Morphology,rheological and crystallization behavior in non-covalently functionalized carbon nanotube reinforced poly(butylene succinate) nanocomposites with low percolation threshold

Multi-walled carbon nanotubes (CNTs) were non-covalently functionalized by surface wrapping of poly(sodium 4-styrenesulfonate) (PSS) with the aid of ultrasound. The functionalized CNTs were incorporated into poly(butylene succinate) (PBS) through solution coagulation to fabricate CNTs filled PBS nanocomposites. The morphologies of the PBS/CNT nanocomposites were studied by scanning electron microscope (SEM) and transmission electron microscope (TEM), and the effect of loading of functionalized CNT on the rheological behavior, electrical conductivity and mechanical properties of the nanocomposites was investigated systemically. SEM observation indicates that functionalized CNTs dispersed in PBS matrix without obvious aggregation and showed good interfacial adhesion with the PBS phase. TEM observation reveals that a CNT network was formed when the loading of CNTs increased from 0.1 to 0.3 wt%. Rheological investigation indicates the formation of a CNT network with a percolation threshold of only 0.3 wt%. Significant improvement in electrical conductivity occurred at CNT loading of 0.3 wt%, with the value of electrical conductivity increasing by six orders of magnitude compared to neat PBS. Differential scanning calorimetry indicates that the melt crystallization temperature of PBS was improved by ∼14 °C with addition of only 0.05 wt% functionalized CNTs. Tensile tests indicate that both the yield strength and Young's modulus of PBS were apparently reinforced by incorporation of functionalized CNTs, while the elongation at break was reduced gradually.     

High-performance supercapacitor based on ultralight and elastic three-dimensional carbon foam/reduced graphene/polyaniline nanocomposites

A novel supercapacitor based on ultralight and elastic three-dimensional porous melamine foam-derived macroporous carbon/reduced graphene oxide/polyaniline nanocomposites were fabricated, which showed great electrical performance and cycle performance.     

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.     

有限域聚合法制备碳纳米管-聚苯胺复合材料及其电化学性能

通过有限域聚合法将聚苯胺(PANI)均匀地生长在碳纳米管(CNTs)表面, 得到CNTs-PANI纳米复合材料. 通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅立叶变换红外(FTIR)光谱对样品的形貌及成分进行表征. 将得到的复合材料组装成电化学超级电容器, 进行电化学的循环伏安和恒流充放电测试. 结果显示, 运用此有限域聚合法所制备的复合材料中PANI 可以非常均匀地包裹在CNTs表面, 复合材料的比容量可以达到117.7 F·g-1(有机电解液), 远远高于所用纯碳纳米管(25.0 F·g-1)和纯聚苯胺(65.0 F·g-1)的比容量, 从而表明有限域聚合法是一良好的纳米复合材料的制备方法.     

Effect of cellulose nanofibers on induced polymerization of aniline and formation of nanostructured conducting composite

Cellulose nanofibers (CNFs), derived from the most abundant and renewable biopolymer, are known as natural one-dimensional nanomaterials because of their high aspect ratio. CNFs also are rich in hydroxyl groups, offering opportunities for functionalization toward development of high-value nanostructured composites. Herein, CNFs were extracted from poplar wood powder by chemical pretreatment combined with high-intensity ultrasonication, and then coated with polyaniline (PANI) through in situ polymerization. The PANI-coated CNFs formed nanostructured frameworks around PANI, thereby conferring the CNF/PANI composite with stability and higher charge transport. The optimum PANI content to achieve maximum conductivity of CNF/PANI composites was determined. The morphology, crystall structure, chemical composition, and conductivity of the samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and four-point probe method, respectivily. Our results demonstrated that CNFs can be effective as a template for a flexible and stable conducting polymer to form higher-order nanostructures.     

