Electroconductive Green Metal-polyaniline Nanocomposites: Synthesis and Application in Sensors

Polyaniline (PANI) is one of the most extensively used conducting polymer due to its fascinating properties including conducting, thermal, optical, magnetic and electrochemical properties, simple synthesis procedure and low cost of monomer. It has attracted major attention in a variety of applications including electrochemical sensors, catalysts, supercapacitors and biosensors. However, its limitations such as insolubility in common solvents, low process-ability and poor mechanical properties have led to the development of new approaches to improve it properties. Metal nanoparticles (MNPs) such as silver, gold, copper and palladium have been combined with PANI to improve on its properties which has led to a new class of materials known as metal/PANI nanocomposites. These hybrid nanocomposites incorporate advantages of both MNPs and polymers which effectively improves the properties of the individual materials. Various synthesis techniques including in situ polymerization, ɤ-radiolysis, electrodeposition, complexation, vacuum deposition and interfacial polymerization have been used in the formation of metal/PANI nanocomposites. These nanocomposites have been used in various sensor and biosensor applications due to their excellent conductivity, ease of synthesis, excellent redox potentials, chemical and thermal stability. This review highlights the various metal/PANI nanocomposites, their various synthesis techniques and their application in sensors and biosensors. The importance of these nanocomposites in sensing and signaling various toxic heavy metals such as mercury, lead and silver and toxic gases such as hydrogen sulphide, ammonia and chloroform has been discussed. In addition the review covers the applications of metal/PANI nanocomposites in biosensor systems for the detection of glucose, DNA, protein, cholesterol, drugs and hydrogen peroxide.     

Graphene‐polymer nanocomposites for biomedical applications

Despite the significant efforts in the synthesis of new polymers, the mechanical properties of polymer matrices can be considered modest in most cases, which limits their application in demanding areas. The isolation of graphene and evaluation of its outstanding properties, such as high thermal conductivity, superior mechanical properties, and high electronic transport, have attracted academic and industrial interest, and opened good perspectives for the integration of graphene as a filler in polymer matrices to form advanced multifunctional composites. Graphene‐based nanomaterials have prompted the development of flexible nanocomposites for emerging applications that require superior mechanical, thermal, electrical, optical, and chemical performance. These multifunctional nanocomposites may be tailored to synergistically combine the characteristics of both components if proper structural and interfacial organization is achieved. The investigations carried out in this aim have combined graphene with different polymers, leading to a variety of graphene‐based nanocomposites. The extensive research on graphene and its functionalization, as well as polymer graphene composites, aiming at applications in the biomedical field, are reviewed in this paper. An overview of the polymer matrices adequate for the biomedical area and the production techniques of graphene composites is presented. Finally, the applications of such nanocomposites in the biomedical field, particularly in drug delivery, wound healing, and biosensing, are discussed.     

Chitosan-based nanocomposites for medical applications

Chitosan as a biobased polymer is gaining increasing attention due to its extraordinary physico-chemical characteristics and properties. While a primary use of chitosan has been in horticultural and agricultural applications for plant defense and to increase crop yield, recent research reports display various new utilizations in the field of advanced biomedical devices, targeted drug delivery, and as bioimaging sensors. Chitosan possesses multiple characteristics such as antimicrobial properties, stimuli-responsiveness, tunable mechanical strength, biocompatibility, biodegradability, and water-solubility. Further, chitosan can be processed into nanoparticles, nano-vehicles, nanocapsules, scaffolds, fiber meshes, and 3D printed scaffolds for a variety of applications. In recent times, nanoparticles incorporated in chitosan matrices have been identified to show superior biological activity, as cells tend to proliferate/differentiate faster when they interact with nanocomposites rather than bulk or micron size substrates/scaffolds. The present article intents to cover chitosan-based nanocomposites used for regenerative medicine, wound dressings, drug delivery, and biosensing applications.     

