Conducting nanocomposites based on polyamide 6,6 and carbon nanofibers prepared by cryogenic grinding

Nanocomposites based on polyamide 6,6 and carbon nanofiber have been obtained following a new procedure. It consists of the physical mixing of the polymer matrix, in the form of powder, and the corresponding amount of additive. Then, samples were prepared by compression molding and their structural characteristics, as well as their thermal and electrical properties were determined. The materials present good electrical conductivity at lower percolation thresholds than those corresponding to systems prepared by melt mixing. The study was carried out with two different grain sizes, and the findings are discussed in terms of the different size ratios of polymer to carbon nanofiber.     

炭化聚甲基丙烯酸甲酯／聚丙烯腈核壳聚合物制备炭纳米空心球

采用炭化聚甲基丙烯酸甲酯(PMMA)/聚丙烯腈(PAN)核壳聚合物的方法制备了炭纳米空心球.以两步无皂乳液聚合法制备了PMMA/PAN核壳粒子:首先以间歇无皂乳聚合法制备出直径约200 nm的PMMA粒子乳液,再以其作为种子乳液,以饥饿滴定法在PMMA外表而聚合一层厚度约30 nm的PAN外壳.将制备的PMMA/PAN乳液冷冻干燥后,分别经过250℃预氧化及1000℃炭化工艺,制备了炭纳米空心球.透射电镜结果显示所有核壳粒子均炭化成空心球并呈现交联状态.     

Evaluation and modelling of electrically conductive polymer nanocomposites with carbon nanotube networks

Superior electrical, thermal, and mechanical properties of carbon nanotubes (CNTs) have made them effective filler for multifunctional polymer nanocomposites (PNCs). In particular, electrically conductive PNCs filled with CNTs have been researched extensively. These studies aimed to increase the PNCs' electrical conductivity (σ) and to minimize the percolation thresholds (ϕ_c). In this work, we have developed an improved model to describe the CNT networks and thereby evaluate the PNCs' ϕ_c and σ. The new model accounts for the electrical conductance contributed by the continued CNT network across the boundary of adjacent representative volume elements. It more realistically represents the interconnectivity among CNTs and enhances the evaluation of the structure-to-property relationship of PNCs' σ.     

乳液模板-自组装法制备石墨烯/聚苯乙烯导电复合材料

利用乳液模板-静电自组装法,以甲基丙烯酰氧乙烯氯化铵(DMC)接枝改性的聚苯乙烯阳离子微球(PS+)为基体模板、石墨烯为导电介质,利用氧化石墨烯(GO)与PS+间强烈的静电相互作用直接在水中共组装,通过水合肼原位还原(in-situ reduction)成功制备了纳米石墨烯片(GNs)填充的聚苯乙烯(PS)导电复合材料。复合材料断口扫描电镜(SEM)和电性能结果表明,静电自组装有利于形成较为完善的石墨烯导电网络,GNs/PS复合材料具有极低的导电逾渗值(0.09%(体积分数))和较高的饱和导电率(25.2S/m)。结合表面zeta电位、复合物微观形貌的表征,对组装机理和结构-性能关系进行了讨论。此外,热重热分析(TGA)结果表明,石墨烯的加入有效地改善了材料的热稳定性。     

多方向生长碳纳米纤维的催化燃烧制备

介绍一种简单的合成具有多方向生长结构的碳纳米纤维的工艺。该工艺采用甲醇作为碳源，在铜基底上，以硝酸镍作为催化剂先体，经甲醇催化燃烧分解直接合成该结构材料，而无需任何模板。通过扫描电子显微镜的表征，不同分支结构的碳纳米纤维被合成。透射电子显微镜的结果表明，该样品具有较好的微结构。     

Thermally conductive polymer nanocomposites for filament-based additive manufacturing

Journal of Materials Science - Thermal management is a crucial factor affecting the performance and lifetime in several applications, such as electronics, generators, and heat exchangers. Additive...     