Enhancing dielectric and mechanical behaviors of hybrid polymer nanocomposites based on polystyrene,polyaniline and carbon nanotubes coated with polyaniline

The dielectric and mechanical properties of hybrid polymer nanocomposites of polystyrene/polyaniline/carbon nanotubes coated with polyaniline(PCNTs) have been investigated using impedance analyzer and extensometer. The blends of PS/PANI formed the heterogeneous phase separated morphology in which PCNTs are dispersed uniformly. The incorporation of a small amount of PCNTs into the blend of PS/PANI has remarkably increased the dielectric properties. Similarly, the AC conductivity of PS/PANI is also increased five orders of magnitude from 1.6 × 10~(-10) to 2.0 × 10~(-5) S·cm~(-1) in the hybrid nanocomposites. Such behavior of hybrid nanocomposites is owing to the interfacial polarization occurring due to the presence of multicomponent domains with varying conductivity character of the phases from insulative PS to poor conductor PANI to highly conductive CNTs. Meanwhile, the tensile modulus and tensile strength are also enhanced significantly up to 55% and 160%, respectively, without much loss of ductility for three phase hybrid nanocomposites as compared to the neat PS. Thereby, the hybrid nanocomposites of PS/PANI/_P CNTs become stiffer, stronger and tougher as compared to the neat systems.     

Coating of multiwalled carbon nanotubes with polymer nanospheres through microemulsion polymerization

We report a simple and noncovalent method for coating multiwalled carbon nanotubes (MWCNTs) with polyaniline (PANI) nanospheres using a microemulsion polymerization method. In this method, aniline polymerization is performed with MWCNTs in the presence of sodium dodecyl sulfate (SDS), which serves as both a surfactant and a dopant. Morphological, structural, thermal, and electrical properties of MWCNT–PANI nanocomposites were analyzed. The TEM results of the nanocomposites prepared with surfactant reveal that 30–50-nm-diameter PANI nanospheres were coated on the surface of the MWCNTs. Composites prepared without surfactant were found to be in core–sheath-type cable structures. The conductivities of the nanocomposites synthesized through microemulsion polymerization were found to be one order of magnitude higher than both the conductivities of pure PANI and the composites prepared via in situ chemical polymerization without an assisting SDS surfactant. The mechanism for the formation of nanostructured composites is presented.     

Carbon nanotube-polyaniline hybrid materials

A hybrid material of carbon nanotubes (CNTs)-polyaniline (PANI) was prepared by in situ emulsion polymerization. The structural characterization showed that some CNTs were linked up by PANI chains, which appears to be like a network including PANI fiber and nanotubes. This network results in the hybrid material having highly conductivity with new conductive passageway. The conductivity and thermal properties of hybrid materials depend on the content of CNTs. The CNTs do not affect the structure of PANI chains.     

Chemically modified polyaniline nanocomposites by poly(2-acrylamido-2-methyl-1-propanesulfonicacid)/graphene nanoplatelet

New conducting polyaniline (PANI) nanocomposites that were chemically modified by poly(2-acrylamido-2-methyl-1-propanesulfonicacid) (PMP) and graphene nanoplatelets (GNPs) were prepared via in situ deposition. PMP was first synthesized using GNPs, and aniline hydrochloride monomer was then polymerized in the presence of PMP-GNPs. The nanopolymer composites were characterized, and its structural morphology was analyzed via transmission electron microscopy and scanning electron microscopy. Fourier transformation infrared spectroscopy results indicate a strong interaction between PANI, PMP, and GNPs. To understand the conduction behavior of the composites, temperature-dependent DC electrical conductivity was measured between 295 K and 503 K, and the mechanism of transport properties of the new composites was analyzed by Mott’s variable range of hopping model. The PANI/PMP-GNP showed higher conductivity than pure PANI polymer. The high electrical conductivity of the nanocomposites may be useful in fabricating multifunctional materials in bulk for future technological applications.     

