Room temperature operating sensitive and reproducible ammonia sensor based on PANI/hematite nanocomposite

ABSTRACT

A facile, ultra-sensitive, quickly recoverable, and room temperature operating ammonia sensor was developed by using polyaniline (PANI) and hematite (α-Fe₂O₃) hybrid nanocomposite. The hematite nanoparticles were obtained by template-free hydrothermal process. The PANI/α-Fe₂O₃ nanocomposite was synthesized by in situ chemical oxidative polymerization process of aniline in presence of α-Fe₂O₃ nanoparticles. The structural and morphological study and compositional analysis of PANI/α-Fe₂O₃ were performed by Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, and scanning electron microscopy. The PANI/α-Fe₂O₃ sensor showed excellent reproducibility, ultra-fast response, and excellent sensitivity (46.72%) as compared to PANI (29.72%) sensor towards ammonia gas at room temperature.     

One-pot synthesis of zinc oxide - polyaniline nanocomposite for fabrication of efficient room temperature ammonia gas sensor

Development of efficient room temperature ammonia (NH₃) gas sensor from one pot synthesized zinc oxide (ZnO) – polyaniline (PANI) nanocomposite is reported in the present article. Prior to gas sensing study, the material is characterized to understand the structural, morphological, compositional, optical and thermal properties. Structural and morphological studies indicate good incorporation of ZnO particles in PANI matrix. The gas sensing efficiency of ZnO-PANI nanocomposite is examined at room temperature for ethanol (C₂H₅OH), methanol (CH₃OH) and NH₃ gas. The results confirm that ZnO-PANI nanocomposite to be highly selective for NH₃ with fast response time and better stability. The response and recovery times are observed to be significantly dependent on NH₃ concentration and the lowest detectivity limit of the sensor for NH₃ is found 10 ppm. ZnO-PANI nanocomposite shows better gas sensing efficiency as compared to the sensors developed from single phase PANI film.     

Poloxamer and gelatin gel guided polyaniline nanofibers: synthesis and characterization

A rapid polymerization technique was successfully employed to synthesize interconnected polyaniline (PANI) nanofibers using chemical oxidative polymerization inside a soft template. The thermoreversible hydrogels of Lutrol F 127 and gelatin were used as templates where the interstices present in the hydrogel were responsible for the formation of PANI nanofibers with a diameter in the range ca 70?75 nm and ca 50?55 nm respectively and several micrometers in length. The doped emeraldine salt of PANI was confirmed by Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy. The crystallinity of as‐synthesized PANI nanofibers for both cases was verified by an X‐ray diffraction study while thermogravimetric analysis was performed to compare the relative stability of the synthesized PANI nanofibers. The electrical conductivities of polymerized PANI are of the order of 10^?3 S cm^?1 and are compared with those of template fabricated PANI. The Lutrol F 127 gel guided PANI nanofibers showed a rectifying property while the gelatin gel guided PANI provided a simple ohmic nature. © 2013 Society of Chemical Industry     

Oxidative solution polymerization of aniline hydrochloride onto electrospun nanofibers mats of polylactic acid: Preparation method and characterization

In this work, we present the preparation of polylactic acid (PLLA)/polyaniline (PANI) conductive composite nanofibers mats. They are prepared by bulk oxidative solution polymerization of PANI onto electrospun non‐woven fibers mats of PLLA. The PANI ratio in the composite is about 70%w/w. Scanning electron microscopy (SEM) shows that PLLA nanofibers are randomly oriented, beads free with diameters of 186 ± 85 nm, The PLLA/PANI composite nanofibers diameter values are 518 ± 128 nm with a good adherence between PANI and PLLA nanofibers. DSC and XRD measurements reveal an amorphous structure of the electrospun PLLA fibers due to the rapid evaporization of the solvent. FTIR and UV–vis spectra reflect good mutual interactions between PANI and PLLA chains. The DC‐conductivities ( ) far better than other published ones for similar composites prepared by bulk oxidative solution polymerization of PANI onto other electrospun nanofiber mats or with electrospun nanofibers from a solution mixture of PLLA and PANI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41618.     

