On the mechanism of conductivity enhancement in plasma treated poly(3,4-ethylenedioxythiophene) films

The conductive poly(3,4-ethylenedioxythiophene): p-toluene sulfonate (PEDOT : PTS) films were prepared by gas-phase polymerization using CVD technique. PEDOT : PTS films with better electrical performance were produced by the additional doping with O₂ plasma after vapor phase polymerization. The mechanism for this conductivity enhancement is studied through surface structural analyses using Raman and X-ray photoelectron spectroscopy (XPS). The increase in conductivity is likely to be due to the generation of new functional groups such as carboxyl and hydroxyl groups that are acted as a dopant and the removal of the impurities on PEDOT: PTS surface with plasma treatment.     

导电聚(3,4-二氧乙基噻吩)应用研究进展

聚(3,4-二氧乙基噻吩)(PEDOT)是目前发现的导电态最稳定的导电高分子之一,在抗静电、塑料内存、电解电容器、有机太阳能电池、有机电致发光显示器件等领域得到了广泛研究和应用.本文简要综述PEDOT在这些领域的应用进展情况.     

3，4-二硝基吡唑(DNP)的研究进展

随着武器装备的不断发展,对弹药能量和安全性的要求也越来越高,传统TNT基熔铸炸药存在易损性差、长期储存渗油、爆轰性能不理想等缺点,已不能满足当前不敏感弹药的发展要求;因此,研究炸药的新型载体是当前熔铸炸药发展的一个重要方向。3,4-二硝基吡唑(DNP)是一种新型的熔铸炸药载体。根据国内外的相关报道,阐述了DNP的合成方法、基本性能、机械感度、热安全性、相容性、应用性等研究发展现状。研究结果表明:目前,经N-硝化、热重排、C-硝化三步法合成DNP的工艺更加稳定,得率较高;DNP的熔点为86.5 ℃,理论密度为1.87 g/cm³,实测爆速为7 633 m/s（ρ=1.65 g/cm³）,爆热为4 326 kJ/kg,理论爆压为28.7 GPa;DNP的机械感度与TNT相当,具有较好的机械安全性;DNP热分解分两个阶段,第一阶段分解放热峰为319.8 ℃,第二阶段分解放热峰为407.2 ℃,与TNT和DNTF相比,DNP的热分解峰温高,热安定性好;DNP与RDX、HMX、CL-20、Al、AP、微晶蜡具有较好的相容性,可以与这些组分组成混合炸药,具有广泛的适用性。     

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite based thin films for Schottky diode application

Transparent, conductive films of poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite were synthesized by in-situ oxidative polymerization and investigated for their Schottky diode property. The prepared films were characterized by UV–Vis spectroscopy, thermal gravimetric analysis (TGA), surface resistivity, cyclic voltametery, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). SEM reveals the formation of homogeneous and adhesive polymer films while HRTEM confirms the uniform wrapping of polymer chains around the nanotube walls for PEDOT-FWCNT film. Improved thermal stability, conductivity and charge storage property of PEDOT in the presence of FWCNT is observed. Among different compositions, 5 wt. % of FWCNT is found to be optimum with sheet resistance and transmittance of 500 Ω sq⁻¹ and 77%, respectively. Moreover, the electronic and junction properties of polymer films were studied and compared by fabricating sandwich type devices with a configuration of Al/PEDOT or PEDOT-FWCNT nanocomposite/indium tin oxide (ITO) coated glass. The measured current density-voltage characteristics show typical rectifying behavior for both configurations. However, enhanced rectification ratio and higher forward current density is observed in case of PEDOT-FWCNT based Schottky diode. Furthermore, reliability test depicts smaller hysteresis effect and better performance of PEDOT-FWCNT based diodes.     

