ZnO/PPy异质纳米复合材料的制备、表征及其气敏特性

室温下, 采用原位聚合法, 以吡咯(PY)为单体, 氯化铁(FeCl₃·6H₂O)为氧化剂, 在塑料基片上聚合生长了聚吡咯(PPy)纳米微球. 然后在聚吡咯基片上生长ZnO种子, 将表面种有ZnO种子的PPy元件置于六次甲基四胺与硝酸锌的混合溶液中, 90 ℃水浴中, 在PPy微球上生长了ZnO纳米棒, 合成了PPy/ZnO异质纳米复合材料. 分别通过X射线衍射仪(XRD)和场发射扫描电镜(FESEM)对PPy/ZnO异质纳米复合材料的结构和形貌进行了表征. 制备了塑料基的PPy/ZnO异质纳米复合材料气体传感器, 在室温下, 对10×10^-6-150×10^-6 (体积分数)浓度范围的氨气进行了气敏测试, PPy/ZnO气敏元件对氨气响应的灵敏度基本呈线性关系, 且对甲醇、丙酮、甲苯等有机气体表现出很好的选择性. 最后, 对PPy/ZnO异质纳米复合材料的形成机理进行了简要分析.     

对甲苯磺酸掺杂聚吡咯的合成、表征及其对金属镁的防腐蚀性能研究

以对甲苯磺酸为掺杂剂, 三氯化铁为氧化剂, 化学氧化吡咯制备了对甲苯磺酸掺杂聚吡咯. 考察了掺杂剂与氧化剂的用量对掺杂聚吡咯电导率的影响, 得到了高电导率聚吡咯的优化条件, 用UV, IR和SEM对其结构和形貌进行了表征. 结果表明, n(对甲苯磺酸)∶n(吡咯)∶n(三氯化铁)＝0.75∶1∶0.5时, 合成的聚吡咯的形貌规则, 电导率达42.7 S•cm^－1. 以聚吡咯为功能成分, 环氧树脂为成膜物质, 得到一种功能膜, 旋涂于金属镁表面, 采用极化曲线和开路电位考察了含有聚吡咯的膜层对金属镁的防腐蚀性能. 结果表明, 含有聚吡咯的膜层对金属镁有很好的防腐蚀性能, 腐蚀电流为0.0981 A, 腐蚀电位为－0.88 V, 在膜层与金属镁之间形成了一层钝化膜.     

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     

Vibrational spectroscopic investigations of ammonia gas sensing mechanism in polypyrrole nanostructures

This paper reports the application of Raman and Fourier transform infrared (FTIR) spectroscopy techniques for the investigation of molecular restructuring of polypyrrole (PPy) nanostructures in ammonia environment. Different types of PPy nanostructures such as nanofibers, nanorods, and nanoparticles were prepared in the presence of different surfactants such as cetyltrimethyl ammonium bromide (CTAB), methyl orange, sodium dodecyl sulfate, and Triton X-100, respectively. The prepared nanostructures were characterized for structural, morphological, and the gas sensing properties. The gas sensing reponse towards ammonia is estimated from change in the surface resistance of the sample. PPy nanofibers prepared in the presence of CTAB have a diameter of ∼63 nm and the gas sensing response of ∼18%, whereas, PPy nanoparticles prepared in the presence of Triton X-100 have a diameter of ∼94 nm and the lowest gas sensing response (6.5%) at 100 ppm level of ammonia. The mechanism of gas sensing has been investigated through vibrational (Raman and FTIR) spectroscopy techniques performed in the presence of analyte (ammonia) gas. The charge compensation via proton transfer process in ammonia environment is found to be main cause for the gas sensing response in the PPy nanostructures.     

Improvement of ammonia sensing properties of polypyrrole by nanocomposite with graphitic materials

The more sensitive and rapid ammonia gas sensors were prepared with nanocomposites of polypyrrole (PPy) and graphitic materials such as graphite, graphite oxide (GO), and reduced graphene oxide (RGO). Pyrrole was polymerized uniformly on the surface of graphitic materials by in situ polymerization method. The structures of nanocomposites were studied by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy indicating the well-exfoliated GO and RGO in PPy matrix with favorable interfacial interaction. PPy/RGO nanocomposite showed the highly improved response in detecting ammonia gas mainly due to the effective electron charge transfer between PPy and ammonia and the efficient transfer of electrical resistance variation by the uniformly dispersed conductive RGO in PPy. PPy/RGO nanocomposite gas sensor also showed the excellent reproducibility in ammonia sensing behavior during the recovery process at lower temperature of 373 K.     

