溴掺杂聚苯胺的导电性能及机理研究

通过化学氧化法制备聚苯胺,对其进行溴和氢溴酸掺杂,聚苯胺(PANI)的电导率比掺杂前提高了11-13个数量级。采用红外光谱、热重分析、紫外可见光谱和X射线光电子能谱分析研究了溴和氢溴酸对PANI的掺杂作用,探讨了掺杂PANI的导电机理。研究表明,不同于氢溴酸对PANI的质子酸掺杂,溴掺杂过程中产生的溴负离子增加了PANI的载流子浓度并形成电子转移复合物,提高了聚苯胺的电导率。     

不同浸润度聚苯胺的制备及性能

采用乳液聚合的方式,分别选取十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTMAB)、聚乙二醇(PEG)作为分散剂,制得了浸润度不同的聚苯胺(PANI)。研究了不同类别分散剂对PANI性能的影响。采用扫描电镜(SEM)、X射线衍射(XRD)、水接触角(WCA)、傅里叶红外光谱(FT-IR)、紫外-可见光光谱(UV-Vis)、激光粒度仪等测试方法对PANI的结构与性能进行了分析,并通过循环伏安和交流阻抗实验研究了PANI的电化学性能。结果表明所有PANI样品均处于掺杂态,以PEG为分散剂的样品亲水性最佳,CTMAB次之,SDS最差。PEG为分散剂能够降低PANI的粒度,提高PANI的规整度进而增强其导电性能。阴离子分散剂SDS亲水端带负电,容易被质子掺杂的聚苯胺吸附,SDS的疏水端向外提供了PANI疏水性。SDS存在下合成的PANI粒度较大,电导率最低。阳离子型分散剂CTMAB因为其亲水端带正电不利于质子酸掺杂PANI,电荷转移阻抗较高。     

碳纳米管网/聚苯胺复合材料的制备及电化学储能性能

分别采用粉末碳纳米管(CNT)和带连接点的碳纳米管网(CNTN)为模板,通过与聚苯胺(PANI)有限域聚合得到了CNT/PANI和CNTN/PANI 2种复合材料.采用透射电子显微镜和扫描电子显微镜对材料的形貌进行了表征,采用氮气吸附-脱附分析研究了材料的孔结构参数,运用双电四探针测试仪对材料的导电性能进行了测试,利用恒流充放电、循环伏安、循环寿命及交流阻抗等电化学测试手段表征了材料的电化学储能性能.结果表明,CNTN/PANI复合材料比CNT/PANI复合材料表现出更好的导电性能和电化学储能性能,其放电比容量可达到143.2 F/g(有机电解液).     

PANI/Ce(OH)3-Pr2O3·3H2O/NanoG复合材料制备与表征

开发了反胶束模板-原位聚合纳米复合法制备聚苯胺(PANI)/Ce(OH)3-Pr2O3·3H2O/石墨纳米薄片(NanoG)纳米复合材料的方法.膨胀石墨在乙醇水溶液中经超声处理制得石墨纳米薄片,以苯胺的氯仿溶液为油相,稀土金属离子Pr3+、Ce3+水溶液为水相,依靠表面活性剂十六烷基三甲基溴化铵(CTAB)自组装形成的反胶束为模板-制备PANI/Ge(OH)3-Pr2O3·3H2O/NanoG复合材料.利用红外光谱(FTIR)、扫描电镜(SEM)、透射电镜(TEM)和 X-射线衍射(XRD)对该复合材料进行了表征和分析,研究了其导电性能和热性能.结果表明,PANI/Ce(OH)3-Pr2O3·3H2O/NanoG复合材料各相分散均匀,稀土纳米粒子在体系中以棒状的形态分布.热重分析表明,该复合材料的热稳定性明显提高;导电性研究说明,石墨纳米薄片的特殊的结构(较大的径厚比)对其在聚合物基体中形成导电网络具有重要作用;PANI/Pr2O3-Ce(OH)3/NanoG纳米复合材料的渗滤阀值低于1.0wt%.     

尺寸可控的聚苯胺复合微球的电纺制备与表征

以十二烷基苯磺酸(DBSA)掺杂的导电聚苯胺与聚乙二醇(PEG)及Fe3O4的混合氯仿溶液,采用静电纺丝(spinning technology)方法制备含Fe3O4纳米颗粒的导电聚苯胺(PANI)/PEG/Fe3O4复合微球.SEM结果表明,电纺所得的PANI/PEG/Fe3O4复合微球结构依赖于PEG聚合物浓度、静...     