图案化与生物功能化聚3,4-乙烯二氧噻吩生物界面

本工作制备了具有可调控蛋白/细胞作用且低阻抗的功能化聚3,4-乙烯二氧噻吩(PEDOT)的图案化生物界面,并在空间上引导细胞的粘附行为.功能化PEDOT共聚物由具有抗非特异性粘附的磷酸胆碱功能化的EDOT(EDOT-PC)和可进行生物耦合反应的羧基功能化的EDOT(EDOT-COOH)两种单体共聚而成.本工作研究了不同组分共聚物的电化学阻抗性能及其对蛋白、细胞的抗粘附性能,同时通过精氨酸-甘氨酸-天冬氨酸(RGD)多肽的引入实现了在抗非特异性粘附背景下对细胞的特异性粘附.在此基础上,通过光刻及电化学沉积技术制备了由细胞特异性粘附区与抗细胞粘附区组成的图案化PEDOT生物界面,可有效地在空间上控制细胞粘附行为.该工作为研究细胞在材料表面的其他行为提供了可能性,在组织修复、再生工程中有着潜在的应用价值.     

聚3,4-乙撑二氧噻吩薄膜制备的研究进展

聚3,4-乙撑二氧噻吩(PEDOT)薄膜的电导率高、稳定性好、透明性佳,有广阔的应用前景。许多科技工作者致力于PEDOT薄膜的制备研究。简要介绍了导电PEDOT薄膜制备方法的研究进展。常用的制备方法有电化学聚合法,物理涂覆法,物理沉积法,原位聚合法。     

3,4-乙撑二氧噻吩(EDOT)的新合成方法

以氯乙酸为原料,通过酯化、Claisen缩合、O-烷基化和脱羧等反应合成出3,4-乙撑二氧噻吩,总产率为23.6%,运用FTIR、GC-MS对产品结构进行了表征,并对其反应机理进行了讨论.     

A Petrov-Galerkin Diffuse Element Method (PG DEM) and its comparison to EFG

The diffuse element method (DEM) pioneered␣by B. Nayroles, G. Touzot and P. Villon is a meshless method for solving partial differential equations. The original version does not pass the patch test. Here an improved version is proposed. This version is based on a Petrov-Galerkin formulation where test functions are required to meet different conditions than trial functions and is labeled here as PG DEM. It is shown that the original DEM derivative approximation is consistent but not integrable; therefore these functions are not suitable as test functions. A set of conditions on test and trial functions is applied. It is shown that the present Petrov-Galerkin (PG DEM) formulation satisfies the patch test and the numerical results show that it exhibits accuracy and rate of convergence superior to the original DEM, while the “stiffness matrix” will be unsymmetric even for self-adjoint problems.     

Virus-poly(3,4-ethylenedioxythiophene) composite films for impedance-based biosensing

Composite films composed of poly(3,4-ethylenedioxythiophene), PEDOT, and the filamentous virus M13-K07 were prepared by electrooxidation of 3,4-ethylenedioxythiophene (EDOT) in aqueous solutions containing 8 nM of the virus at planar gold electrodes. These films were characterized using atomic force microscopy and scanning electron microscopy. The electrochemical impedance of virus-PEDOT films increases upon exposure to an antibody (p-Ab) that selectively binds to the M13 coat peptide. Exposure to p-Ab causes a shift in both real (Z(RE)) and imaginary (Z(IM)) impedance components across a broad range of frequencies from 50 Hz to 10 kHz. Within a narrower frequency range from 250 Hz to 5 kHz, the increase of the total impedance (Z(total)) with p-Ab concentration conforms to a Langmuir adsorption isotherm over the concentration range from from 6 to 66 nM, yielding a value for K(d) = 16.9 nM at 1000 Hz.     

Syntheses of titania and poly(3,4-ethylenedioxythiophene) bilayer nanotubes

Synthesis of bilayer tubes of poly(3,4-ethylenedioxythiophene) (PEDT) and titania by electrochemical polymerization of PEDT and chemical deposition of titania in the pores of anodic alumina was reported. Electron diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and fourier transformed infrared spectroscopy (FTIR) were used to characterize these bilayer tubes. SEM photographs show the tubes of uniform diameters around 200 nm. TEM photographs confirm the formation of titania and PEDT bilayer tubes of 230 nm and 100 nm diameter, the thickness of outside TiO2 layer and inner PEDT layer are around 20 nm under the experimental condition. The XPS spectra of the bilayer tubes show that the Ti2p peak shifts to a lower binding energy and S2p peak shifts to a higher binding energy. Electron diffraction patterns show that TiO2 nanotubes formed was single crystals of anatase phase. I-V characteristic curves were measured for samples prepared under various conditions.     