Conductive Composite Materials of Polyethylene and Polypyrrole with High Modulus and High Strength

Composite films of polyethylene (PE) and polypyrrole (PPy) were prepared by polymerization of PPy on an ultradrawn polyethylene film with high modulus and high strength in ferric chloride (FeCl₃) aqueous solution. The electrical conductivity of the composite film was found to be related to the polymerization conditions, such as polymerization temperature, polymerization time, the concentration and the oxidation potential of the FeCl₃ solution. Scanning electron microscopy, FTIR and ¹³C NMR spectra were used to elucidate the morphological and structural variations of PPy prepared under different conditions, which lead to the differences in the electrical properties of the resultant composite films. The best electrical conductivity of the composite was about 5.5 S/cm for the film prepared under optimum conditions. The Young's modulus and the tensile strength reached 80 GPa and 3.2 GPa, respectively, which indicated the successful production of a conductive polymer with high strength and high modulus.     

Development of an optical ammonia sensor based on polyaniline/epoxy resin (SU-8) composite

Polyaniline (PANI)/glycidyl ether of bisphenol A (SU-8) composite film is elaborated in order to detect ammonia gas. These composite films are characterized by ultraviolet-visible (UV-vis) spectroscopy, Fourier transformed infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The sensitivity to ammonia is measured by optical absorption changes. The ammonia sensing properties of PANI/SU-8 composite films are studied, and then are compared to pure PANI films elaborated by chemical way. Experimental results show that the PANI/SU-8 optical sensor has simultaneously a rapid response to ammonia gas and regenerates easily, that is advantageous compared to pure PANI films.     

Optical rubbery ormosils sensor for the detection of ammonia

Rubbery ormosil films with immobilized aminofluorescein (AF) were investigated to develop an optochemical sensor for the determination of ammonia in water. The gel precursors with tetramethoxysilane (TMOS) and dimethyldimethoxysilane (DiMeDMOS) were deposited on glass supports, and characterized in terms of response to pH, and to dissolved ammonia at constant pH. After preconditioning the sensing film was stable for 6 months. The detection limit for ammonia in water was 0.2 microg mL(-1) (S/N 2), the response being linearly dependent on concentration in the range of 0.5 to 80 microg mL(-1) ammonia. The response time was less than 5 min. The effects of sodium chloride concentration, temperature, and coexisting metal ions and compounds were investigated.     

Catalytic Behaviour of Transition Metal Cations In Electrosynthesis and Growth of Nanostructure Conducting Polypyrrole Films On/Between the Passive Cu Interdigital Electrodes: Application In Gas Sensors

The electrosynthesis of nanostructured polypyrrole (PPy) on copper interdigital electrodes (Cu‐IDEs) surfaces was performed by anodic oxidation of pyrrole in the presence of oxalic acid in aqueous solution (passivation technique) by potentiostatic method. Some divalent transition metal ions (Fe(II), Co(II), Ni(II), Cu(II), Zn(II)) as catalyst can be used to polymers growth on/between spacing between passive Cu‐IDEs by using potentiostatic technique. The morphology of the conducting films was examined by field emission scanning electron microscope, indicating a dependence of the film morphology to catalyst type. The PPy films on Cu‐IDEs were used to investigate the properties of the gas sensing ability.     

磷酸铁纳米薄膜复合光波导氨气传感元件的制备

将硝酸铁和甲醇、磷酸溶液按一定比例混合后,通过旋涂法制备了磷酸铁（FePO₄）纳米薄膜,测定了匀胶机转速对膜厚及烘干温度对膜厚和折射率的影响,并发现薄膜的烘干温度超过150 ℃时,薄膜的厚度（130 nm）和折射率(1.7)变化不大。将该薄膜固定在钾离子交换玻璃光波导表面,研制出FePO₄膜/K⁺交换玻璃复合光波导。酸碱指示剂溴百里酚兰（BTB）作为敏感试剂,固定在复合光波导表面,研制了BTB膜-FePO₄膜/K⁺交换玻璃复合光波导氨气传感元件。采用自装的光波导气体传感检测系统对不同浓度的氨气进行了检测。结果表明,该传感元件能够检测0.35 mg/m³浓度的氨气,并具有响应（10 s）及恢复（90 s）速度快、可逆性好、连续使用等特点。     

Effect of ammonia on the temperature‐dependent conductivity and thermopower of polypyrrole

We report the first measurements of the effect of ammonia gas on the temperature dependence of the conductivity and thermoelectric power of polypyrrole films. Our data are for samples of very different conductivities, extending down to a temperature of 200 K for low‐conductivity polypyrrole gas sensors, and down to 4.2 K for more highly‐conducting PPy(PF₆) samples. We demonstrate that (except for the most metallic case) our polypyrrole samples show greater sensitivity to ammonia as the temperature is lowered (i.e. the fractional reduction in conductivity is greater at lower temperatures). Remanent decreases in conductivity are present after the removal of ammonia for higher pressure exposures, and remanent increases in the metal‐like thermoelectric power for the PPy(PF₆) for samples grown at higher temperatures. Our results indicate that the mechanism of this conductivity decrease in PPy(PF₆) is that ammonia causes a reduction in the size of metallic regions as disordered barrier regions are thickened. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1331–1338, 2006     

