STUDIES ON ENHANCED CONDUCTIVITY OF STRETCHED CONDUCTING POLYMERS

A physical model of series of the conductivity on chain and the interchain conductivitybetween chains is proposed to explain enhanced conductivity of stretched conducting polymers.This model suggests that the enhanced conductivity for stretched conducting polymers might bedue to increasing of the interchain conductivity between chains along the elongation direction afterdrawing processes if the conductivity on chain is assumed much larger than that of the interchainconductivity between chains. According to this model, it is expected that the temperaturedependence of conductivity measured by four-probe method for stretched conducting polymers iscontrolled by a variation of the interchain conductivity between chains with temperature, whichcan be used to explain that a metallic temperature dependence of conductivity for stretchedconducting polymers is not observed although the conductivity along the elongation direction isenhanced by two or three orders of magnitude.

STUDIES ON THE ELECTRICAL CONDUCTIVITY OF FREE-STANDING FILMS OF POLYANILINE

An insulate to metal transition was investigated based on the measurements of the dependence of the conductivity, activation energy on the protonation state of polyaniline (PANI). An isotropy in conductivity for stretched salt form of PANI was observed.For salt film of PANI, the Ⅰ-Ⅴ curve obeys Ohm's law, which shows a typical metal behavior, however, for base film or film with low protonation state, it can be explained by Space Charge Limited Current (SCLC). It is also found that the Ⅰ-Ⅴ curve of base film of PANI is independent of the work function of electrodes and the polymerization temperature.

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

This paper reports on electrical resistance vs. aging time for the response of polyaniline films under exposure to water, ethanol and nitric acid （HNO3） solution. Camphor sulfonic acid-doped polyaniline 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 polyaniline 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.

IONIC CONDUCTIVITY IN CROSSLINKED POLY (METHYLSILOXANE-g-ETHYLENE OXIDE) NETWORK FILMS CONTAINING LITHIUM PERCHLORATE

Polymer electrolytes based on poly (methylsiloxane-g-ethylene oxide) and LiClO_4 have been prepared. The network films crosslinked by a crosslinking agent are found to exhibit a considerably high ionic conductivity of about 10^(-4) Scm^(-1) at room temperature and have good flexibility.

INFRARED EMISSIVITY OF CONDUCTING POLYMERS

The infrared emissivity of conducting polymers in 8—20μm and at 50—150℃ in the direction of normal line has been measured as a function of wavelength, conductivity at room temperature, counterion, doping levels, measuring temperature and thickness of sample.

Determination of Volume Conductivity of Thin Polymeric Films Using Corona Triode, When the Current through the Sample Depends Quadratically on Grid Potential

In this paper is determined the volume conductivity of thin polymeric films using the corona triode method, when the current through the sample exhibits a quadratic dependence on the grid potential. Based on the experimental data, for the first time, an effective methodology for the determination of volume conductivity, graphically and analytically, is composed. The results obtained by the proposed analytical formula, for polypropylene and Trespaphan, with two different configurations of structures, are closely similar to the graphical method results. In addition, the satisfying accordance of our results, with the results, found out with the consulted literature, obtained by the “static” methods, confirms the accuracy of the proposed methodology, for the determination of volume conductivity of thin polymeric films, using the corona triode.

Enhancing the thermal conductivity of polymer-assisted deposited Al_2O_3 film by nitrogen doping

Polymer-assisted deposition technique has been used to deposit Al2O3 and N-doped Al2O3 （AION） thin films on Si（100） substrates. The chemical compositions, crystallinity, and thermal conductivity of the as-grown films have been characterized by X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and 3-omega method, respectively. Amorphous and polycrystalline Al2O3 and AlON thin films have been formed at 700 ℃ and 1000 ℃. The thermal conductivity results indicated that the effect of nitrogen doping on the thermal conductivity is determined by the competition of the increase of Al-N bonding and the suppression of crystallinity. A 67% enhancement in thermal conductivity has been achieved for the samples grown at 700 ℃, demonstrating that the nitrogen doping is an effective way to improve the thermal performance of polymer-assisted-deposited Al2O3 thin films at a relatively low growth temperature.

FERROFLUID CONTAINING SOLUBLE CONDUCTIVE POLYANILINE AND ITS FREESTANDING FILMS

Ferrofluid containing highly conductive polyaniline (PANI) was prepared, in which soluble PANI solutions dopedwith 10-camphorsulfonic acid (CSA) and dodecyl benzenesulfonic acid (DBSA) were used as the basic solution and Fe_3O_4nanoparticles (d = 10 nm) as the magnetic material. Moreover, the freestanding films of the resulting ferrofluid can beobtained by an evaporation method. The electrical and magnetic properties of the ferrofluid or its films can be adjustedthrough changing the content of PANI and Fe_3O_4. High saturated magnetization (≈ 30 emu/g) and high conductivity(≈ 250 S/cm) of the composite films can be achieved when the composite film contains 26.6 wt% of Fe_3O_4. In particular, itwas found that the composite films exhibit a super-paramagnetic behavior (Hc = 0) attributed to the size of Fe_3O_4 particles on the nanometer scale.

