间甲酚溶液中掺杂聚苯胺的氧化-还原行为研究

在有、无外加恒定磁场(0.4T)条件下,采用乳液聚合法合成了十二烷基苯磺酸掺杂聚苯胺(PAn),通过傅立叶红外光谱(FT-IR)、在有/无外电场作用下产物/m-cresol溶液的电导率、pH及其颜色随温度变化的分析表征,系统研究了温度对PAn/m-cresol溶液中PAn氧化-还原(掺杂-脱掺杂)行为的影响.溶液电导率和pH的测试结果显示,溶液电导率与溶液中游离掺杂酸的浓度成正比,PAn的掺杂度随温度的升高而降低,随温度的降低而增大,且在相同温度下,有、无外电场作用时PAn/m-cresol溶液的电导率存在突跃.与无磁场条件下合成的PAn所制备的m-cresol溶液相比,磁场条件下合成的PAn所制备的m-cresol溶液电导率的突跃更加显著.经脱掺杂处理后的PAn/m-cresol溶液的电导率均较低,对温度变化的响应极其微弱,且在有、无外电场作用时不发生突跃.分析认为,这是由于外电场作用下m-cresol溶液中掺杂态的PAn分子发生了取向重排,而脱掺杂的PAn则无此变化.PAn在外电场作用下的取向重排及氧化-还原性均与其掺杂程度相关,掺杂程度越高,氧化-还原及取向重排越显著.     

聚苯胺/顺丁橡胶复合导电膜的制备与性能(Ⅱ)

采用再掺杂方法制得了樟脑磺酸掺杂的聚苯胺(PAn-CSA),用溶液共混法制备PAn／BR导电复合膜．研究了聚苯胺与顺丁橡胶(BR)复合膜在间甲酚二次掺杂前后电导率的变化。实验表明:CSA对聚苯胺有较好的掺杂作用;二次掺杂使PAn复合膜电导率明显提高,其导电渗滤阈值略有降低,使卷曲的二次掺杂PAn链展开并通过分子链间的相互作用而自行组成导电通路．     

沉淀聚合制备磺酸掺杂的聚苯胺

以二丁基萘磺酸(DBNSA)或十二烷基苯磺酸(DBSA)为有机酸,水为主要反应介质的条件下进行沉淀聚合直接制备有机酸掺杂的聚苯胺(PAn).讨论了酸度、温度和氧化剂用量等反应条件对产物的影响。2L规模扩大实验的产率约为75%～80%,所得PAn具有高电导率(3.0S·cm^-1),并易溶于普通有机溶剂。其中PAn-DBNSA在各方面较具优势。     

聚苯胺/顺丁橡胶复合导电膜的制备与性能

采用溶液共混与浇铸法制备聚苯胺（PAn ）/顺丁橡胶（BR）复合导电膜,确定了本征态聚苯胺以顺丁橡胶为弹性基体材料,甲苯为溶剂,过氧化二苯甲酰为交联剂,十二烷基苯磺酸作为共混分散剂和聚苯胺掺杂剂的复合膜制备工艺,并对复合膜的导电性能和形态结构进行了测试与表征.     

绝缘聚合物对聚苯胺复合物导电性能的影响

将十二烷基苯磺酸掺杂的聚苯胺(PAn DBSA)与乙烯丙烯酸共聚物(EAA)或聚烯烃弹性体(POE)进行溶液共混制得了PAn DBSA/EAA或PAn DBSA/POE导电复合物。研究了绝缘聚合物的化学结构对聚苯胺导电复合物形态结构及电性能影响。结果表明,极性聚合物EAA中的羧基能与PAn形成氢键并发生掺杂作用,复合物中卷曲的PAn主链能充分展开,导致PAn/EAA复合物具有非常低的逾渗域值(1.5%),PAn含量为20.0%时,电导率高达7.1S/cm。POE为非极性共聚物,与极性较强的PAn相容性较差,导致PAn/POE复合物具有较高逾渗域值(5.0%),PAn含量为20.0%时,电导率仅为3.0×10-5S/cm。     