Sensitivity and Selectivity of Polypyrrole Based AC‐Amperometric Sensors for Electroinactive Ions – Frequency and Applied Potential Influence

Oxidation/reduction of polypyrrole films coupled with ion exchange on the polymer/solution interface can be utilized for amperometric sensing of electroinactive ions. Anion or cation exchanging films (polypyrrole doped by chloride or poly(4‐styrenesulfonate) ions, respectively) can be used to determine common anions (as Cl^?, NO , SO etc) or cations (K⁺, Na⁺, Li⁺, Ca²⁺, Mg²⁺) under conditions of alternating current (AC) amperometry in the range 10^?4–1 M. A sensitivity can be tuned by choosing appropriate electrode potential, corresponding to polypyrrole oxidation (anion‐exchanging films) or reduction (cation‐exchangers). Electrochemical impedance spectroscopy and AC‐voltammetry studies have shown that applied frequency and potential could also affect the observed dependence of the signal (admittance or AC‐current) on ion concentration. For high frequency the sensitivity is higher but selectivity lower, due to influence of solution conductivity on the response. For low frequencies the sensitivity is lower; however, a selectivity increase was observed due to diverse mobility of ions in the polymer film. Selectivity of AC‐amperometric responses was studied both in separate and mixed solutions.     

Electrical and mechanical properties of the zone-drawn polypyrrole films

The zone-drawing method (ZD) was applied to electrochemically synthesized polypyrrole films containing tosylate (PPy/TsO) and the mechanical and electrical properties of the resulting films were investigated. It was found that the electrical conductivity of the zone-drawn film reached 365 S cm⁻¹ in the drawing direction, which was 4.7 times that of the original film. The tensile properties of the zone-drawn film were improved and Young's modulus and strength at break increased to 4.32 GPa and 90.1 MPa from 0.53 GPa and 40.4 MPa of the as-synthesized film, respectively. The dynamic storage modulus (E) increased by the zone-drawing over a whole experimental temperature range and attained 7.0 GPa at room temperature and 4.0 GPa even at 200°C. © 1996 John Wiley & Sons, Inc.     

Optical rubbery ormosils sensor for the detection of ammonia

Rubbery ormosil films with immobilized aminofluorescein (AF) were investigated to develop an optochemical sensor for the determination of ammonia in water. The gel precursors with tetramethoxysilane (TMOS) and dimethyldimethoxysilane (DiMeDMOS) were deposited on glass supports, and characterized in terms of response to pH, and to dissolved ammonia at constant pH. After preconditioning the sensing film was stable for 6 months. The detection limit for ammonia in water was 0.2 μg mL^–1 (S/N 2), the response being linearly dependent on concentration in the range of 0.5 to 80 μg mL^–1 ammonia. The response time was less than 5 min. The effects of sodium chloride concentration, temperature, and coexisting metal ions and compounds were investigated. Received: 22 December 2000 / Revised: 5 March 2001 / Accepted: 7 March 2001     

Growth of aligned polypyrrole acicular nanorods and their application as Pt‐free semitransparent counter electrode in dye‐sensitized solar cell

Polypyrrole films on fluorine doped tin oxide (FTO)‐coated glass substrate were prepared in situ by placing FTO/glass substrates where pyrrole was polymerized by methyl orange‐ferric chloride complex. The atomic force microscopy image indicated growth of acicular nanorods of polypyrrole. These films exhibited catalytic activity towards I₃⁻/I⁻ redox couple and have been investigated for counter electrode application in dye‐sensitized solar cell (DSSC). The fabricated DSSC with N719 dye/TiO₂ as photoanode, and PPy/FTO as counter electrode shows ~1.7% efficiency.     

Active sol–gel thin film on nanostructured plasmonic surface

Sol–gel hybrid films based on alkyl bridged polysilsesquioxanes and doped with phenol red molecules, were synthesized for sensing purposes. Doped films changes colour from yellow to orange to red when exposed to hydrochloric acid (HCl) both in solution and gas phases. The synthesis was optimized in order to produce porous films after spin coating. The porosity increases reacting surface area and chemical reactivity of the sensing thin film. Porosity, optical and structural characterizations of these films were investigated by transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR) and Spectroscopic Ellipsometry (SE). Variation of optical characteristics upon immersion of the film in the solution was characterized by UV–visible (UV–vis) spectroscopy. Moreover the same porous sensitive hybrid film was deposited on gold sinusoidal grating in order to detect variations of the dielectric film optical constant after HCl solution dip. This variation was revealed by monitoring surface plasmon polariton excitations.     