有机化学接枝-电化学沉积聚合制备CNTs/PANI纳米复合材料

通过有机化学合成法先在碳纳米管表面接枝上苯胺单体,然后在不锈钢电极表面在硫酸溶液中采用循环伏安法电化学沉积聚合制得碳纳米管/聚苯胺(CNTs/PANI)纳米复合材料.扫描电子显微镜和傅立叶变换红外光谱表征所得材料的微观结构和基团,循环伏安和恒流充放电测试用于考察所得CNTs/PANI纳米复合材料的电化学性能.所得结果与...     

原位聚合法制备PANI/PET导电织物及其性能分析

在聚酯纤维基材及其织物表面,原位聚合形成厚度约1~2μm聚苯胺包覆层,制得聚苯胺(PANI)/聚酯(PET)导电织物.PANI层优异的导电性能使之成为有广阔发展前景的柔性电磁屏蔽材料.正交试验分析研究了苯胺单体浓度、氧化剂:苯胺摩尔比、掺杂酸浓度、反应时间对PANI包覆层外观形态、与基体结合牢度以及导电性的影响.实验表明:在经适当前处理的PET基材表面,以苯胺单体浓度为0.25mol/L、氧化剂与苯胺摩尔比为1∶1、掺杂酸浓度0.5 mol/L、反应时间60 min、反应温度为0~20℃时制备的PANI/PET导电织物方阻最小,导电性最好;掺杂酸酸性越强,导电性越好.SEM、FTIR及XRD测试表明涤纶织物表面有均匀连续的聚苯胺膜存在.分析表明聚苯胺分子链中氧化结构与还原结构含量基本相等,说明聚苯胺渗入纤维内部,使纤维无定形区面积增加,结晶度减小.     

PI/PANI复合材料的制备与表征

以纳米聚苯胺为电磁波的吸收剂,高强度、耐高温的聚酰亚胺为基体设计与制备了高强度、耐热、质轻、薄和吸收宽的新型纳米复合吸波材料.利用微乳液法,以十二烷基苯磺酸(DBSA)为乳化剂和掺杂剂,以过硫酸铵(APS)为氧化剂合成了纳米级聚苯胺(PANI).在此基础上,以PANI的NMP溶液为均苯四甲酸二酐(PMDA)与4,4′-二氨基二苯醚(ODA)的聚合场所,室温下,原位聚合出PANI/聚酰胺酸(PAA)复合材料,再经过亚胺化制备出了PANI/PI复合材料.利用XRD表征了聚合物的结晶形态.红外光谱表征了中间体和聚合物.利用场发射扫描电镜发现PANI/PI复合材料呈现海岛结构,PANI像岛屿一样分散在PI的连续相中,两种材料复合并没有破坏各自的结晶形态.利用数字电桥和自制电极表征了不同含量复合材料的损耗性能,当聚苯胺加到3.4%以上时,复合材料的损耗因数提高了,并且随着频率的增大损耗因数直线增大.     

三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

一维有序聚苯胺纳米阵列的制备及电化学储能性能

以导电玻璃FTO为基底电极, 在硫酸溶液中, 分别研究了苯胺单体浓度和恒定电流大小对聚苯胺(PANI)形貌的影响; 同时恒定苯胺单体的浓度和工作电流, 探究了不同类型的质子酸对PANI阵列形貌的影响. 结果表明, 采用恒电流方法可以制备出一维有序PANI纳米线阵列, 而且当苯胺的浓度为0.1 mol/L, 恒电流法的工作电流密度为0.03 mA/cm²时, 所制备的PANI纳米线阵列形貌最佳; 当用HCl, HNO₃和对甲苯磺酸(p-TSA)作为合成PANI的支持液时, 得到树桩状的PANI 纳米结构, 不能得到均一的纳米线阵列结构. 电化学性能测试结果表明, 制备的最佳形貌PANI纳米线阵列的比电容值可达560 F/g; 循环1000周后电容损失率为11%.     

Conductive Nanocomposites Based on Cellulose Nanofibrils Coated with Polyaniline-DBSA Via In Situ Polymerization

Summary: Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI-DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet-visible-near infrared (UV-Vis - NIR) and Fourier-transform infrared (FTIR) spectroscopies and X-ray diffraction (XRD). FTIR and UV-Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10⁻¹ S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X-ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils.     

