Simultaneously depositing polyaniline onto bacterial cellulose nanofibers and graphene nanosheets toward electrically conductive nanocomposites

In this study, we report the construction of a ternary flexible nanocomposite of bacterial cellulose/graphene/polyaniline (BC/GE/PANI) via a facile two-step strategy. Bacterial cellulose/graphene (BC/GE) is first prepared by a novel in situ membrane-liquid-interface method, in which the three-dimensional continuous BC nanofibers can be maintained and the introduced GE can improve the mechanical properties mainly due to the uniform dispersion of GE in the BC matrix. To construct the effectively interconnected conductive paths between separated GE nanosheets, polyaniline (PANI) is simultaneously deposited on the surfaces of both BC nanofibers and GE nanosheets to obtain BC/GE/PANI with excellent electrical conductivity. It is found that the as-prepared BC/GE/PANI has an electrical conductivity of 1.7 ± 0.1 S cm⁻¹, which is higher than most of PANI-based composites. It is believed that the BC/GE/PANI nanocomposite possesses great potential for applications in electromagnetic shielding and flexible electrodes.     

In Situ Synthesis of Oil-Based Polymer/Silver Nanocomposites by Photoinduced Electron Transfer and Free Radical Polymerization Processes

In this study, in situ synthesis of oil-based polymer–silver nanocomposites was achieved by using photoinduced free radical polymerization processes in which silver nanoparticles were formed by electron transfer reaction. An oil-based macromonomer was prepared and then copolymerized with styrene in the presence of AgNO₃. Copolymerization was started with free radicals formed by photolysis of 2,2-dimethoxy-2-phenyl acetophenone and simultaneously silver nitrate was reduced to metallic silver in nanosize by electron transfer reaction. The amount of photoinitiator influenced the size of silver nanoparticles formed within the polymer films. Nanocomposite films were characterized by TEM and TGA analysis. The obtained polymer nanocomposite film was also examined in respect of surface coating material that would have an antibacterial effect against Gram-positive, Gram-negative and spore-forming bacteria. It was demonstrated that suitably coated nanocomposite samples exhibited an antibacterial effect against these bacteria.     

Surface morphology of cellulose films prepared by spin coating on silicon oxide substrates pretreated with cationic polyelectrolyte

Flat cellulose films were prepared and morphologically modified by spin coating a cellulose/N-methylmorpholine-N-oxide/H₂O solution onto silicon oxide substrates pre-coated with a cationic polyelectrolyte. Spin-coated cellulose films were allowed to stably form on the silicon oxide substrates by pretreatment with either polydiallyldimethylammonium chloride (PDADMAC) or polyvinylamine (PVAm). The film surfaces obtained were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). AFM topographical images of the cellulose film surfaces showed a different morphology depending on the underlying polymer, where PVAm pretreatment brought about an anisotropic surface topology. These results suggest that the specific attraction acting at the cellulose/polymer interface influences both the film formation and surface morphology of the cellulose layer. Differences in the solvent used to precipitate cellulose caused variations in the surface roughness by affecting the cellulose separation behavior. The morphological features of spin-coated cellulose film surfaces could be altered to some extent by these film preparation techniques.     

Freestanding conducting polyaniline film for the control of electromagnetic radiations

Electromagnetic interference is pollution generated due to dense nature of circuitry in electronic devices and is required to be control at its source. Polyaniline is an environmentally stable conducting polymer which can be cast as thin film, which can replace the corrosive metals as a shield for the control of electromagnetic radiations. In this communication we discuss our results on the preparation of flexible freestanding conducting polyaniline film of varied thickness using either p-toluenesulphonic acid (PTSA) or camphor-10-sulphonic acid as a primary dopant and 4-chloro-3-methyl phenol (CMC) as a secondary dopant. The resulting films were characterized by conductivity, scanning electron micrograph and shielding effectiveness measurements (SE). The SE measurements were carried out using co-axial transmission line method in the frequency range of 0.1–1000 MHz. We noticed that only the change of 2% in the shielding effectiveness of these films over the period of 3 years indicating the environmental stability of polyaniline films.     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

Thermoplastic starch nanocomposites reinforced with cellulose nanocrystals: effect of plasticizer on properties

The objective of this study was to characterize cellulose nanocrystals /TPS-based nanocomposites. Nanocrystalline cellulose was isolated from cotton linters using sonochemical method and characterized through WXRD, TEM, and FTIR. These nanocrystals were then dispersed in glycerol and sorbitol plasticized starch using a Fluko high shear homogenizer in varying proportions and films were cast. The films were characterized using WXRD, SEM, and mechanical properties. TEM images of nanocrystals revealed a diameter of 20–30 nm and length 200–300 nm. XRD results for nanocomposite films for both the plasticizers showed 2θ peaks at 14.8°, 16.7,° and 22.5°. Elastic modulus increased with addition of cellulose nanocrystals and tan δ shifted toward higher temperature for both the plasticizers. Mechanical properties improved more than 200% for both glycerol and sorbitol plasticized nanocomposites.     