Enhanced magnetoconductivity and electrical property of MWCNT-CdS nanocomposite embedded in polyaniline

PANI/MWCNT-CdS nanocomposites with different content of CdS wt.% has been synthesized by the chemical oxidative in-situ polymerization reaction of aniline in the presence of multi-walled carbon nanotubes (MWCNT). TEM, XRD, FTIR, and TGA studies were done for the structural and thermal characterization of the samples respectively. The particle size of CdS nanoparticles distributes in between 2.7 and 4.8 nm. XRD spectrum reveals that the co-existence of MWCNT, CdS in PANI matrix, where CdS forms a hexagonal structure. TGA result shows that nanocomposite becomes more thermally stable with the increase in CdS content. The dc electrical transport property of PANI/MWCNT-CdS nanocomposites has been investigated within a temperature range 77 ≤ T ≤ 300 K. The dc conductivity follows a 3D variable range hopping (VRH) model. A large magnetoconductivity change (19%) is observed for 2 wt% CdS content in PANI/MWCNT-CdS, which is explained by the wave function shrinkage model.     

The Electrochemical Properties of Nanocomposite Films Obtained by Chemical In Situ Polymerization of Aniline and Carbon Nanostructures

Interactions between the π bonds in the aromatic rings of polyaniline (PANI) with carbon nanostructures (CNs) facilitate charge transfer between the two components. Different types of phenyleneamine‐terminated CNs, including carbon nano‐onions (CNOs) and single‐walled and multi‐walled carbon nanotubes (SWNTs and MWNTs, respectively), were prepared as templates, and the CN/PANI nanocomposites were easily prepared with uniform core–shell structures. By varying the ratio of the aniline monomers relative to the CNs in the in situ chemical polymerization process, the thickness of the PANI layers was effectively controlled. The morphological and electrical properties of the nanocomposite were determined and compared. The thickness and structure of the PANI films on the CNs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and infrared spectroscopy. TEM and SEM revealed that the composite films consisted of nanoporous networks of CNs coated with polymeric aniline. The electrochemical properties of the composites were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. These studies showed that the CN/PANI composite films had lower resistance than pure polymeric films of PANI, and the presence of CNs much improved the mechanical stability. The specific electrochemical capacitance of the CNO/PANI composite films was significantly larger than for pure PANI.     

Ru/CNFs 催化剂催化氨分解制氢

 研究了鱼骨式碳纤维 (CNFs) 和管式碳纤维 (CNTs) 负载 Ru 催化剂的氨分解反应活性. 结果表明, Ru/CNFs 催化剂上氨分解活性高于 Ru/CNTs 催化剂. 通过改变 Ru 负载量或载体表面的含氧基团来调节 Ru 的粒径. Ru 的活性位随着 Ru 颗粒尺寸的增大而增加. CNFs 上的含氧基团对 Ru 颗粒的氨分解活性影响很大. 在相同粒径的 Ru 颗粒上, CNFs 表面的含氧基团增加了 Ru 的活性.     

The preparation and performance of flocculent polyaniline/carbon nanotubes composite electrode material for supercapacitors

Polyaniline (PANI)/carbon nanotubes (CNTs) composite electrode material was prepared by in situ chemical polymerization. The structure and morphology of PANI/CNTs composite are characterized by Fourier infrared spectroscopy, scanning electron microscope, and transmission electron microscopy. It has been found that a flocculent PANI was uniformly deposited on the surface of CNTs. The supercapacitive behaviors of the PANI/CNTs composite materials are investigated with cyclic voltammetry, galvanostatic charge/discharge, impedance, and cycle life measurements. The results show that the PANI/CNTs composite electrodes have higher specific capacitances than CNT electrodes and better stability than the conducting polymers. The capacitance of PANI/CNTs composite electrode is as high as 837.6 F g⁻¹ measured by cyclic voltammetry at 1 mV s⁻¹. Besides, the capacitance retention of coin supercapacitors remained 68.0% after 3,000 cycles.     