Antibacterial Effect of the Conducting Polyaniline

Excellent antibacterial performance of polyaniline （PAni） against Escherichia coli and Gram-positive Staphylococcus aureus microorganisms has been demonstrated under both dark and visible light conditions. The electrostatic adherence between the PAni molecules and the bacteria may play a very important role for the antibacterial reaction of the PAni. As a result of our investigation, conducting PAni and its composites/blends are believed to be useful as a new type of antibacterial agent, self-clean as well as multifunctional material for improving the human health and living environment.

Conductive Polyaniline/Cellulose/Graphite Composite Films with High Thermal Stability and Antibacterial Activity

Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.

Preparation and Properties of Polyaniline Composite Films

Polyaniline (PAn) was synthesized by chemical oxidation polymerization. The conductive polymer doped by camphor sulfonic acid (CSA) and a matrix polymer, polyamide66, polyamide1010 or polyamide11, were dissolved in m-cresol and the blend solution was cast in a glass and dried for preparing polyaniline composite films. Conductivity was from 10 -6 to 10 0 Ω -1 ·cm -1 with different weight fraction of PAn-CSA. The crystallization of the films was studied by means of differential scanning calorimeter (DSC). The treatment of the composite films in different pH value solution would result in decrease of conductivity, especially in an alkaline solution.

Charge transport in conducting polyaniline co-doped with sulfosalicylic acid and dodecylbenzoyl sulfonic acid

We prepared conducting polyaniline （PAn） co-doped with sulfosalicylic acid （SSA） and dodecylbenzoyl sultonic acid （DBSA） in micro-emulsive polymerization, and studied its charge transport behaviors based on the measurement of its electrical conductivity in the temperature range between 203 K and 298 K. The conductivity was found to increase with temperature, similar to the case in semiconductors. Analyzing the experimental data with three models, namely the charge-energy-limitedtunneling model, Kivelson model and the three-dimensional variable range hopping （3D-VRH） model demonstrated that these models all describe well the charge transport behaviors of PAn co-doped with SSA and DBSA within the mentioned temperature range. From calculation with the 3D-VRH model, the hopping distance of the conducting PAn is obviously larger than its localization length. The PAn doped with SSA and DBSA enjoys desirable crystallinity due to the co-doping of two functional sulfonic acids. The macroscopic conductivity may correspond to three-dimensional transport in the network of the bundles, and the metallic islands may be attributed to quasi-one-dimensional bundles.

填充型聚合物基导热复合膜的研究进展

随着柔性电子器件的飞速发展和应用,传统的热管理材料无法满足高导热、高韧性、良好机械适应性的应用需求。具有高导热系数的柔性导热薄膜材料在下一代器件的热管理应用中显示出巨大的潜力,因此引起了广大学者的关注。目前,导热薄膜材料在智能手机、超薄笔记本、柔性可穿戴设备和智能家电设备中均展现巨大的应用潜能。本文从提升填充型导热复合膜的导热性能出发,介绍了填充型导热复合膜的分类和填充型导热复合膜的导热机理。由设计填料构筑低热阻高导热通路和构筑三维导热网络两种思路提升复合膜的导热性能,阐明了填充型导热复合薄膜的研究进展。

电沉积法制备三种碳材料/导电聚合物复合涂层在金属双极板表面的应用进展

简单介绍了质子交换膜燃料电池在酸性环境下金属双极板容易发生腐蚀,导致燃料电池输出效率降低的问题;概述了导电聚合物涂层在金属双极板表面的四种防腐机制,包括物理屏障机理、阳极保护、智能释放机理和电场屏蔽机理。以聚吡咯(PPY)、聚苯胺(PANI)为例,综述了近年来电沉积制备的碳纳米管、石墨烯和碳粉三种碳材料/导电聚合物复合涂层在金属双极板表面的应用,从制备方法、涂层材料、基底材料、测试环境、耐蚀性能和形貌对应用情况做总结对比。最后展望了碳材料/导电聚合物复合涂层面临的挑战和未来的要求。

PREPARATION OF POLYANILINE/ACETYLENE BLACK COMPOSITE AS HOLE CONDUCTOR IN SOLID-STATE DYE-SENSITIZED SOLAR CELL

A clay-like conductive material comprising polyaniline（PANI）-acetylene black particles is fabricated as a hole conductor for dye sensitized solar cell（DSSC）.The results show that the introduction of acetylene black into the polymer electrolyte improves the photovoltaic behavior of solid-state DSSC,owing to the increase of the hole mobility of PANI electrolyte,the improvement of the wetting quality of the composite electrolyte,and the reinforcement of interface contact between electrode and the electrolyte.Finally,the overall energy conversion efficiency of DSSC with PANI-50%（in weight）acetylene black electrolyte is 48% of that of liquid DSSC.Therefore,the PANI-acetylene black composition is a credible alternative to hole conductor in application of solid DSSC.