Orientation of cellulose nanowhiskers in polyvinyl alcohol

The goal of this study was to align cellulose nanowhiskers in a polymer using a strong magnetic field and thereby obtain a unidirectional reinforced nanocomposite. Cellulose whiskers (2 wt. %) were incorporated in a polyvinyl alcohol matrix using solution casting with water as the solvent. The suspension was cast and the water was evaporated while a homogeneous magnetic field of 7 T was applied. Different microscopy investigations of prepared nanocomposites indicated that the cellulose whiskers were oriented perpendicular to the direction of the magnetic field. Dynamic mechanical thermal analysis further strengthened the idea of alignment because the results showed that the dynamic modulus of the nanocomposite was around 2 GPa higher at room temperature in the aligned direction compared to the transverse direction. PACS 81.05.Lg; 81.05.Qk; 82.35.Np     

Electrocatalytic oxidation of formaldehyde on platinum well-dispersed into single-wall carbon nanotube/polyaniline composite film

Single-walled carbon nanotubes (SWNTs)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The composite films were dispersed Pt by electrodeposition technique. The presence of SWNTs and platinum in the composite film was confirmed by XRD analysis and scanning electron microscopy (SEM). Four-point probe investigation and electrochemical impedance spectroscopy (EIS) revealed that the well arrangement of PANI coated SWNTs in these films enhanced electric conductivity and facilitated the charge-transfer of the composite films. Cyclic voltammogram (CV) and chronoamperogram showed that Pt-modified SWNT/PANI composite film performs higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formaldehyde oxidation. The results imply that the SWNT/PANI composite film as a promising support material improves the electrocatalytic activity for formaldehyde oxidation greatly.     

Fabrication and Thermal Characteristics of Liquid Crystalline Copolyester/OMMT Nanocomposite Films

Liquid crystalline copolyester (LCC)/organically modified-montmorillonite (OMMT) nanocomposite films were prepared by a solvent casting method with different OMMT contents, using p-chlorophenol as a solvent. Both LCC and LCC/OMMT were heat treated to obtain the smectic structure. To examine their internal structure and morphology, the prepared LCC/OMMT nanocomposite films were characterized by an X-ray diffraction method and TEM (transmission electron microscopy). The d-spacing of the silicate layers for each LCC/OMMT nanocomposite film was shifted, indicating that the OMMT particles were dispersed in the LCC matrix and formed intercalated structures. Thermal characteristics of the LCC/OMMT nanocomposite films were investigated by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and thermo-mechanical analysis (TMA). The gel-to-liquid crystal transition (T_c-lc) and degradation temperatures (T_d) of both LCC and LCC/OMMT nanocomposite films with different heat treatment time were examined. The T_c-lc and T_d of the LCC/OMMT were found to be enhanced compared with those of the LCC film, exhibiting their improved thermal characteristics.     

发光薄膜沉积技术中薄膜晶体管的优化设计

为了能制备高均匀性、大尺寸高清RGB-OLED显示终端,发展了一种全新的、无掩膜低成本的彩色薄膜沉积技术——薄膜晶体管导向的薄膜沉积技术,并研究了薄膜晶体管的宽长比及栅压对电聚合发光薄膜性能的影响,寻找最佳的制备条件。实验中采用像素尺寸大小为200μm×200μm的AMOLED基板,通过TFT来控制发光薄膜在ITO像素上的电化学聚合过程。首先对不同宽长比的TFT性能进行表征,再对不同宽长比的TFT在不同栅压条件下制备的电化学聚合薄膜进行表征和分析。实验结果表明,在同一宽长比的TFT控制下,施加栅压越大,制备的薄膜越厚,发光效果越好;在不同宽长比的TFT控制下,宽长比越大,聚合薄膜越厚,发光效果越好。在较大栅压下,选择宽长比为50μm/10μm的TFT最为适宜。研究结果为电化学聚合技术在AMOLED显示中的应用奠定了良好基础。     

Electrical conductivity and optical transparency of bacterial cellulose based composite by static and agitated methods

Composites consisting of bacterial cellulose (BC) and ionic conducting polymer (ICP) were prepared. BC was biosynthesized in media at 0, 25, 50 and 100 rpm. ICP was chemically synthesized at different concentrations of ionic salt. The corresponding electrical conductivity of the composites was measured as a function of ionic salt concentration. ICP improved the optical transparency and electrical conductivity of the BC/ICP composites. Morphological images of BC/ICP composites showed that the pore size of the BC pellicle increased while the diameter and density of the BC fibers decreased. The cultivation method was critical in affecting the structure and electrical conductivity of the composites.     