BaTiO_3包覆粉煤灰漂珠/聚苯胺复合材料的制备及电流变性能

首先利用原位化学氧化聚合法将聚苯胺包覆在粉煤灰漂珠表面(FAFB/PAn),再利用低温溶胶凝胶-水热法制备BaTiO_3包覆FAFB/PAn的复合材料(FAFB/PAn/BaTiO_3),形成内核为空心漂珠、外壳依次为导电层、绝缘层的核/壳结构.采用FTIR、XRD、SEM、数字式四探针以及LCR介电谱仪对FAFB/PAn/BaTiO_3复合材料的结构与性能进行分析;以FAFB/PAn/BaTiO_3为分散相制备的电流变液,对其悬浮性及外加电场下的剪切应力进行测试.FTIR和XRD结果证明了利用本文的实验方法可成功将PAn和BaTiO_3引入到FAFB表面.电导率测试结果表明,复合材料电导率为7.8×10~(-4)S·cm~(-1),相对BaTiO_3提高了近2个数量级.在1~2000 k Hz交变电场频率测试范围内,FAFB/PAn/BaTiO_3具有相对较好的介电性能:当f=1 k Hz时εr最大为598,随电场频率的增加介电常数逐渐减小,对应的介电损耗tanδ最大为1.14,且随电场频率的增加介电损耗逐渐减小,当f=200 k Hz时tanδ=0.75,后趋于平稳.比较了7天的悬浮稳定性发现,FAFB/PAn稳定性最好,悬浮率可达88%,而包覆BaTiO_3后与纯BaTiO_3相当,仅为60%.在电场作用下FAFB/PAn/BaTiO_3表现出较明显的电流变性能,即当E=4.0 k V/mm时,剪切应力达631 Pa,且具有较好的抗击穿能力.     

氧化剂对PAn/PTFE复合导电膜结构和性能影响的研究

分别以过硫酸铵和正钒酸钠作氧化剂,应用膜相渗透原位化学聚合法制备聚苯胺(PAn)/聚四氟乙烯(PTFE)复合导电膜,比较考察了两种氧化剂条件下膜孔中苯胺的聚合生长行为.扫描电镜、孔径分布及电化学测试结果表明:选用两种氧化剂分别制备的复合膜,均具有较小的膜孔径;与过硫酸铵相比,使用正钒酸钠作氧化剂时,复合膜的结构更为致密,且在保持较高表面电导率(2.62S·cm-1)的同时,断面电导率提高了1～2个数量级,电化学活性增强.     

磁场及反应条件对十二烷基苯磺酸掺杂聚苯胺聚合成膜速率的影响

在恒定磁场(0.6 T)条件下, 采用过硫酸铵(APS)为引发剂, 在乳液体系中合成了十二烷基苯磺酸(DBSA)掺杂的聚苯胺(PAn). 借助石英晶体微天平(QCM)实时监测苯胺(An)在金电极表面聚合成膜过程, 探讨了磁场、APS浓度、DBSA浓度及反应温度对DBSA掺杂聚苯胺聚合成膜速率的影响. 实验结果表明, PAn在金电极表面的成膜速率随磁场强度的增加而增大; 由反应物浓度与PAn成膜速率的关系, 得出相应的动力学反应级数; 由PAn膜的增长速率与温度的关系, 得到成膜过程的活化能为41.08 kJ/mol. 考察了PAn聚合过程的UV-Vis光谱, 并与QCM所得的结果进行了比较. 结果显示, 在相同时间内, 磁场环境下合成的PAn的吸收强度大于无磁环境下合成的PAn.     

磁场对苯胺微乳液聚合体系相行为的影响

通过十二烷基苯磺酸钠(SDBS)/正丁醇(n-butanol)/苯胺/水微乳液体系的拟三元相图,考察了恒定磁场(0.4T)和助表面活性剂与表面活性剂的质量比(Km=mn-butanol/mSDBS)对苯胺微乳液聚合体系的相行为、电导行为以及微乳化作用的影响.结果表明:随着体系醇含量的增加,微乳区面积先增大后减小,当Km值为1.0时,形成的微乳区最大;外加磁场可以增大微乳区面积.通过对外加磁场条件下溶液电导率随水含量变化规律的分析,印证了拟三元相图的表征结果.透射电镜分析结果表明,磁场条件下合成的聚苯胺颗粒比无磁场条件下合成的聚苯胺颗粒小.     