导电聚苯胺与磁性CoFe2O4纳米复合物的合成及其电磁性能

在利用HNO3处理CoFe2O4磁性纳米粒子使其表面离子化、分散性得到改善的基础上, 采用苯胺在其表面原位聚合, 制备了具有电磁功能的聚苯胺(PANI)/CoFe2O4纳米复合物. 借助TEM、XRD、FT-IR、四探针电导率仪和VSM(振动样品磁强计)等分析手段研究了复合物的形貌、结构及其电磁性能. 结果表明, CoFe2O4以25 nm左右的粒子分散于聚苯胺基体中, 被其完全包覆, CoFe2O4与PANI之间存在化学键合作用; 复合物同时具有电性能和磁性能, 其导电率随CoFe2O4含量增加而降低, 饱和磁化强度随之升高, 而矫顽力在所研究的范围内则先增大而后又减小, 且均高于CoFe2O4的矫顽力.     

聚苯胺/Co_(0.5)Zn_(0.5)Fe_2O_4纳米复合材料的制备及电磁性能

采用高分子凝胶法制备尖晶石型Co0.5Zn0.5Fe2O4,原位聚合法制备纯聚苯胺和聚苯胺/Co0.5Zn0.5-Fe2O4纳米复合材料.使用傅立叶红外光谱(FTIR)、紫外可见吸收光谱(UV-Vis)、X射线衍射仪(XRD)和透射电子显微镜(TEM)对复合材料进行了表征.FTIR和XRD的结果表明样品为纯聚苯胺和聚苯胺/Co0.5Zn0.5-Fe2O4.UV-Vis光谱表明聚苯胺/Co0.5Zn0.5Fe2O4苯环上的π-π*和n-π*分别红移了23nm和5nm.TEM照片可知,聚苯胺和聚苯胺/Co0.5Zn0.5Fe2O4粒子的平均粒径分别约为50nm和70nm.在8.2～12.4GHz测试频率范围内,聚苯胺/Co0.5Zn0.5Fe2O4的ε″数值在9.2～12.3之间,u″数值在0.15～0.16之间;聚苯胺/Co0.5-Zn0.5Fe2O4介电损耗低于纯聚苯胺,而磁损耗高于纯聚苯胺.     

Controllable Preparation of Polyaniline–Graphene Nanocomposites using Functionalized Graphene for Supercapacitor Electrodes

In order to explore the effect of graphene surface chemistry on electrochemical performance based on polyaniline–graphene hybrid material electrodes, four different polyaniline–graphene nanocomposites were fabricated with graphene oxide, reduced graphene oxide, aminated graphene and sulfonated graphene as carriers, respectively. The nanocomposites feature various structures and morphologies, which could be used to more deeply understand the morphology and structure effects caused by surface chemistry on electrochemical performance. The experimental results reveal that functionalized electronegative graphene was conducive to the vertical and neat growth of polyaniline (PANI) nanorods. The array architecture endowed the PANI–GS nanocomposite with a large ion‐accessible surface area and high‐efficiency electron‐ and ion‐transport pathways. Meanwhile, the introduction of sulfonic acid functional groups accelerated the redox reaction with doping and dedoping of the PANI. Thereby, the PANI–GS nanocomposite exhibited a high specific capacitance of 863.2 F g^?1 at a current density of 0.2 A g^?1 and the excellent rate capability of 67.4 % (581.6 F g^?1 at 5 A g^?1), which were much better than the other three nanocomposites produced.     