Fabrication of stable, transparent and superhydrophobic nanocomposite films with polystyrene functionalized carbon nanotubes

Stable, transparent and superhydrophobic carbon nanotube (CNT) nanocomposite films were fabricated by one-step spray casting process using the polystyrene functionalized CNTs, which were prepared by “living” free-radical polymerization and analyzed by means of infrared spectroscopy and thermal gravimetric analysis. The CNT film has a high water contact angle of 160° and a sliding angle of less than 3°. The surface topography of the fabricated film was characterized by field emission scanning electron microscopy. The transparency of the CNT film was investigated by UV–vis spectroscopy. The result shows that the CNT film has light transmittance of about 78% in the visible light region.     

Synthesis and characterization of polyester bionanocomposite membrane with ultrasonic irradiation process for gas permeation and antibacterial activity

Optically active bionanocomposite membranes composed of polyester (PE) and cellulose/silica bionanocomposite (BNCs) prepared with simple, green and inexpensive ultrasonic irradiation process. It is a novel method to enhance the gas separation performance. The novel optically active diol containing functional trifluoromethyl groups was prepared in four steps reaction and it was fully characterized by different techniques. Commercially available silica nanoparticles were modified with biodegradable nanocellulose through ultrasonic irradiation technique. Transmission electron microscopy (TEM) analyses showed that the cellulose/silica composites were well dispersed in the polymer matrix on a nanometer scale. The mechanical properties nanocomposite films were improved by the addition of cellulose/silica. Thermo gravimetric analysis (TGA) data indicated an increase thermal stability of the PE/BNCs in compared to the pure polymer. The results obtained from gas permeation experiments showed that adding cellulose/silica to the PE membrane structure increased the permeability of the membranes. The increase in the permeability of the gases was as follows: P_CH4 (38%) <P_N2 (58%) <P_CO2 (88%) <P_O2 (98%) Adding silica nanoparticles into the PE matrix, improved the separation performance of carbon dioxide/methane and carbon dioxide/nitrogen gases. Increasing the cellulose/silica mass fraction in the membrane increased the diffusion coefficients of gases considered in the current study. Further, antimicrobial test against pathogenic bacteria was carried out.     

Synthesis and characterization of silanized-SiO2/povidone nanocomposite as a gate insulator: The influence of Si semiconductor film type on the interface traps by deconvolution of Si2s

The polymer nanocomposite as a gate dielectric film was prepared via sol-gel method. The formation of cross-linked structure among nanofillers and polymer matrix was proved by Fourier transform infrared spectroscopy (FT-IR). Differential thermal analysis (DTA) results showed significant increase in the thermal stability of the nanocomposite with respect to that of pure polymer. The nanocomposite films deposited on the p- and n-type Si substrates formed very smooth surface with rms roughness of 0.045 and 0.058 nm respectively. Deconvoluted Si_2s spectra revealed the domination of the SiOH hydrogen bonds and SiOSi covalence bonds in the structure of the nanocomposite film deposited on the p- and n-type Si semiconductor layers respectively. The fabricated n-channel field-effect-transistor (FET) showed the low threshold voltage and leakage currents because of the stronger connection between the nanocomposite and n-type Si substrate. Whereas, dominated hydroxyl groups in the nanocomposite dielectric film deposited on the p-type Si substrate increased trap states in the interface, led to the drop of FET operation.     

Electrical resistance response of polyaniline films to water, ethanol, and nitric acid solution

<正>This paper reports on electrical resistance vs.aging time for the response of polyanihne films under exposure to water,ethanol and nitric acid(HNO_3) solution.Camphor sulfonic acid-doped polyanihne films were prepared by a "doping-dedoping-redoping" method,the morphology and microstructures of the films were characterized by a scanning electron microscope and an x-ray diffractometer,the electrical resistance was measured by a four-probe method.It was found that a lower amount of water molecules infiltrating the film can decrease the film's resistance possibly due to an enhancement of charge carrier transfer between polyanihne chains,whereas excessive water molecules can swell inter-chain distances and result in a quick increase of resistance.The resistance of the film under exposure to ethanol increases and becomes much larger than the original value.However,HNO3 solution can decrease the film's resistance sharply possibly owing to doping effect of protonic acid.These results can help to understand the conduction mechanism in polyaniline films,and also indicate that the films have potential application in chemical sensors.     