3,4-乙撑二氧噻吩水相的电化学聚合

以水为溶剂,在不添加乳化剂的条件下,分别以高氯酸锂、聚苯乙烯磺酸钠(PSS)、硫酸钠、氟硼酸钠、对甲苯磺酸为电解质进行电化学聚合,得到了不同氧化态的聚3,4-乙撑二氧噻吩薄膜(PEDOT)。探讨了这5种电解质对单体初始氧化电位和薄膜电化学稳定性的影响。结果表明,采用PSS为电解质时初始氧化电位最低为878mV,得到的聚合物薄膜电化学稳定性最好。并采用扫描电镜表征了以PSS为电解质电化学聚合所得薄膜的表面形貌,采用光谱电化学法表征了薄膜的电致变色性能,结果表明聚合物薄膜均质连续,具有优异的电致变色性能。     

Ultraporous poly(3,4-ethylenedioxythiophene) for nanometric electrochemical supercapacitor

Ultrathin films of poly(3,4-ethylenedioxythiophene) (PEDOT) have been prepared by electropolymerization on steel and indium-tin oxide (ITO) substrates under identical experimental conditions. Scanning electron microscopy and atomic force microscopy indicate that the substrate affects dramatically both the morphology and topography of films when the polymerization times are very short. An ultraporous three-dimensional network involving ultrathin sticks with a fiber-like morphology was formed on ITO. Asymmetric and symmetric supercapacitors have been fabricated by assembling electrodes of PEDOT deposited on ITO and steel. The specific capacitance, electrochemical stability, supercapacitor behavior and Coulombic efficiency measured for devices with an ITO/steel configuration were similar to those reported for advanced PEDOT-inorganic hybrid composites. Furthermore, the performance of the ITO/steel assembly is higher than those determined for symmetric supercapacitors derived from two identical electrodes of PEDOT deposited on steel or on ITO. The unique properties of the asymmetric supercapacitors have been attributed to the ultraporous structure of the ultrathin films deposited on ITO, which is not significantly perturbed when the device is submitted to a very high number of consecutive oxidation-reduction processes, and the different electroactivities of the two electrodes.     

Electrochemistry of Poly(3,4‐alkylenedioxythiophene) Derivatives

An overview of the electrochemistry of poly(3,4‐alkylenedioxythiophene)s (PXDOTs) is presented. As a class of conducting and electroactive polymers that can exhibit high and quite stable conductivities, a high degree of optical transparency as a conductor, and the ability to be rapidly switched between conducting doped and insulating neutral states, PXDOTs have attracted attention across academia and industry. Numerous fundamental aspects are addressed here in detail, ranging from the electrochemical synthesis of PXDOTs, a variety of in‐situ characterization techniques, the broad array of properties accessible, and morphological aspects. Finally, two electrochemically‐driven applications, specifically electrochromism and chemical sensors of PXDOTs are discussed.     

Synthesis and characterization of regioregular alkyl-substituted poly(3,4-ethylenedioxythiophenes)

In order to increase the solubility of PEDOT, we introduced an alkyl chain into polymer backbone. Depending on the position of the alkyl bond, the steric hindrance between the alkyl chains can also leads to regioregularity in the polymer. The regioregular polymers can easily occur self-assembly, both in solution and in the solid state, resulting in highly ordered two- and three-dimensional polymer architectures. A series of soluble regioregular alkyl-substituted PEDOTs were synthesized using the Grignard Metathesis (GRIM) for the purpose of study on regiorandom and regioregular PEDOT. The ethylene proton adjacent to the oxygen atom of regioregular methoxydodecyl-PEDOT appears at 3.51 ppm, whereas the corresponding peak of regiorandom methoxydodecyl-PEDOT appears at 3.42 ppm.     