Structural and thermal properties of polysulfone-ZnO nanocomposites

Polymer nanocomposite thin film of polysulfone with different concentration of ZnO was prepared by solution grown technique. This paper presents a study on the structural and thermal properties of ZnO filled Polysulfone (PSF) nanocomposites. The structural morphology of the resulting nanocomposites was investigated by X-ray diffraction (XRD), Scanning electron microcopy (SEM), and Atomic force microscopy (AFM). Thermal properties of PSF nanocomposites samples were investigated by Differential thermal analysis, Thermal gravimetric, and Differential thermal gravimetric. Structural result shows that the ZnO nanofiller with different mass% in polymer matrix cause the significant variation of lattice spacing, crystallite size, and percentage crystallinity. XRD result shows that the amorphous behavior of PSF (Pristine) is increasing with incorporation of ZnO nanoparticle in PSF matrix. The SEM and AFM images show the change in structural morphology of PSF due to incorporation of ZnO nanoparticles. The thermal analysis result shows that the significant thermal degradation of polysulfone nanocomposites due to catalytic behavior of ZnO nanoparticles.     

Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and perspectives

Utilization of metallic nanoparticles in various biotechnological and medical applications represents one of the most extensively investigated areas of the current materials science. These advanced applications require the appropriate chemical functionalization of the nanoparticles with organic molecules or their incorporation in suitable polymer matrices. The intensified interest in polymer nanocomposites with silver nanoparticles is due to the high antimicrobial effect of nanosilver as well as the unique characteristics of polymers which include their excellent structural uniformity, multivalency, high degree of branching, miscellaneous morphologies and architectures, and highly variable chemical composition. In this review, we explore several aspects of antimicrobial polymer silver nanocomposites, giving special focus to the critical analysis of the reported synthetic routes including their advantages, drawbacks, possible improvements, and real applicability in antibacterial and antifungal therapy. A special attention is given to "green" synthetic routes exploiting the biopolymeric matrix and to the methods allowing preparing magnetically controllable antimicrobial polymers for targeting to an active place. The controversial mechanism of the action of silver against bacteria, fungi and yeasts as well as perspectives and new applications of silver polymeric nanocomposites is also briefly discussed.     

Recent advances in starch–clay nanocomposites

Biological nanocomposites are a valuable addition to the existing nanocomposite materials and eventually can substitute petroleum-based composite materials in numerous applications due to their inherent advantages such as biodegradability, eco-friendliness, low cost, and easy availability to name a few. Recently, polymer–clay nanocomposites have achieved much more attention due to their enhanced properties such as size dispersion and significant enhancement in physicochemical and mechanical properties in comparison to the pure polymer systems. Among various biopolymers, starch is one of the most abundant natural polymers on the earth and is highly valuable due to its chemical and physical properties. Starch polymer has highly increased potential as an alternative to petroleum-based materials. However, starch cannot be used alone and starch–clay nanocomposite has emerged as a new potential green sustainable material. This article focuses on recent progress in starch-based nanocomposites with particular emphasis on starch–clay nanocomposite preparation, properties, and applications.     

Polymer Nanocomposites for Emulsion‐Based Coatings and Adhesives

Emulsion‐based coatings and adhesives are in growing demand due to an increased awareness of health and safety issues arising from solvent‐based polymer manufacturing processes. However, emulsion‐based techniques often require additional development to achieve equal or better application performance compared to solvent‐based processes. The inclusion of nanoparticles in emulsion‐based coatings and adhesives can be considered as a promising means to enhance performance. This paper reviews the current progress on the synthesis of emulsion‐based nanocomposites for coating and adhesive applications and addresses the principles and techniques for nanoparticle dispersions and their inclusion into polymer latexes. The effects of nanoparticle shape and size on the enhancement of nanocomposite properties are also highlighted. Among the reinforcing nanoparticles such as nanoclays, carbon nanotubes, and cellulose nanocrystals (CNCs), CNCs are promising due to their abundance, nontoxicity, and accessible surface hydroxyl groups, which facilitate their compatibility with polymer latexes via physical and chemical treatments.     