Facile fabrication of polyaniline/polypyrrole copolymer nanofibers with a rough surface and their electrorheological activities

Hierarchical polyaniline/polypyrrole (PANI/PPy) copolymer nanofiber was prepared via a two‐step method and adopted as dispersing materials for electrorheological (ER) fluids. The first step was used to synthesize PANI nanofibers by a rapid mixing method. Subsequently, the PANI/PPy copolymer nanofibers with a rough surface were obtained using an in situ polymerization method continuously. The morphology of the resultant PANI/PPy copolymer nanofibers can be controlled by varying the amount of Py monomer in the secondary in situ polymerization method. The rough surface of PANI/PPy copolymer nanofibers were confirmed by scanning electron microscopy and transmission electron microscopy. The diameter of PANI/PPy nanofiber is within the range 100–200 nm. The obtained PANI/PPy copolymer particles all exhibit amorphous structure through X‐ray diffraction measurement. We also demonstrated that the hierarchical PANI/PPy copolymer nanofibers exhibited characteristic ER behaviors, which were investigated using a Haake rotational rheometer at various electric field strengths. The ER efficiency e for PANI‐1mLPPy and PANI‐2mLPPy ER fluids at shear rate 0.1 s⁻¹ is 36.6 and 28.5 under electric field strength E = 3 kV/mm, respectively. Low leaking current density is observed even at high electric field strength and wide plateau region appeared, which show a strong ER activity for the PANI/PPy composite nanofibers. The results also indicate that the PANI/PPy composite particles have distinctly enhanced ER effect compared with the pure PANI and PPy particles under electric stimuli. The significantly improved ER property of PANI/PPy‐based ER fluid is ascribed to the enhanced interfacial polarization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46289.     

Optimization of waste quail eggshells as biocomposites for polyaniline in ammonia gas detection

A simple, cost-effective, and novel chemical sensor for ammonia (NH₃) gas detection was developed from polyaniline (PANI)/quail eggshell (QES) composites. QES is a natural waste enriched in calcium carbonate. In this work, pure PANI was synthesized from chemical oxidation method and PANI/QES composites were prepared from physical mixing of QES with the synthesized PANI at different mass ratio. A series of complementary techniques including Fourier transform infrared and ultraviolet-visible spectrometers, scanning electron microscope with energy dispersive detection coupled with mapping, thermogravimetric analysis, and X-ray diffractometer were used to characterize the physicochemical and textural properties of the biocomposites. From the results, PANI/QES composite with a mass ratio of 1 exhibited the lowest NH₃ detection limit of 5.24 ppm with a linear correlation coefficient (R²) of close to unity (0.9932) between the signal and NH₃ gas concentration. As a whole, the PANI/QES biocomposites synthesized from this work exhibited excellent selectivity toward NH₃ gas even in the presence of other gas impurities, such as acetone, ethanol, and hexane. For the sensor reusability, the PANI/QES biocomposites can be reused in the application of NH₃ gas detection for at least 4 cycles.     

Polyaniline benefited from poly(vinyl alcohol) in both conductivity and energy storage

Polyaniline (PANI) is an important conductive polymer because of its wide potential. In this article, we present a modified chemical polymerization method, which employs poly(vinyl alcohol) (PVA) as a doping assistant, for the synthesis of PANI. In this study, the introduced PVA contributed both to the conductivity and specific capacitance. The conductivity markedly increased more than two orders of magnitude from 5.2 to 1052 S/m after a small amount of PVA was introduced. A combination of the amphoteric polymer and acid together as the dopant extended the doping method for the synthesis of conductive PANI. The specific capacitance of PANI occurred up to 382.9 F/g at a current density of 0.5 A/g. The PANIs exhibited fast redox reactions, good ion response, and a short diffusion path of electronic transport. By feat of the hydrophilicity of PVA, the as‐prepared PANI showed a good dispersibility in aqueous solution; this is important for its potential applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42989.     

Fabrication and characterization of electrospun Plantago major seed mucilage/PVA nanofibers

Electrospinning is a well-known technique for producing nanofibers using synthetic and natural polymers like mucilage. In this study, Plantago major Mucilage (PMM) was blended with polyvinyl alcohol (PVA) as a nontoxic adding agent, in order to produce electrospun nanofiber. Electrospinning parameters (voltage, tip-to-collector distance, feed rate, and PMM/PVA ratio) were optimized and solution properties were analyzed. The morphology of nanofibers was investigated using scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET). Mechanical strength of nanofibers was determined, and cell viability on nanofibers was discussed by MTT assay. The results of SEM indicated that the PMM/PVA (50/50) nanofibers obtained with average diameter of 250 nm. Viscosity, electrical conductivity, and surface tension of PMM/PVA solution were 550 Cp, 575 μS/cm, and 47.044 mN/m, respectively. FTIR and XRD results verified the exiting PMM in produced nanofibers and no chemical reaction between PMM and PVA. Improvement in mechanical strength and cell viability of nanofibers by adding PMM to PVA nanofibers indicated the potential application of PMM-based nanofibers for medical and food industries. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47852.     