高性能聚苯胺自支撑膜

本文通过对可溶性聚苯胺(PAn)的特殊处理及成膜工艺的改造,采用溶液浇铸法,首次成功地制备出力学和电学性能均较好的大面积聚苯胺自支撑膜(HSPAn膜).研究结果表明,HSPAn膜的抗张强度、杨氏模量和伸长率分别为87.9MPa,1563.9MPa和10.2％;该膜具有金属光泽、较高的致密性和较好的韧性。分子尺寸较小的质子酸(如HCl,HClO_4,等)可有效掺杂HSPAn膜,使其电导率可达到导电型PAn粉末的数量级。有效掺杂的HSPAn膜均可轻度拉伸(断裂伸长率大于40.0％),拉伸膜的电导率可高达36.7s/cm。本征和掺杂的HSPAn膜均具有良好的环境稳定性,空气中放置数月后,其强度和电导率基本不变。     

Influence of the preparation procedure on the properties of polyaniline based magnetic composites

A versatile process for the preparation of composite films consisting of magnetite (Fe₃O₄) nanoparticles embedded in a polyaniline (PANI) matrix is reported. Spectroscopic properties of polyaniline matrix (PANI-EB), polyaniline protonated with camphor sulfonic acid (PANI-CSA_0.5) PANI-ES and PANI/Fe₃O₄-CSA_0.5 composites were studied, both in the state of the solutions of m-cresol and in thin films processed from the same solvents. The results of these studies indicate that m-cresol can be used for PANI/Fe₃O₄ composite preparation. Such films show both reasonably high electrical conductivity and magnetic permeability. A controlled application of a magnetic field during the casting process resulted in the formation of the materials with an unusual combination of magnetic and transport properties. The obtained films show the behavior that can be explained by the presence of both ferromagnetic and paramagnetic phases. The superparamagnetic contribution, if any, is very small. Application of the external magnetic field during fabrication of the composites stimulates creation of the aggregates of magnetic particles which, although keeps conductivity at a relatively high level, leads to a small decrease of the conductivity value.     

ANALYSIS AND CHARACTERIZATION OF MICROSCOPIC MORPHOLOGY AND ORIENTATION STRUCTURE OF POLYANILINE POLYMERIZED IN A CONSTANT MAGNETIC FIELD

Conductive polyaniline(PAn-_M and PAn-_O) doped with dodecylbenzene sulfonic acid(DBSA) was synthesized by using emulsion polymerization method in the presence of a constant magnetic field(0.4 T) and the absence of magnetic field, respectively.The effects of magnetic field on the microscopic morphology and orientation structure of PAn were generally analyzed and characterized by using transmission electron microscope(TEM),X-ray diffraction(XRD) and through the conductivity anisotropy of unit resistance o...     

Flow injection-spectrophotometric determination of cresol compounds in water by reaction withp-aminophenol

A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO₄ and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO₄ and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of detection of 10 g 1^–1 foro-cresol and 30 g 1^–1 form-cresol were found. The flow injection method has a lower sensitivity but permits more than 80 injections per hour. Based on the different maximum absorbance wavelengths obtained for the reaction products of PAP witho-cresol (614 nm) andm-cresol (632 nm), both compounds can be simultaneously determined in water samples and recoveries of 90 to 115% were found in spiked water samples of different types.     

Electrochemical Polymerization of Aniline at Low Supporting-Electrolyte Concentrations and Characterization of Obtained Films

Conductive polymers of aniline were synthesized in aqueous acidic media such as perchloric, sulfuric, hydrochloric, phosphoric, and trifluoroacetic acids and the effect of supporting electrolyte was investigated. The conductivity of each polyaniline (PAn) sample was determined by the four-probe technique. PAn (H₂SO₄) sample was shown to have the highest conductivity, specifically, 3.55 S cm^–1. The effect of concentrations of monomers and acids on the conductivity of PAn's was studied. It was observed that the conductivity decreased with increasing aniline concentration and increased with increasing sulfuric acid concentration. The conductivities of PAn (CF₃COOH) were also investigated in different supporting electrolytes and highly good increments of its conductivities were obtained. Magnetic properties of the PAn salts were analyzed by Gouy balance measurements and it was found that their conducting mechanisms are of bipolaron nature. From the FTIR analysis it was found that polymerization occurs via the –NH₂ group in a head-to-tail mechanism. The thermal analyses revealed that PAn (HCl) among the PAn salts studied shows the highest thermal stability. Surface analyses of polymers were clarified by scanning electron microscopy. From elemental analysis results, PAn salts were concluded to be in emeraldine structure.     

