWCNTs) were functionalized with riboflavin as a biological molecule under microwave irradiation. Solution blending method was used to incorporate different modified MWCNTs content (5, 10, and 15 wt %) into a chiral and biodegradable poly(ester‐imide) (PEI) to fabricate PEI‐based nanocomposites. The products were characterized for assessing the spectroscopic, thermal, and morphological properties by Fourier‐transform infrared spectroscopy, thermogravimetric analysis (TGA), X‐ray diffraction, transmission electron microscopy (TEM), and field‐emission scanning electron microscopy (FESEM). Optically active PEI was prepared by step‐growth polymerization of amino‐acid‐based diacid and aromatic diol. Functionalized MWCNTs were well dispersed in the PEI matrix and their distribution was homogeneous. This was confirmed by morphology study of the fractured surfaces of nanocomposites by FESEM and TEM. The addition of functionalized MWCNTs improved the thermal stability of NCs compared to the pure PEI. It was found from TGA data that temperature at 10% weight loss was increased from 409°C for pure PEI to 417, 420, and 424°C for nanocomposites containing 5, 10, and 15% functionalized MWCNTs, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42908.