Electrospinning carbon nanotube polymer composite nanofibers

The unique and exceptional physical properties of carbon nanotubes have inspired their use as a filler within a polymeric matrix to produce carbon nanotube polymer composites with enhanced mechanical, thermal and electrical properties. A powerful method of synthesising nanofibers comprising these polymer composites is electrospinning, which utilises an applied electric stress to draw out a thin nanometer-dimension fiber from the tip of a sharp conical meniscus. The focussing of the flow due to converging streamlines at the cone vertex then ensures alignment of the carbon nanotubes along the fiber axis, thus enabling the anisotropic properties of the nanotubes to be exploited. We consider the work that has been carried out to date on various aspects encompassing preprocessing, synthesis and characterisation of these electrospun polymer composite nanofibers as well as the governing mechanisms and associated properties of such fibers. Particular attention is also dedicated to the theoretical modelling of these fiber systems, in particular to the electrohydrodynamic modelling of electrospinning polymer jets.     

聚合物/石墨导电纳米复合材料研究进展

石墨是近几年国内外研究的热点无机层状材料之一,它与聚合物有效复合形成的纳米复合材料是一类具有广阔应用前景的新型材料。从石墨的应用形式、聚合物基体的种类、复合材料的制备方法几个方面概述了聚合物/石墨导电纳米复合材料的研究进展及其发展趋势。     

Reinforcing polyamide 1212 nanocomposites with aligned carbon nanofibers

In this study, the mechanical properties and structure orientation of pure polyamide 1212 (PA1212) were compared with those of PA1212–carbon nanofibers (CNFs) nanocomposites. The tensile strength of the composite containing 0.3 wt.% modified CNFs was improved from 328 MPa (pure PA1212) to 373 MPa after drawing. The reinforcing effect was investigated in terms of crystallization behavior, crystal morphology, alignment of CNFs, and crystal orientation degree. Spherulites developed into oriented crystals after drawing, and the CNFs aligned along the drawing direction. The heterogeneous nucleation effect of the aligned CNFs improved the crystal orientation degree, which produced the reinforcing effect. The oriented fibril structures with rigid nanofibers acting as nuclei reinforced the entire oriented crystals in the composites.     

Titanium carbide/carbon composite nanofibers prepared by a plasma process

The incorporation of metal or metal carbide nanoparticles into carbon nanofibers modifies their properties and enlarges their field of application. The purpose of this work is to report a new non-catalytic and easy method to prepare organized metal carbide-carbon composite nanofibers on nanopatterned silicon substrates prepared by laser interference lithography coupled with deep reactive ion etching. Titanium carbide-carbon composite nanofibers were grown on the top of the silicon lines parallel to the substrate by a hybrid plasma process combining physical vapor deposition and plasma enhanced chemical vapor deposition. The prepared nanofibers were analyzed by scanning electron microscopy, x-ray photoelectron spectroscopy, Raman spectroscopy and transmission electron microscopy. We demonstrate that the shape, microstructure and the chemical composition of the as-grown nanofibers can be tuned by changing the plasma conditions.     

聚合物共混技术制备酚醛基纳米碳纤维

以聚丙烯（PP）为热解高聚物、酚醛树脂（PF）为碳纤维前躯体进行共混，采用熔融纺丝法将共混体系纺丝，对得到的纤维拉伸之后碳化去除去聚丙烯，得到酚醛基纳米碳纤维。采用红外光谱、扫描电镜等对PP／PF共混体系的相容性及微观结构进行分析，研究了纺丝牵伸比、降温母粒含量对纳米碳纤维形态的影响；用x射线衍射技术对纳米碳纤维的微晶结构进行研究。结果表明：随着降温母粒加入量的增加，酚醛树脂的分散尺寸增大；随着牵伸比的增加，纳米碳纤维的直径减小。XRD测试分析发现PP／PF共混纤维600℃碳化处理后已经开始产生一些石墨微晶，随碳化温度的升高，微晶长大，碳结构开始更趋规整、有序。     

Electrical conductivity of polyvinylidene fluoride nanocomposites with carbon nanotubes and nanofibers

Polyvinylidene fluoride nanocomposites with low loading levels of pristine multiwalled carbon nanotubes, carboxyl functionalized multiwalled carbon nanotubes and vapor grown carbon nanofibers were prepared by a versatile coagulation method. The alternating current electrical conductivity of these composites in the frequency range of 40-12 MHz was investigated. The alternating current conductivity of percolating nanocomposites followed a universal dynamic response. Therefore, both the direct current plateau and frequency dependent regime were observed. The percolation threshold of three composite systems was determined to be 1.0, 0.98, and 1.46 vol.%, respectively. Moreover, the percolative nanocomposites exhibited nonlinear current-voltage responses, demonstrating the presence of tunneling conduction.     