Photovoltaic properties of Pt/BiFeO3 thin film/fluorine-doped tin oxide capacitor

We study the photovoltaic properties of the Pt/BiFeO₃ (BFO) thin film/fluorine-doped tin oxide capacitor and obtain the open circuit voltage (V _oc) of 0.44 V and short circuit photocurrent (J _sc) of 0.14 mA/cm² under purple laser illumination. As compared to the BFO film with random orientations, the BFO film with a strong preferred orientation exhibits larger photovoltaic output as a result of its larger spontaneous polarization in the unpoled state. We further demonstrate that there is remarkable influence of external electric field poling on the photovoltage in the two polycrystalline BFO films, and the larger net change of the photovoltage after positive and negative poling in the highly preferred oriented BFO film is believed to be due to its improved crystalline structure. Our experiment results indicate that the responsiveness to external electric field and photovoltaic performance of the narrow-band-gap BFO film can be optimized by structural modification, making it possible to apply in the photosensitive and other optoelectronic devices.     

Effect of stereosequences on crystallinity and properties of zone‐drawn poly(vinyl alcohol) microfibrils

To effectively orient the molecular chains of novel syndiotactic poly(vinyl alcohol) (PVA) microfibrillar fiber (PVA fibril), a high‐temperature zone‐drawing method was adopted. The PVA fibrils were directly prepared from the saponification and in situ fibrillation without a spinning procedure. The maximum draw ratio of the PVA fibril increased with a decrease in the syndiotactic diad (r‐diad) content, indicating that the deformability of PVA molecules was lowered in higher syndiotactic PVA. Degree of crystal orientations up to 0.990 were achieved by stretching the PVA fibril with the r‐diad content of 65.1% and the original degree of crystal orientation of 0.902 at 250 °C close to its crystal melting temperature (T_m). When the same draw ratio was applied to the fibrils, a higher crystal orientation was achieved for the fibrils having higher syndiotacticity. Wide‐angle X‐ray data show that the longitudinal crystal sizes of drawn PVA fibrils were larger in higher syndiotacticities. The degree of crystal orientation, crystallinity, T_m, longitudinal crystal size, and tensile strength of the maximum drawn PVA fibril with a r‐diad content of 65.1% were 0.99, 0.97, 279 °C, 187 Å, and 4.66 N/tex, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1263–1271, 2001     

Synthesis and characterization of 1,3,4-oxadiazole-containing polyazomethines

Novel 1,3,4-oxadiazole-containing polyazomethines were synthesized by the polycondensation of diamines, 2,5-bis (m-aminophenyl)-1,3,4-oxadiazole (BMAO) and 2,5-bis (p-aminophenyl)-1,3,4-oxadiazole (BPAO), with aromatic dialdehydes, isophthalaldehyde and terephthalaldehyde, in m-cresol at 20°C. These polymers were yellow to orange in color and had reduced viscosities up to 1.13 dL/g and electric conductivity as high as 10^?11?10^?12 S cm^?1. All the polyazomethines were insoluble in common organic solvents but dissolved in concentrated sulfuric acid. Thermogravimetry showed that thermal degradation started at around 400°C in air and nitrogen atmospheres. Doping with iodine markedly increased the conductivity and produced the black-colored semiconductive polyazomethines with a maximum conductivity of the order of 10^?6 S cm^?1. Electronic spectra of the undoped polymers indicated a large bathochromic shift of the absorption maxima due to C?N bonds of the monomer diamines (285 nm for BMAO and 315 nm for BPAO). This suggests that π-electrons of the polymers are extensively delocalized along the main chain.     

Preparation and dielectric properties of highly preferred-(100) orientation (Pb,La)(Zr,Ti)O<Subscript>3</Subscript> antiferroelectric thick films by sol–gel processing

Pb_0.97La_0.02Zr_0.95Ti_0.05O₃ (PLZT) antiferroelectric thick films of highly preferred-(100) orientation with different thickness were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates depending on the sol–gel process technique. The effects of the PLZT thick films in the preparation and electric properties are investigated. The films show polycrystalline perovskite structure with a (100) preferred orientation by X-ray diffractometer analyses. The antiferroelectric nature of the thick films is demonstrated by P (polarization)–E (electric field). The temperature dependence of the dielectric constant and dielectric loss displays the similar behavior in both cases at 100 kHz while the values of polarization characteristic are decreased with the increase of the film thickness. The phase switching current are studied as a function of a gradually change dc electric field and the voltage dependent current density of the most highly (100)-oriented PLZT film is 1.49 × 10⁻⁸ A/cm² over electric field range from 0 to ±261 kV/cm. The film at 2,498 nm exhibits excellent dielectric properties and highly preferred-(100) orientation.