Ultra low field emission characteristics of chloride doped polypyrrole films

Field emission characteristics of chloride doped polypyrrole (Cl‐PPy) films have been investigated. For this purpose, freestanding Cl‐PPy films have been synthesized by interfacial polymerization from two different monomer (pyrrole) concentrations (1 and 0.1 M), keeping the monomer to oxidant (FeCl₃) concentration ratio equal to 1. The surface morphology of these Cl‐PPy films, as revealed from scanning electron microscopy, was found to be granular in nature. The average grain size of films prepared using 1 and 0.1 M pyrrole concentrations were ～2.5 and ～1 µm, respectively. The measured threshold field, that is, field required to draw an emission current density of 10 µA/cm², for these two films were 0.27 and 0.15 V/µm, respectively. From these films, a maximum current density of 1 mA/cm² could be drawn at an electric field of 0.42 and 0.29 V/µm, respectively. The field emission current (investigated at a preset value of 1 µA) was found to be very stable up to 3h, suggesting utility of Cl‐PPy films as a novel material for field emission based applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Flexible NH3 sensors fabricated by in situ self-assembly of polypyrrole

Novel flexible NH₃ gas sensors were formed by the in situ self-assembly of polypyrrole (PPy) on plastic substrates. A negatively charged substrate was prepared by the formation of an organic monolayer (3-mercapto-1-propanesulfonic acid sodium salt—MPS) on a polyester (PET) substrate using a pair of comb-like Au electrodes. Two-cycle poly(4-styrenesulfonic acid) sodium salt/poly(allylamine hydrochloride) (PSS/PAH) bilayers (precursor layer) were then layer-by-layer (LBL) deposited on an MPS-modified substrate. Finally, a monolayer of PPy self-assembled in situ and PPy multilayer thin films self-assembled LBL in situ on a (PSS/PAH)₂/MPS/Au/Cr/PET substrate. The thin films were analyzed by atomic force microscopy (AFM). The effects of the precursor layer (PSS), the deposition time of the monolayer of PPy and the number of PPy multilayers on the gas sensing properties (response) and the flexibility of the sensors were investigated to optimize the fabrication of the film. Additionally, other sensing properties such as sensing linearity, reproducibility, response and recovery times, as well as cross-sensitivity effects were studied. The flexible NH₃ gas sensor exhibited a strong response that was comparable to or even greater than that of sensors that were fabricated on rigid substrate at room temperature.     

Preparation and characterization of electrostrictive polyurethane films with conductive polymer electrodes

All-polymer electrostrictive soft films were developed for the first time by depositing conductive polymer (polypyrrole) directly on both sides of solution-cast electrostrictive polyurethane elastomer films. The final composite films are flexible with strong adhesion between the polyurethane film and the conductive polymer electrode. The conductivity (sheet resistivity ∼1000 Ω/□), of the polymer electrode is appropriate for its intended use. The compatible interface between the polypyrrole electrode polymer and the electrostrictive polyurethane significantly improves the acoustic and optical transparency of these composite films, compared with using a metal electrode film. The all-polymer films also exhibit comparable dielectric properties to gold-electroded polyurethane films in the temperature range from −40^°C to +80^°C. The temperature range covers the soft segment glass transition temperature of the polyurethane elastomers, which is about −20^°C. The films also show large electric field induced strain responses which are dependent on film thickness and measurement frequency. The electrostrictive characteristics in the all-polymer films show similarities to those of the films with gold electrodes under identical measurement conditions. © 1998 John Wiley & Sons, Ltd.     

HIGHLY SENSITIVE CATALASE ELECTRODE BASED ON POLYPYRROLE FILMS WITH MICROCONTAINERS

Highly sensitive catalase electrodes for sensing hydrogen peroxide have been fabricated based on polypyrrole films with microcontainers. The microcontainers have a cup-like morphology and are arranged in a density of 4000 units cm^-2. Catalase was immobilized into the polypyrrole films with microcontainers （Ppy-mc）, which were coated on a Pt substrate electrode. The catalase/Ppy-mc/Pt electrode showed linear response to hydrogen peroxide in the range of 0-18 mmol/L at a potential of-0.3 V （versus SCE）. Its sensitivity was measured to be approximately 3.64 μA （mmol/L） ^-1 cm^- 2, which is about two times that of the electrode fabricated from a flat Ppy film （catalase/Ppy-flat/Pt electrode）. The electrode is highly selective for hydrogen peroxide and its sensitivity is interfered by potential interferents such as ascorbic acid, urea and fructose. Furthermore, such catalase electrodes showed long-term storage stability of 15 days under dry conditions at 4℃.