Polyaniline–maleicacid–dodecylhydrogensulfate salt as sensor material for toxic gases

This article reports the results of novel polyaniline material as gas sensor, capable of operating at room temperature for toxic gases. Polyaniline–maleicacid–dodecylhydrogensulfate salt (PANI‐MA‐DHS) was prepared by emulsion polymerization pathway, which is soluble in N, N‐dimethyl formamide. PANI‐MA‐DHS was coated on a ceramic bead by simple brush coating method and used as sensor material. The resistance change of PANI‐MA‐DHS material for NH₃, CO₂, SO₂, and H₂S gases at different concentrations (10, 100, 1000, and 10,000 ppm level) was monitored for sensor characteristics. The stability of the polyaniline material under continuous exposure of gas level from 10 to 10,000 ppm was also studied. This novel gas sensor material has advantages such as excellent sensing ability, low cost, fast regeneration time (～ 1–2 min), simple experimental setup, and operable at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of polyaniline nanofiber colloids

Polyaniline (PANI) nanofibers were prepared via the reaction of aniline with ammonium persulfate carried out in ethylene glycol (EG) medium without water. These purified PANI nanofibers could be dispersed in water and other polar solvents, such as ethanol, EG, and N,N‐dimethylformamide, to form colloids. The morphology and structure of the PANI nanofibers were characterized and the effects of mechanical stirring on the morphology, structure, and electrical performance of PANI were investigated. The results indicated that the intermolecular H‐bonding interaction between molecules of PANI and alcohol is advantageous to the one‐dimensional growth of PANI, and a stirring reaction results in a lager size, a higher doping level, conductivity, degree of crystallinity, and oxidation than a nonstirring reaction. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers.     

Electrospun polyaniline nanofibers web electrodes for supercapacitors

Polyaniline nanofibers (PANI‐NFs) web are fabricated by electrospinning and used as electrode materials for supercapacitors. Field‐emission scanning electron microscope micrographs reveal nanofibers web were made up of high aspect ratio (>50) nanofibers of length ～30 μm and average diameter ～200 nm. Their electrochemical performance in aqueous (1M H₂SO₄ and Na₂SO₄) and organic (1M LiClO₄ in propylene carbonate) electrolytes is compared with PANI powder prepared by in situ chemical oxidative polymerization of aniline. The electrochemical properties of PANI‐NFs web and PANI powder are studied using cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. PANI‐NFs web show higher specific capacitance (～267 F g^?1) than chemically synthesized PANI powder (～208 F g^?1) in 1M H₂SO₄. Further, PANI‐NFs web demonstrated very stable and superior performance than its counterpart due to interconnected fibrous morphology facilitating the faster Faradic reaction toward electrolyte and delivered specific capacitance ～230 F g^?1 at 1000th cycle. Capacitance retention of PANI‐NFs web (86%) is higher than that observed for PANI powder (48%) indicating the feasibility of electro spun PANI‐NFs web as superior electrode materials for supercapacitors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of polyaniline nanofiber and copolymerization with acrylate through in situ emulsion polymerization

Polyaniline (PANI) was prepared, respectively, by direct mixed oxidation method in different acids. Scanning electron microscopy showed that high quality of PANI nanofibers can be obtained easily in hydrochloric acid, sulfuric acid, and acetic acid, especially in the sulfuric acid; infrared and ultraviolet spectra characterization showed all products were the doped PANI. Then, using complex emulsifiers, PANI was dispersed in acrylate emulsion by supersonic dispersion assisted with mechanical stirred to obtain mixed pre‐emulsion, the result showed different PANI performed different dispersing stability in the pre‐emulsion. More importantly, PANI–polyacrylate copolymer was prepared through multi‐steps in situ emulsion polymerization using water‐soluble azo (VA‐044) as initiator. Experiment showed that good dispersing stability of PANI in the pre‐emulsion was premise to obtain the final stable copolymer emulsion. Further, the micro‐morphology and thermal property of the copolymer were studied by transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analyzer. The result proved that acrylate occurred in situ polymerization on surface of PANI nanofibers, the presence of PANI increased glass transition temperature (T_g) and thermal decomposed temperature of the copolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dispersion of soybean stock‐based nanofiber in a plastic matrix