Electrically conductive carbon nanotube/polypropylene nanocomposite with improved mechanical properties

Conductive polymer nanocomposites based on carbon nanotubes (CNTs) have wide range of applications in the electronics and energy sectors. For many of these applications, such as the electromagnetic interference (EMI) shielding, high nanofiller loading is typically needed to achieve the desired properties. The high nanofiller concentration deteriorates the composite's tensile strength due to the increase in nanofiller aggregation. In this work, highly conductive CNT/polypropylene (PP) nanocomposite with improved tensile strength was prepared by melt mixing. The effects of CNT content on the processing behavior, microstructure, mechanical and electrical properties of the nanocomposite were investigated. Scanning electron microscopy was used to investigate the composite microstructure. Good level of CNT dispersion with remarkable adhesion at the CNT/PP interface was observed. Based on a theoretical model, the interfacial strength was estimated to be in the range of 36–58 MPa. As a result of this microstructure, significant enhancement in ultimate tensile strength was reported with the increase of CNT content. The tensile strength of the 20 wt.% CNT/PP nanocomposite was 80% higher than that of the unfilled PP. Moreover, and due to the good dispersion of CNT particles, an electrical percolation threshold concentration of 0.93 wt.% (0.5 vol.%) was obtained.     

Characterization and electrical properties of conductive polymer/colloidal graphite oxide nanocomposites

Conductive polymers such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT) have been synthesized in the presence of colloidal graphite oxide (CGO) prepared via Hummers and Offerman’s method, thus obtaining PPy/CGO and PEDOT/CGO nanocomposites. The resulted nanocomposites provide high and adjustable electrical conductivity when doped with different dopants, and a much better thermal stability than pristine CGO. For the case of doped PPy/CGO nanocomposites, CGO is confirmed experimentally to be exfoliated and thus could offer more “active sites” for the polymerization of pyrrole. For the case of doped PEDOT/CGO nanocomposites, X-ray diffraction analyses indicate the formation of PEDOT with the aid of CGO in aqueous media in spite of its monomeric water insolubility and a possible part intercalation of PEDOT between the layers of CGO. The temperature dependence of conductivity supports the three-dimensional Mott’s variable range hopping mechanism for doped PPy/CGO and PEDOT/CGO nanocomposites. The Fourier-transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectra data, as evidence verifies that the charge carriers in doped PPy/CGO nanocomposites are polarons, while bipolarons serve as charge carriers in doped PEDOT/CGO nanocomposites.     

Titania nanofibers prepared by electrospinning

TiO₂ nanofibers with a diameter of 54-78 nm have been successfully prepared by electrospinning method using a solution that contained poly(vinyl pyrrolidone) (PVP) and Ti(IV)-isopropoxide. The effect of viscosity and applied electric field on the morphology of the electrospun titania fibers was investigated. It has been observed that the increase in electric field causes bead formation and discontinuity in nanofiber morphology.     