A general synthetic strategy for oxide-supported metal nanoparticle catalysts

Despite recent exciting progress in catalysis by supported gold nanoparticles, there remains the formidable challenge of preparing supported gold catalysts that collectively incorporate precise control over factors such as size and size-distribution of the gold nanoparticles, homogeneous dispersion of the particles on the support, and the ability to utilize a wide range of supports that profoundly affect catalytic performance. Here, we describe a synthetic methodology that achieves these goals. In this strategy, weak interface interactions evenly deposit presynthesized organic-capped metal nanoparticles on oxide supports. The homogeneous dispersion of nanoparticles on oxides is then locked in place, without aggregation, through careful calcination. The approach takes advantage of recent advances in the synthesis of metal and oxide nanomaterials and helps to bring together these two classes of materials for catalysis applications. An important feature is that the strategy allows metal nanoparticles to be well dispersed on a variety of oxides with few restrictions on their physical and chemical properties. Following this synthetic procedure, we have successfully developed efficient gold catalysts for green chemistry processes, such as the production of ethyl acetate from the selective oxidation of ethanol by oxygen at 100 degrees C.     

Time-dependent Diffusion Coefficient and Conventional Diffusion Constant of Nanoparticles in Polymer Melts by Mode-coupling Theory (cited: 2)

Time-dependent diffusion coefficient and conventional diffusion constant are calculated and analyzed to study diffusion of nanoparticles in polymer melts. A generalized Langevin equa-tion is adopted to describe the diffusion dynamics. Mode-coupling theory is employed to calculate the memory kernel of friction. For simplicity, only microscopic terms arising from binary collision and coupling to the solvent density fluctuation are included in the formalism. The equilibrium structural information functions of the polymer nanocomposites required by mode-coupling theory are calculated on the basis of polymer reference interaction site modelwith Percus-Yevick closure. The effect of nanoparticle size and that of the polymer size are clarified explicitly. The structural functions, the friction kernel, as well as the diffusion coefficient show a rich variety with varying nanoparticle radius and polymer chain length. We find that for small nanoparticles or short chain polymers, the characteristic short time non-Markov diffusion dynamics becomes more prominent, and the diffusion coefficient takes longer time to approach asymptotically the conventional diffusion constant. This constant due to the microscopic contributions will decrease with the increase of nanoparticle size, while increase with polymer size. Furthermore, our result of diffusion constant from mode-coupling theory is compared with the value predicted from the Stokes-Einstein relation. It shows that the microscopic contributions to the diffusion constant are dominant for small nanoparticles or long chain polymers. Inversely, when nanonparticle is big, or polymer chain is short, the hydrodynamic contribution might play a significant role.     

银/聚合物纳米复合材料

银/聚合物纳米复合材料是一种典型的聚合物基复合材料, 其结构和性能依赖于合成方法,因此开发材料的优异性能必须以深入研究纳米材料的先进合成技术为前提。本文综述了纳米银粒子及其与聚合物形成的纳米复合材料的最新合成进展, 重点介绍了基于液相化学还原方法合成纳米银粒子的新方法, 如溶胶-凝胶法、沉淀法、微乳液法和离子液体法, 以及纳米银粒子的分散技术和原位法合成银/聚合物纳米复合材料的新技术, 并介绍了纳米银复合材料的电绝缘性、表面增强拉曼散射性能、抗菌性及其在生物医学等领域中的应用。     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007     

粒子-聚合物相互作用与粒子-粒子相互作用对聚合物基纳米复合物力学性能的影响

聚合物基纳米复合物(PNCs)具有比传统高分子材料更加优异的光学、力学、热力学等性能,广泛应用于各个工程领域.而纳米粒子(NPs)对材料性能提高的机理则是当前聚合物纳米复合物领域研究的重要问题,聚合物纳米复合体系相互作用的影响因素众多,至今尚未明确并完整建立复合体系相互作用与性能增强之间的关系.本文总结了近年来关于纳米粒子填充聚合物基体力学性能的研究,从粒子-聚合物相互作用和粒子-粒子相互作用角度阐述了聚合物纳米复合体系力学性能的增强机理,并根据体系中不同的结构关系分别总结了聚合物/未改性纳米粒子复合体系和聚合物/聚合物接枝纳米粒子复合体系中影响力学性能的因素.该部分内容具有重要的理论和实践意义,有助于构建复合体系微观结构与宏观性能之间的关系,进而对微观层面调控PNCs的力学性能提供指导.     