The focus of this work is the study of the dispersion mechanism of soybean stock‐based nanofibers in a plastic matrix. The cellulose nanofibers were extracted from soybean stock by chemo‐mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 and 100 nm and lengths of thousands of nanometers. These nanofibers were characterized by atomic force microscopy and transmission electron microscopy. X‐ray diffraction studies showed that the soybean stock nanofibers had a relative percentage crystallinity of about 48%. Selective chemical treatments increased the cellulose content of soybean stock nanofibers from 41 to 61%. The matrix polymers used in this project were poly(vinyl alcohol) (PVA) and polyethylene (PE). The mechanical properties of nanofiber‐reinforced PVA film demonstrated a 4‐ to 5‐fold increase in tensile strength, as compared to the untreated fiber‐blend‐PVA film. One of the problems encountered in the use of nanoreinforcements lies in the difficulty in ensuring good dispersion of the filler in the composite material. Improved dispersion level of nanofibers within a thermoplastic was achieved by adding ethylene‐acrylic oligomer emulsion as a dispersant. In the solid phase of nanofiber‐blend‐PE composites, the compression‐molded samples showed that improved mechanical properties were achieved with coated nanofibers. Copyright © 2006 Society of Chemical Industry     

Thermal conductivity of PVDF/PANI-nanofiber composite membrane aligned in an electric field

Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.     

Superior ammonia sensing properties of PET-supported polyaniline/reduced graphene oxide/zinc ferrite ternary nanocomposite thin film at room temperature

This article introduces a ternary nanocomposite-based flexible thin film ammonia sensor developed on transparent polyethylene terephthalate (PET) substrate in the well-known in situ chemical oxidative polymerization technique. The nanocomposite consists of three different materials: polyaniline (PANI), reduced graphene oxide (rGO), and zinc ferrite (ZF). Keeping the PANI amount constant, seven PANI/rGO/ZF (PRZ) samples are produced by performing stoichiometric variation between rGO and ZF. Later on, various structural, morphological, and spectroscopic analysis of all the composite materials is accomplished with field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and ultraviolet–visible spectroscopy (UV–Vis). The sensing performance of the as-produced sensors toward ammonia (NH₃) is examined in the concentration range from 250 ppb to 100 ppm. The study reveals the excellent sensing ability of the PRZ3 sensor (rGO = 30%, ZF = 20%) achieving minimum and maximum responsivity values of ~51% and ~1052%, respectively, at the lowest (250 ppb) and highest (100 ppm) concentration of ammonia. The sensor also exhibits admirable repeatability, good dynamic responsivity, rapid response (t_res ~2.9–5 s), moderately faster recovery (t_rec ~37.9–69.7 s), superb linearity against ppm variation (R² ~ 0.989), low detection limit (~123 ppb), and exceptional selectivity toward ammonia. The substrate temperature variation divulges that room temperature (30°C) is the ideal temperature for getting outstanding responsivity of the sensor. The study is further accompanied by humidity variation in the incoming air and bending flexibility test of the substrate. A compulsory and legitimate model regarding the sensing mechanism is presented at the end.     

Fabrication and characterization of novel nanofibers from cress seed mucilage for food applications

Cress seed mucilage (CSM) as a new source of biomacromolecule has gained attraction in food science due to its biodegradability and biocompatibility. In this research CSM–poly(vinyl alcohol) (PVA) nanofibers were produced under different conditions by electrospinning technique. Viscosity and electrical conductivity of the produced biopolymers were analyzed. The effect of CSM to PVA volume ratio and applied electrical field were evaluated on nanofiber morphology by scanning electron spectroscopy. The optimum nanofibers showed smooth and uniform surfaces with diameter size range of 95–278 nm. The results of Fourier transform infrared spectroscopy of CSM–PVA nanofiber with volume ratio of 60:40 showed characteristic peaks of CSM and PVA. X‐ray diffractometer data clearly revealed the amorphous structure of the electrospun nanofibers. Thermogravimetric and derivative thermogravimetric analysis indicated that thermal stability of electrospun nanofibers increased in comparison to CSM and PVA. The results of this study indicated that CSM can be applied as a new source of biopolymer for production of nanofibers that could be used for different applications such as delivery systems and packaging film fabrication. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45811.     