Conductive elastomeric nanocomposites based on oxidation of aniline with silver nitrate via inverse emulsion polymerization

The present investigation describes a facile and rapid approach of conductive nanocomposites production and assesses the opportunity of their use as electro‐mechanical sensors. Hybrid materials containing silver and polyaniline nanoparticles reinforcing a thermoplastic elastomeric matrix were studied. The approach developed includes ultrasonically assisted in situ inverse emulsion polymerization of aniline oxidized by a weak oxidant and silver nitrate, and supported with a strong oxidant, ammonia peroxydisulfate. Aniline was doped with dodecylbenzene sulfonic acid in the presence of dissolved styrene–isoprene–styrene thermoplastic elastomer. While conventional polymerization of aniline with silver nitrate takes 2 weeks, by utilization of inverse emulsion polymerization, the reaction time reduces to 5 days. The assistance of a strong oxidant dramatically shortens the reaction time to 30 min. The technique developed results in uniform distribution of polyaniline/silver (PANI/Ag) conductive nanoparticles in the elastomeric matrix. The morphological studies of the films reveal spherically shaped 45 nm Ag particles. The presence of PANI/Ag in the styrene–isoprene–styrene elastomeric matrix enhances the electrical, thermal, and mechanical properties of the nanocomposites. The approach described provides an opportunity of the development of tunable structures and a remarkably distinctive architecture. A rapid electrical resistance response to an applied strain makes the nanocomposites developed useful as sensitive strain sensors. Copyright © 2014 John Wiley & Sons, Ltd.     

Ternary Ag/Polyaniline/Au nanocomposites: Preparation,characterization and electrochemical properties

Ternary Ag/Polyaniline/Au nanocomposites were synthesized successfully by immobilizing of Au nanoparticles (NPs) on the surface of Ag/Polyaniline (PANI) nanocomposites. Ag/PANI nanocomposites were prepared via in situ chemical polymerization of aniline in the presence of 4-aminothiophenol (4-ATP) capped silver colloidal NPs. Then, uniform gold (Au) NPs were assembled on the surface of resulted Ag/PANI nanocomposites through electrostatic interaction to get Ag/Polyaniline/Au nanocomposites. The nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), ultraviolet visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Moreover, Ag/PANI/Au nanocomposites were immobilized on the surface of a glassy carbon electrode and showed enhanced electrocatalytic activity for the reduction of H₂O₂ compared with Ag/PANI.     

聚苯胺/离子液体/蒙脱土纳米复合材料的制备及其导电性能研究

采用1-羧甲基-3-甲基咪唑氯化盐离子液体对钠化蒙脱土进行插层改性,然后用苯胺的盐酸溶液进行二次插层,以过硫酸铵为氧化剂,盐酸溶液为掺杂剂,使进入离子液体/蒙脱土(CMMIm/MMT)层间的苯胺(An)发生氧化聚合反应,制备了一种具有良好导电性的聚苯胺/离子液体/蒙脱土复合材料(PANI/CMMIm/MMT).用红外光谱、X-射线衍射,热重分析和DSC对样品进行了表征.结果表明当离子液体/蒙脱土用量为7.5%、盐酸浓度为1mol/L、过硫酸铵与苯胺的摩尔比为1∶1、0℃下反应6h时制备的PANI/CMMIm/MMT纳米复合材料电导率最高,达到了0.3S/cm,是相同条件下聚苯胺/钠化蒙脱土纳米复合材料电导率的2.5倍,聚苯胺的7.5倍.     

TiO2纳米微粒对聚苯胺性能的影响

纳米微粒具有量子尺寸效应, 其光、电、声及磁等方面的性能与常规材料有显著的不同, 其中以TiO2纳米微粒的电荷载体、光电活性中心、光学微腔和光电特性等特征[1,2]尤为引人注目. 导电聚合物的纳米复合材料是纳米材料的研究热点之一, 在导电材料、电流体和高密度信息存储材料等方面具有良好的应用前景[3]. 在导电聚合物中, 聚苯胺(PANI)因其具有较高的电导率, 原料便宜, 稳定性好而成为目前最有希望获得实际应用的导电聚合物[4～6]. 将纳米微粒和PANI制成复合材料, 其光电性能等与PANI相比均有所改变. 目前已相继有PANI-ZrO2, PANI-MnO2, PANI-SiO2纳米复合材料的报道[7,8], 而有关PANI-TiO2研究工作尚少见报道. 本文制备了PANI-TiO2纳米复合材料, 通过红外光谱、紫外可见光谱及透射电镜等探讨了复合材料的微结构及性能.     