碳纳米管/聚苯胺/石墨烯复合纳米碳纸及其电化学电容行为

通过真空抽滤的方法制备碳纳米管纸,并对其进行循环伏安电化学氧化处理.以该电化学氧化处理的碳纳米管(CV-CNT)纸为基体,采用电化学聚合沉积聚苯胺(PANI),随后吸附石墨烯(GR),制备具有三明治夹心结构的碳纳米管/聚苯胺/石墨烯(CV-CNT/PANI/GR)复合纳米碳纸.该结构外层为GR,内层由PANI包裹的CNT形成网络骨架,充分发挥三者各自优势构建柔性电极材料.用场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)、拉曼光谱对其形貌与结构进行表征,并测试其电化学性能.研究发现:PANI呈纳米晶须状,并均匀包裹在CV-CNT表面;该复合碳纸具有良好的电容特性、大电流充放电特性以及良好的循环稳定性能.电流密度为0.5A·g-1时,比电容可达415F·g-1;20A·g-1时仍能保持106F·g-1的比电容.由于GR的保护作用,1000次循环之后较CV-CNT/PANI保持更高的有效比电容.该CV-CNT/PANI/GR复合碳纸展现出在高性能超级电容器柔性电极材料的潜在应用价值.     

Controllable deposition of a platinum nanoparticle ensemble on a polyaniline/graphene hybrid as a novel electrode material for electrochemical sensing

We demonstrate for the first time an interfacial polymerization method for the synthesis of high-quality polyaniline-modified graphene nanosheets (PANI/GNs), which represents a novel type of graphene/polymer heterostructure. The interfacial polymerization at a liquid-liquid interface allows PANI to grow uniformly on the surface of the GNs. An ultra-high loading of Pt nanoparticles was then controllably deposited on the surface of the PANI/GNs to form a Pt/PANI/GNs hybrid. The obtained composites were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pt/PANI/GNs hybrid shows excellent electrocatalytic activity toward methanol oxidation and oxygen reduction. H(2)O(2) and glucose were used as two representative analytes to demonstrate the sensing performance of a Pt/PANI/GNs-modified electrode. It is found that this sensing element shows high sensitivity and a low detection limit for H(2)O(2) and glucose. The results demonstrate that the Pt/PANI/GNs hybrid may be an attractive and advanced electrode material with potential applications in the construction of electrochemical sensors and biosensors.     

Preparation,morphology and electrical conductivity of polyaniline/polyoxyalkylene–montmorillonite exfoliated nanocomposites

Polyaniline (PANI)/organoclay exfoliated nanocomposites containing different organoclay contents (14–50 wt%) were prepared. PANI emeraldine base (EB) and oligomeric PANI (o‐PANI) were intercalated into montmorillonite (MMT) modified by four types of polyoxyalkylene diamine or triamine (organoclay) using N‐methyl pyrolidinone (NMP) as a solvent in the presence of 0.1 M HCl. o‐PANI and EB have been synthesized by oxidative polymerization of aniline using ammonium peroxydisulfate (APS). Infrared absorption spectra (IR) confirm the electrostatic interaction between negatively charged surface of MMT and positively charged sites in PANI. X‐ray diffraction (XRD) studies disclosed that the d₀₀₁ spacing between interlamellar surface disappeared at low content of the organoclay. The morphology of these materials was examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electrical conductivities of the PANI‐organoclay and o‐PANI‐organoclay nanocomposites were 1.5 × 10^?3–2 × 10^?4 and 9.5 × 10^?7–1.8 × 10^?9 S/cm, respectively depending on the ratio of PANI. Copyright © 2007 John Wiley & Sons, Ltd.     

石墨烯及其聚合物复合材料

近些年来,石墨烯以其独特的结构和优异的性质成为备受瞩目的研究前沿和热点。石墨烯作为纳米增强组分,少量添加可以使聚合物的物理性能得到大幅地提高。本文就石墨烯及其在聚合物复合材料的研究进展进行了综述,着重阐述了现已工业化制备石墨烯的氧化还原法,以及石墨烯/聚合物复合材料的制备方法(溶液共混、原位聚合和熔融共混)和性能(电学性能、导热性能、力学性能、热性能以及气体阻隔性能),并指出其待解决的关键技术及工业化前景。