Cross-linked electrospun polyvinyl alcohol/sodium caseinate nanofibers for antibacterial applications

In this study, the polyvinyl alcohol (PVA) and sodium caseinate (SC) nanofibers were produced by a single-fluid electrospinning method from their blends. Afterward, the cross-linking process with two different methods was applied to the PVA/SC (70/30, v/v) ratio, which was selected according to the surface and mechanical properties of the electrospun mat. In the first method, different ratios (15%, 20%, 25%, and 30%) of glutaraldehyde (GLA) cross-linking agents were added to the PVA/SC solution and then, PVA/SC/GLA nanofibers were obtained. In the second method (in-situ method), the nanofibers obtained from the PVA/SC solution were cross-linked by dipping into the cross-linking solution. After, PVA/SC/GLA/Zinc oxide nanoparticles (ZnO NP) mats were obtained by adding ZnO NP at different rates to the PVA/SC/GLA (7030-25GLA) solution, which was chosen according to the results of thermal, mechanical, and moisture test. In addition, performing tests, a cytotoxicity test for fibroblast cell line (L929), and in vitro antibacterial test for Escherichia coli and Staphylococcus aureus were also applied to them. Therefore, the usability of PVA/SC/GLA/ZnO NP nanofibers as an antibacterial effective wound dressing was investigated. Due to the high toxic effect of GLA, it was found that PVA/SC/ZnO cross-linked nanofibers are not suitable for wound dressing use. However, it was determined that the PVA/SC nanofiber cross-linked by the in-situ method had high cell viability according to the cytotoxicity test result and thus could be used as a fibroblast tissue scaffold.     

Large‐scale synthesis of polyaniline nanofibers based on renewable resource molecular template

We report reproducible large‐scale synthesis of polyaniline (PANI) nanofibers up to 100 g scale via micelle mediated soft template approach. A unique built‐in amphiphilic azobenzenesulfonic acid based on renewable resource dopant was synthesized for large‐scale production of PANI nanofibres. The amphiphilic surfactant exists as 4.3 nm micelle in water and it self‐organized with aniline to form long cylindrical aggregates, which template for PANI nanofibers. The PANI nanofibers were found soluble in water and organic solvents and they were characterized by ¹H‐NMR, FT‐IR, and viscosity techniques. The mechanism of the PANI nanofiber formation was investigated by dynamic light scattering, scanning electron microscopy, and high resolution transmission electron microscopy. The width of the nanofibers was precisely controlled from 130–200 nm with length up to ～ 5 μm. The absorption spectroscopic analysis of nanofibers in water revealed that the large‐scale samples (10, 50, and 100 g) were found to posses expanded chain conformation compared to that of 1 g scale sample. The wide angle X‐ray diffraction patterns showed two new peaks at lower angles at d spacing of 25.5 and 13.6 Å corresponding to lamellar ordering of PANI chains followed by interdigitation of the amphiphilic dopant in the nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

纳米结构聚苯胺/PVP复合纤维及其气敏传感特性研究

以双氧水为氧化剂在超声环境中制备了具有灵敏化学活性的聚苯胺纳米棒,并与聚乙烯吡咯烷酮溶液复合,通过静电纺丝技术制备了稳定有序纳米结构的纤维。将所制产物放置于特定的化学环境中,对其化学传感特性进行了研究。发现材料的电学行为对被测气体浓度有良好的响应,并对气敏响应的产生机理进行了初步的探讨。     

Preparation of polyaniline/phosphorylated poly(vinyl alcohol) nanoparticles and their aqueous redispersion stability

A novel approach for the preparation of the colloidal conducting polyaniline (PANI) nanoparticles was developed. The polyaniline/partially phosphorylated poly(vinyl alcohol)(PANI/P‐PVA) nanoparticles were prepared by the chemical oxidative dispersion polymerization of aniline monomer in 1.0 M HCl aqueous media with the partially phosphorylated poly(vinyl alcohol) (P‐PVA) as the stabilizer and codopant. The PANI/P‐PVA nanoparticles were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), electrical conductivity measurement, and redispersion stability testing. All the results were compared with the properties of the conventional polyaniline in the emeraldine salt form (PANI ES). It was found that the P‐PVA/aniline feeding ratio obviously affected the morphology, redispersion stability and electrical conductivity of the PANI/P‐PVA nanoparticles. When the P‐PVA/aniline feeding ratio ranged from 50 to 60 wt %, the PANI/P‐PVA nanoparticles showed spherical shape with good uniformity, significant redispersion stability in aqueous media, and good electrical conductivity up to 7 S/cm. © 2010 American Institute of Chemical Engineers AIChE J, 2011