一种水中可溶性导电聚苯胺的制备与表征

分别以聚乙二醇(PEG)的水、乙醇溶液为反应媒介, 制备了Keggin结构杂多酸(H₄SiW₁₂O₄₀)掺杂的导电聚苯胺材料. 此聚苯胺经IR, XRD, UV-Vis光谱进行了表征, 并采用标准的四探针法对其电导率进行了测定. 同时系统地研究了杂多酸、氧化剂和单体的比例、反应混合体系温度的改变等对所合成聚苯胺的产率、导电率、水中溶解性等方面的影响. 结果表明, 在PEG乙醇溶液中制备的聚苯胺比在水溶液中制备的有较高的产率、电导率和溶解率. 其最高电导率可达到1.87 S/cm, 溶解率可达53%.     

Polyaniline/Silver Nanoparticle-Doped Multiwalled Carbon Nanotube Composites

A simple method was used to synthesize the hybrid nanocomposites consisting of the functionalized multiwalled carbon nanotube composites (MWCNTs) with the polyaniline incorporated silver nanoparticles (a-MWCNT/PANI-Ag) through an emulsion polymerization at room temperature in order to enhance the electrical conductivity of polyaniline. The electrical conductivity of the composite with the incorporated Ag nanoparticles was 5% higher than the same weight percent for the composite without Ag nanoparticles, and the thermal stability was dramatically increased from 54% for the composite (a-MWCNT/PANI) to 69% through the incorporation of the Ag nanoparticles at 830°C. Additionally, the advantages of the Ag nanoparticles, including the improved electrical and thermal properties without damage to the polyaniline structure, were confirmed using FTIR and Raman spectroscopy.     

Soluble,Antibaterial, and Anticorrosion Studies of Sulfonated Polystyrene/Polyaniline/Silver Nanocomposites Prepared with the Sulfonated Polystyrene Template

In this work, multifunctional sulfonated polystyrene/polyaniline/silver (SPS /PANI /Ag) nanocomposites are prepared through using sulfonated polystyrene (SPS ) spheres as templates and utilizing polyvinylpyrrolidone (PVP ) as reducing agent and stabilizing agent. Our method is an environmentally friendly method because no toxic reagents are added during the preparation process. Fourier transform infrared spectrum (FTIR ), field emission scanning electron microscopy (FESEM ), and energy disperse spectroscopy (EDX ) results confirmed the formation of PS spheres, SPS spheres, SPS /PANI nanocomposites, and SPS /PANI /Ag nanocomposites. Powder X‐ray diffraction (XRD ) patterns indicate that the obtained Ag nanoparticles are crystalline. Solubilities measurements show that SPS /PANI /Ag nanocomposites have improved solubilities when compared to pure PANI in common organic solvents and deionized water. Antibacterial studies show that SPS /PANI /Ag nanocomposites can greatly inhibit the growth of Escherichia coli and Staphylococcus aureus . Anticorrosion studies show that the incorporation of SPS /PANI /Ag nanocomposites in waterborne alkyd resin can greatly promote the anticorrosive efficiency of waterborne alkyd resin.     

Cerium dioxide/polyaniline core-shell nanocomposites

The preparation of CeO2/polyaniline (CeO2/PANI) core-shell nanocomposites via chemical oxidation of aniline using CeO2 as an oxidant is reported. TEM, TGA, FT-IR, XPS, and conductivity measurement are used to characterize the resulting composites. TEM measurements reveal that the shape of PANI/CeO2 nanocomposites is different from CeO2 nanoparticles and fibular PANI oxidized with soluble oxidant. Electron diffraction (ED) patterns of CeO2/PANI nanocomposites reveal single crystal of CeO2. FT-IR spectra confirmed the formation of PANI; the amount of PANI in the nanocomposites is estimated by TGA results. The conductivities increase with the increasing ratio of PANI/CeO2. XPS results reveal that in the nanocomposites Ce4+ of CeO2 is reduced to Ce3+. In addition, the degree of protonation of polyaniline obtained from N 1s XPS results in cerium dioxide/polyaniline composites is about 48.52%.     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012