聚合物基透明导电薄膜断裂韧性的测量方法

在航空透明件领域,厚聚合物基底上透明导电薄膜的断裂韧性是量化抗开裂性的关键力学特性,因此基于纳米压痕和通道开裂试验评估了薄膜的断裂韧性。采用磁控溅射法将氧化铟锡(ITO)薄膜沉积在聚碳酸酯(PC)基底上。纳米压痕试验中,纳米压痕在ITO薄膜上引起脆性断裂,通过对所得的载荷-深度曲线进行积分来计算断裂韧性;通道开裂试验中,使用原位拉伸法获得开裂应变,并结合力学模型计算断裂韧性。结果表明,不考虑残余应力时,2种测试方法获得了相对一致的断裂韧性,500 nm厚ITO薄膜的断裂韧性为1.62~1.81 MPa·m^(1/2);对于200 nm以下厚度的薄膜或存在大残余应力的薄膜,宜选择通道开裂试验以确定断裂韧性。

导电高分子材料制备及应用进展

导电高分子材料是一类具有导电性能的聚合物材料,通常是由一些有机单体聚合而成,由于其含有共轭的π-电子体系组成,使得电子能够在材料中进行自由移动,从而具有良好的导电性能。导电高分子材料在传感器技术、能源存储和转换、生物医学、电磁屏蔽材料、涂料和涂层等领域得到广泛的应用,主要综述了近几年来导电高分子材料最新研究进展,以及其在相关领域的应用。

ELECTROACTIVE AND NANOSTRUCTURED POLYMERS AS SCAFFOLD MATERIALS FOR NEURONAL AND CARDIAC TISSUE ENGINEERING

Conducting polymer, polyaniline （PANI）, has been studied as a novel electroactive and electrically conductive material for tissue engineering applications. The biocompatibility of the conductive polymer can be improved by （i） covalently grafting various adhesive peptides onto the surface of prefabricated conducting polymer films or into the polymer structures during the synthesis, （ii） co-electrospinning or blending with natural proteins to form conducting nanofibers or films, and （iii） preparing conducting polymers using biopolymers, such as collagen, as templates. In this paper, we mainly describe and review the approaches of covalently attaching oligopeptides to PANI and electrospinning PANI-gelatin blend nanofibers. The employment of such modified conducting polymers as substrates for enhanced cell attachment, proliferation and differentiation has been investigated with neuronal PC-12 cells and H9c2 cardiac myoblasts. For the electrospun PANI- gelatin fibers, depending on the concentrations of PANI, H9c2 cells initially displayed different morphologies on the fibrous substrates, but after one week all cultures reached confluence of similar densities and morphologies. Furthermore, we observed, that conductive PANI, when maintained in an aqueous physiologic environment, retained a significant level of electrical conductivity for at least 100 h, even though this conductivity was decreasing over time. Preliminary data show that the application of micro-current stimulates the differentiation of PC-12 cells. All the results demonstrate the potential for using PANI as an electroactive polymer in the culture of excitable cells and open the possibility of using this material as an electroactive scaffold for cardiac and/or neuronal tissue engineering applications that require biocompatibility of conductive polymers.

Hybrid supercapacitor based on polyaniline doped with lithium salt and activated carbon electrodes

Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon electrode were fabricated and compared with the redox type capacitors （PLi/PLi） based on two uniformly Li-doping polyaniline electrodes. The electrochemical performances of the two types of supercapacitors were characterized in non-aqueous electrolyte. PLi/C supercapacitors have a wider effective energy storage potential range and a higher upper potential. At the same time, the PLi/C supercapacitor exhibits a specific capacity of 120.93 F/g at initial discharge and retains 80% after 500 cycles. The ohmic internal resistance （REs） of PLi/C supercapacitor is 5.0 Ω, which is smaller than that of PLi/PLi capacitor （5.5 Ω）. Moreover, it can be seen that EtgNBF4 organic solution is more suitable for using as organic electrolyte of PLi/C capacitor compared with organic solution containing LiPFr.