Tunable topographical cellulose matrices for electro-optical liquid crystal cells

In this work we have used acetoxypropylcellulose (APC) to produce free standing solid films (∼60 μm) that were used for assembling electro-optical devices. Thin films were obtained from concentrated lyotropic solutions of cellulose derivatives. Induced by the cast and shearing preparation conditions wrinkles and band textures can be observed in their free-surface plane. In order to eliminate and control these textures we used a process similar to that introducted in literature [1] which consists of storing the films in the same solvent-vapour atmosphere as the solution system. Lyotropic APC liquid crystalline solutions in dymethylacetamide (DMA) with crosslinker were prepared, thin films were obtained by using a shear/casting technique and stored in the solvent-vapour atmosphere until a planar structure was achieved. The dried crosslinked films were analyzed by optical polarised microscopy (POM) and scanning electron microscopy (SEM). The films with different topographies were used to produce optical cells composed by the cellulose derivative film covered on both free surfaces by a layer of the nematic liquid crystal E7 and placed between two transparent conducting substrates. The electro-optical properties of these cells were obtained.     

Structural and electrical studies of sodium iodide doped poly(vinyl alcohol) polymer electrolyte films for their application in electrochemical cells

Solid polymer electrolyte films based on poly(vinyl alcohol) (PVA) complexed with sodium iodide (NaI) were prepared using solution cast technique. The structural properties of pure and complexed PVA polymer electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD results revealed that the amorphous domains of PVA polymer matrix was increased with the increase in NaI salt concentration. The variation of film morphology was examined by scanning electron microscopy (SEM) studies. Fourier transform infrared spectral studies for pure and complexed PVA films revealed the vibrational changes that occurred due to the effect of dopant salt in the polymer. Direct current conductivity was measured in the temperature range of 303–373 K, and the conductivity was found to increase with the increase in dopant concentration as well as temperature. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions. Using these polymer electrolytes, solid-state electrochemical cells were fabricated. Various cell parameters like open-circuit voltage, short circuit current, power density, and energy density were determined.     

Quantum confinement effects in highly conducting,ultrathin polyaniline films pursued through spectroscopic investigations

Polyaniline (PANI) is well-known for its remarkable electrical and optical properties which find immense applications in polymer optoelectronics. Though extensive work has been reported in polyaniline samples both in bulk and thin film forms, much attention has not been paid to investigate the quantum confinement effects in ultrathin polyaniline films. The present work is devoted to the search for quantum confinement effects in ultrathin polyaniline films having nanometer thickness, prepared from m-cresol, through conventional and less sophisticated spectroscopic techniques. Remarkable blue-shift has been observed in the absorption spectrum of these samples. Much intense photo-luminescent emission with considerable blue-shift observed in these ultrathin films is cited as the clear evidence for confinement effects.     

Effect of dopant concentration on the properties of HCl-doped PANI thin films prepared at different temperatures

Polyaniline thin film doped with hydrochloric acid (PANI-HCl) has been prepared by chemical oxidative polymerization at three different temperatures (4 °C, 13 °C and 31 °C) with two different dopant concentrations (1 M, 2 M). Fourier transform infrared spectroscopy indicated the presence of dopant and increase in degree of polymerization with decrease in temperature. X-ray diffraction revealed that all the films are of amorphous nature. Scanning electron microscopy showed fiber morphology with high dense inter-fiber fusion. Hall-effect analysis showed that appreciable increase in conductivity of the PANI-HCl films with 2 M-dopant concentration prepared at low temperatures (4 °C, 13 °C) occurs due to increase in carrier concentration. It also indicates the films as P-type semiconductors. UV–vis absorption spectra and photoluminescence spectra revealed that the role of dopant concentration is highly effective in the films prepared at low temperatures. High intense absorption cum emission peaks observed for the films with 2 M dopant concentration prepared at low temperatures is due to the decreased fiber diameter which increased the surface to volume ratio of the fibers and increased localized defect states. Photoluminescence spectra of the films excited using 300 nm show high intense emission peaks at 360 nm, 494 nm and a weak peak at 409 nm confirming the semiconductor nature.     

Synthesis and electrical characteristics of polyaniline nanoparticles and their polymeric composite

Monodisperse polyaniline nanoparticles (PAPSSA) were synthesized from an oxidative dispersion polymerization using poly(sodium 4-styrenesulfonate) (PSSA) as both a polymeric stabilizer and a dopant agent due to its acidity. The nanoparticles were being stabilized with two different molecular weight of PSSA. Size effect of PAPSSA particles were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The d.c. electrical conductivity of composite films on the glass substrate was measured by a four-probe method. It was found that the electrical properties of the composite films are affected by the content of nano-sized polyaniline and different molecular weights of stabilizer in the poly(vinyl alcohol) (PVA) matrix.