Mechanical properties of carbon nanotubes and their polymer nanocomposites

More than 10 years have passed since carbon nanotubes (CNT) have been found during observations by transmission electron microscopy (TEM). Since then, one of the major applications of the CNT is the reinforcements of plastics in processing composite materials, because it was found by experiments that CNT possessed splendid mechanical properties. Various experimental methods are conducted in order to understand the mechanical properties of varieties of CNT and CNT-based composite materials. The systematized data of the past research results of CNT and their nanocomposites are extremely useful to improve processing and design criteria for new nanocomposites in further studies. Before the CNT observations, vapor grown carbon fibers (VGCF) were already utilized for composite applications, although there have been only few experimental data about the mechanical properties of VGCF. The structure of VGCF is similar to that of multi-wall carbon nanotubes (MWCNT), and the major benefit of VGCF is less commercial price. Therefore, this review article overviews the experimental results regarding the various mechanical properties of CNT, VGCF, and their polymer nanocomposites. The experimental methods and results to measure the elastic modulus and strength of CNT and VGCF are first discussed in this article. Secondly, the different surface chemical modifications for CNT and VGCF are reviewed, because the surface chemical modifications play an important role for polymer nanocomposite processing and properties. Thirdly, fracture and fatigue properties of CNT/polymer nanocomposites are reviewed, since these properties are important, especially when these new nanocomposite materials are applied for structural applications.     

Ultrasonically prepared polystyrene/multi-walled carbon nanotube nanocomposites

Polystyrene (PS) and multi-walled carbon nanotube (MWNT) nanocomposites were synthesized via an in situ bulk polymerization by employing an ultrasonicator without adding an initiator, in which the ultrasonication was found to do a favor in producing well-dispersed MWNT in the PS matrix. Morphology of the as-synthesized PS/MWNT nanocomposite was investigated by both scanning electron microscopy and transmission electron microscopy. Electrical conductivity of the PS/MWNT nanocomposite film fabricated by a solvent casting method was also examined to be enhanced with MWNT content, while average molecular weights of the synthesized PS in the PS/MWNT nanocomposites analyzed by a gel permeation chromatography increased and then saturated at 2 wt% MWNT. Rheological properties of MWNT containing PS were enhanced because of improved dispersion of the MWNT through an interaction between MWNT and PS.     

Mechanical performance of styrene-butadiene-rubber filled with carbon nanoparticles prepared by mechanical mixing

Reinforcement of styrene-butadiene-rubber (SBR) was investigated using two different carbon blacks (CBs) with similar particle sizes, including highly structured CB and conventional CB, as well as multi-walled carbon nanotube (MWCNT) prepared by mechanical mixing. The attempts were made to examine reinforcing mechanism of these two different classes of carbon nanoparticles. Scanning electron microscopy and electrical conductivity measurement were used to investigate morphology. Tensile, cyclic tensile and stress relaxation analyses were performed. A modified Halpin-Tsai model based on the concept of an equivalent composite particle, consisting of rubber bound, occluded rubber and nanoparticle, was proposed. It was found that properties of CB filled SBR are significantly dominated by rubber shell and occluded rubber in which molecular mobility is strictly restricted. At low strains, these rubber constituents can contribute in hydrodynamic effects, leading to higher elastic modulus. However, at higher strains, they contribute in stress hardening resulting in higher elongation at break and higher tensile strength. These elastomeric regions can also influence stress relaxation behaviors of CB filled rubber. For SBR/MWCNT, the extremely great inherent mechanical properties of nanotube along with its big aspect ratio were postulated to be responsible for the reinforcement while their interfacial interaction was not so efficient.     

Surface modification of carbon nanofibers by glycidoxysilane for altering the conductive and mechanical properties of epoxy composites

Carbon nanofibers (CNFs) were functionalized with 3-glycidoxypropyltrimethoxysilane and dispersed into epoxy resin. The chemical modification of CNFs was confirmed by FTIR, SEM, EDX and TGA measurements. After silanization, FTIR showed the existance of epoxy ring; EDX detected Si element; while TGA indicated 1.1 wt.% Si on CNFs. Mechanical properties were analyzed by DMA. Silanized CNFs/epoxy composites demonstrated improved dispersion of CNFs in the matrix, and an enhancement of storage modulus for about 20% compared to the neat matrix, which indicated that the modification of CNFs improved the adhesion between fillers and matrices. DC electrical conductivity of CNFs was reduced about 7-fold compared to the original CNFs due to the silane coating. Accordingly, the composites containing silanized CNFs also had lower electrical conductivity than those containing original CNFs. In spite of decreased electrical conductivity, thermal conductivity of silanized CNFs/epoxy composites was increased due to the surface modification of CNFs.