Impact of in situ polymer coating on particle dispersion into solid laser-generated nanocomposites

The crucial step in the production of solid nanocomposites is the uniform embedding of nanoparticles into the polymer matrix, since the colloidal properties or specific physical properties are very sensitive to particle dispersion within the nanocomposite. Therefore, we studied a laser-based generation method of a nanocomposite which enables us to control the agglomeration of nanoparticles and to increase the single particle dispersion within polyurethane. For this purpose, we ablated targets of silver and copper inside a polymer-doped solution of tetrahydrofuran by a picosecond laser (using a pulse energy of 125 μJ at 33.3 kHz repetition rate) and hardened the resulting colloids into solid polymers. Electron microscopy of these nanocomposites revealed that primary particle size, agglomerate size and particle dispersion strongly depend on concentration of the polyurethane added before laser ablation. 0.3 wt% polyurethane is the optimal polymer concentration to produce nanocomposites with improved particle dispersion and adequate productivity. Lower polyurethane concentration results in agglomeration whereas higher concentration reduces the production rate significantly. The following evaporation step did not change the distribution of the nanocomposite inside the polyurethane matrix. Hence, the in situ coating of nanoparticles with polyurethane during laser ablation enables simple integration into the structural analogue polymer matrix without additives. Furthermore, it was possible to injection mold these in situ-stabilized nanocomposites without affecting particle dispersion. This clarifies that sufficient in situ stabilization during laser ablation in polymer solution is able to prevent agglomeration even in a hot polymer melt.     

Flexible ureasil hybrids with tailored optical properties through doping with metal nanoparticles

Hybrid organic-inorganic nanocomposites containing uniform distributions of metal nanoparticles have been prepared by mixing a preformed nanoparticle colloid with the precursors of a ureasil, prior to the sol-gel transition. These nanocomposites possess not only high optical quality and optical features dictated by the size and shape of the nanoparticle dopants but also a high degree of flexibility, which can largely enhance the range of applications in practical devices. The deposition of a uniform silica shell on the nanoparticle surface prior to the sol-gel transition was found to be required to maintain the colloidal stability during the process and, thus, to retain the optical properties in the final nanocomposite material. This method can be readily extended to other materials, such as semiconductor and magnetic nanoparticles.     

Synthesis and applications of mesoporous nanocomposites containing metal nanoparticles

Metal nanoparticles (NP) and mesoporous (MP) oxides are complementary materials, since the size scale of pores in MP oxides matches that of NP and both systems have potential applications in similar fields. Besides, nanocomposites obtained through their combination possess not only the intrinsic properties of each component, but also new features derived from the synergy between them, mainly due to the high interfacial area between the metal and the oxide. Thus, new optical, catalytic and sensing properties can be achieved that are not easily available from the individual components. In this review, we focus our attention on such NP@MP composites, not only from the point of view of the most common synthesis pathways but also briefly describing their applications in fields as diverse as (photo)catalysis, sensing, photochromism and other optical properties, as well as patterning.     

A novel method to synthesize polystyrene nanospheres immobilized with silver nanoparticles by using compressed CO2

In this work, a novel route to synthesize polymer/metal composite nanospheres has been proposed. This method combines the advantages that the polymer chains collapse and entangle in the presence of compressed CO(2), which acts as antisolvent, and the metal nanoparticles and polymers can be precipitated simultaneously from micellar solutions by the easy control of CO(2) pressure. Ag/polystyrene (PS) nanocomposites have been successfully prepared using this method. The transmission electronic micrographs (TEM) of the obtained nanocomposites show that the smaller Ag nanoparticles are immobilized by PS nanospheres of about 50 nm; the phase structure was characterized by X-ray diffraction (XRD). The Ag/PS nanocomposites show absorption properties at a wavelength of approximately 417 nm. The results of X-ray photoelectron spectra (XPS) and FT-IR spectra indicate that there is no chemical linkage or strong interaction between PS and Ag nanoparticles in the resultant products. This method has many potential advantages for applications and may easily be applied to the preparation of a range of inorganic/ polymer composite nanoparticles.     