Preparation and characterization of conducting poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Langmuir-Blodgett film

The self-assembly of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) nanoparticles at an air/water interface was achieved by means of the electrostatic force between an octadecylamine (ODA) monolayer and PEDOT-PSS nanoparticles. A surface pressure (π)-area (A) isotherm and X-ray photoelectron spectroscopy of the composite film were used to confirm the electrostatic force between the SO₃⁻ group of PSS and the NH₄⁺ group of aliphatic amines. Monolayer and multilayer composite films of ODA/PEDOT-PSS and ODA-stearic acid (SA)/PEDOT-PSS were fabricated. These solid Langmuir-Blodgett films were investigated by the UV-Vis spectrum, atomic force microscopy, and X-ray diffraction method. It is observed that ODA-SA/PEDOT-PSS films had a higher film-forming capability than ODA/PEDOT-PSS films and an ordered multilayer structure was developed. The conductive properties of ODA-SA/PEDOT-PSS LB films were investigated in detail. Factors influencing the film conductivity such as the layer number and surface pressure were discussed and the conductive mechanism was also studied.     

Nanoclays reinforced glass ionomer cements: dispersion and interaction of polymer grade (PG) montmorillonite with poly(acrylic acid)

Montmorillonite nanoclays (PGV and PGN) were dispersed in poly(acrylic acid) (PAA) for utilization as reinforcing filler in glass ionomer cements (GICs). Chemical and physical interaction of PAA and nanoclay (PGV and PGN) was studied. PAA–PGV and PAA–PGN solutions were prepared in different weight percent loadings of PGV and PGN nanoclay (0.5–8.0 wt%) via exfoliation-adsorption method. Characterization was carried out by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and fourier transform infrared (FTIR) spectroscopy. XRD results of PAA–PGN demonstrated that the interlayer space expanded from 12.83 to 16.03 Å indicating intercalation whereas the absence of the peak at d ₀₀₁ in PAA–PGV indicated exfoliation. XPS scans of PGV and PGN nanoclays depicted the main peak of O 1s photoelectron due to Si–O–M (M = Mg, Al, Fe) whereas, Si–O–Al linkages were identified by Si 2p or Si 2s and Al 2p or Al 2s peaks. The disappearance of the Na peak confirmed that PAA molecules exchanged sodium ions present on surface of silicate layers and significantly reduced the electrostatic van-der-Waals forces between silicate plates resulting in intercalation or exfoliation. FTIR spectra of PAA–nanoclay suspensions demonstrated the presence of a new peak at 1,019 cm^?1 associated with Si–O– stretching vibrations which increased with increasing nanoclays concentration. Information concerning the dispersion of nanoclay in PAA aqueous solutions, chemical reaction and increase interlayer space in montmorillonite nanoclay is particularly useful regarding dispersion and reinforcement of nanoclay in PAA.     

新型有机导电发光材料聚乙撑二氧噻吩的研究现状

PEDOT是一种新型的有机导电发光材料,具有高电导率、好的环境稳定性、薄膜易制且透明性好等优点,是制备有机电致显示、太阳能电池、超级电容器等电子设备的理想材料。由于其独有的电学和光学特性及广泛的应用领域,PEDOT必将引起人们广泛关注。本文简述了PEDOT的研究现状及合成中尚存在的问题。     

不同溶剂中导电聚合物PEDOT的化学氧化聚合及光谱研究

利用3,4-乙撑二氧噻吩单体和对甲苯磺酸铁,分别以异丙醇、四氢呋喃和乙氰为溶剂,用化学氧化法合成了导电聚合物聚（3,4-乙撑二氧噻吩）,3种溶剂中的反应速率有较大差异,乙氰中反应速率最快,四氢呋喃中反应速率最慢.三者的聚合产物都具有较高的电导率,但四氢呋喃中合成产物的电导率略高于另外两个产物.红外光谱和拉曼光谱显示,3种溶剂中合成的聚（3,4-乙撑二氧噻吩）在化学结构、分子共轭长度、掺杂情况等方面基本相同.