Facile synthesis of fluorescent quantum dot‐polymer nanocomposites via frontal polymerization

We report an available approach for quickly fabricating CdS QD‐polymer nanocomposites via frontal polymerization (FP). First, we synthesized (3‐mercaptopropyl)‐1‐trimethoxysilane (MPS)‐capped CdS quantum dots (QDs). With these MPS‐capped CdS QDs containing mercapto groups, MPS‐capped CdS QDs can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP. A variety of features for preparing QD‐polymer nanocomposites, such as initiator concentration and CdS concentration, were thoroughly investigated. The fluorescence properties of QD‐polymer nanocomposites prepared via FP are comparatively investigated on the basis of ultraviolet–visible (UV–vis) spectra and photoluminescence (PL) spectra. Results show that the PL intensity of QD‐polymer nanocomposites prepared via the FP method is superior to that obtained by the traditional batch polymerization (BP) method. In addition, by measuring the changes of PL intensity of the samples immersed in different concentrations of copper acetate solution, we found the QD‐polymer nanocomposites can be ultrasensitive to copper ions. This FP process can be exploited as a facile and rapid way for synthesis QD‐polymer nanocomposites on a large scale, avoiding the fluorescence quenching of nanocrystals during incorporation nanocrystals into polymer matrices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2170–2177, 2010     

An overview of boron nitride based polymer nanocomposites

Recently, boron nitride (BN) based materials have received significant attention in both academic and industrial sectors due to its interesting properties like large energy band gap, good resistance to oxidation, excellent thermal conductivity, thermal stability, chemical inertness, significant mechanical property and widespread applications. This review article deals with the preparation and properties of boron nitride and its nanocomposites with various polymers. Diverse polymers have been explored for the preparation of boron nitride filled polymer nanocomposites by adopting different mixing methods. Properties of the resulting polymer nanocomposites mainly depend up on filler size and dispersion, mixing conditions and type of interaction between polymer matrix and the filler. Herein, the structure, preparation and properties of various boron nitride based polymer nanocomposites are reviewed in detail along with a brief overview of different classes of BN nanomaterials.     

聚苯胺纳米复合材料的优良性能

聚苯胺纳米复合材料因结合了聚苯胺和纳米粒子的特殊性能,从而改善了基体的物理化学性能,赋予了材料前所未有的独特的性能,成为目前研究最为广泛的导电高分子纳米复合材料之一.本文基于国内外最新研究文献,结合典型事列详细综述了聚苯胺纳米复合材料在生物传感、催化、电磁、微波吸收和光电等方面呈现出的独特性能,简单评述了其在生物传感、催化、电磁、微波吸收、防腐等领域的应用前景.     

高分子/棒状纳米粒子复合物的分子动力学模拟

采用非平衡态分子动力学模拟研究了剪切场下棒状纳米粒子对高分子基体的结构、 动力学和流变性质的影响. 通过比较多种体积分数(0.8%~10%)的纳米复合物及纯熔体的模拟结果发现, 随着纳米粒子的增加, 高分子链的扩散和松弛逐渐受到抑制, 而链尺寸几乎保持不变. 从Weissenberg number(W_i)角度看, 在剪切流场下, 高分子链的结构性质(如归一化的均方回转半径、 回转张量和取向抑制参数)几乎与纳米粒子的体积分数无关, 而高分子链的Tumbling运动受到抑制. 研究还发现, 纳米复合物与纯熔体的剪切黏度曲线趋势基本一致, 即W_i=1将曲线分为平台区和剪切变稀区. 纳米棒的加入仅定量地改变了流体的剪切黏度.