Electrochemical fabrication of polyaniline/multi-walled carbon nanotube composite films for electrooxidation of methanol

Polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite films were fabricated by electropolymerization of aniline containing well-dissolved MWNTs. The films can be used as catalyst supports for electro-oxidation of methanol. Cyclic voltammogram and Chronoamperogram results show that platinum particles deposited on PANI/MWNT composite films exhibit higher electrocatalytic activity towards methanol oxidation than that deposited on pure PANI films. The porous structure and electrical conductivity of PANI films has been significantly changed by introduction of MWNTs, higher surface areas of PANI/MWNT composites has been achieved therefore. It favors for platinum particles to be highly dispersed on the PANI/MWNT composite films and the better electrocatalytic activity of Pt/PANI/MWNT electrode is induced consequently.     

Multi-walled carbon nanotube/silver nanoparticles used for thermal transportation

A green method was applied to prepare composites of multi-walled carbon nanotubes (MWNTs) decorated with silver nanoparticles (Ag-NPs). MWNTs were functionalized using ball milling technology in the presence of ammonium bicarbonate, and the traditional method of silver mirror was used to decorate MWNTs to obtain Ag/MWNT composite. The obtained Ag/MWNT composites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transmission infrared spectroscopy, and Brunauer–Emmet–Teller (BET) surface area analysis. SEM characterization showed that Ag-NPs distributed uniformly on the walls of MWNTs. The content and size of Ag-NPs could be controlled by adjusting the redox time. XRD patterns demonstrated that the Ag-NPs are composed of pure Ag and crystallized well. BET analysis indicated that the specific surface areas of Ag/MWNT decrease with increasing the content of Ag-NPs, and this result is similar to that of the literature. The measurement results of the thermal property showed that the thermal conductivity of the nanofluid containing Ag/MWNT composites was higher than that of nanofluid containing pristine or functionalized MWNTs.     

Synthesis and characterization of multi-walled carbon nanotubes functionalized with hyperbranched poly(urea-urethane)

Two types of hyperbranched poly(urea-urethane)-functionalized multi-walled carbon nanotubes (GHPU) have been synthesized in the presence of bis- and tris-hydroxy terminated carbon nanotubes (MWNT-OH). For comparison of the grafting efficiency on carbon nanotubes, pure hyper-branched poly(urea-urethane)s (HPUs) were also synthesized to prepare pristine carbon nanotubes-reinforced nanocomposites (HPNTs). Better MWNT dispersion in the polymer matrix was obtained for GHPU than for HPNT, and the effect was superior in the case of highly branched GHPU from tris-hydroxy-functionalized MWNTs, compared to GHPU from bis-hydroxy-functionalized MWNTs. TEM measurements for GHPUs clearly showed hyperbranched polymer-wrapped MWNT structures. Crystallization of hyperbranched polymers in GHPU was more developed than that of the HPNT nanocomposites, although MWNT-induced crystallization was observed for both the GHPU and HPNT samples. The hyperbranched polymer-grafting effect on MWNTs resulted in greater enhancement of the mechanical properties of GHPU at the same nanotube loading, compared to the case of HPNT nanocomposites. However, a too highly branched structure was found to lower the crystallization and mechanical properties of both the GHPUs and HPNTs.     

熔融纺丝方法制备纳米碳管/聚丙烯复合纤维及其拉伸性能

采用传统的熔融纺丝技术大量制备了定向性良好的纳米碳管／聚丙烯复合纤维。扫描电镜观察证实了纳米碳管在纤维里的定向性以及分散性都得到了较大的改善。通过拉伸实验测试了纳米碳管／聚丙烯复合纤维的力学性能，采用weibull统计分析发现纳米碳管的添加显著提高了复合纤维的拉伸强度，当添加纳米碳管的质量分数达到3％时，纤维强度最高，达到61MPa，超过聚丙烯纤维强度120％。复合纤维拉伸断口的形貌特征也证实了纳米碳管添加对复合纤维拉伸性能影响存在临界现象。     

Preparation of carbon nanotube/chitosan/gold nanoparticle composite microspheres

The electrostatic layer-by-layer (LbL) assembly of acid-modified multi-walled carbon nanotubes (MWNTs) and biopolymer chitosan (CHIT) is realized on planar substrates and polystyrene (PS) microsphere templates, respectively. The successful stepwise growing process of the composite films on planar substrates is investigated and confirmed by scanning electron microscopy and UV-vis spectroscopy. The transfer of the LbL assembly of MWNTs and CHIT to spherical PS microspheres leads to novel (MWNT/CHIT)PS core-shell structure, on which the gold nanoparticles (GNPs) are deposited to fabricate GNP(MWNT/CHIT)PS composite microspheres. The glass carbon electrodes modified with such (MWNT/CHIT)PS or GNP(MWNT/CHIT)PS composites exhibit satisfactory electrocatalytic activities for biomolecule dopamine.     

Spark Plasma Sintered Hydroxyapatite/Multiwalled Carbon Nanotube Composites With Preferred Crystal Orientation

Hydroxyapatite (HA) and its nanocomposites reinforced with low loading levels of multiwalled carbon nanotubes (MWNTs) are prepared by spark plasma sintering process. The structure, morphology, and hardness of sintered HA and MWNT/HA nanocomposites are characterized by means of X‐ray diffraction (XRD), scanning electron microscopy and nanoindentation techniques. XRD results show that the orientation of crystallographic planes of sintered HA are highly related to the applied pressure direction. The perpendicular section of sintered MWNT/HA nanocomposites shows predominantly oriented HA a‐and b‐planes while the parallel section displays a dominant c‐plane orientation. The hardness of MWNT/HA nanocomposites improves considerably with increasing MWNT content.     

Carbon nanotube/graphene nanocomposite as efficient counter electrodes in dye-sensitized solar cells

We demonstrated the replacement of the Pt catalyst normally used in the counter electrode of a dye-sensitized solar cell (DSSC) by a nanocomposite of dry spun carbon multi-walled nanotube (MWNT) sheets with graphene flakes (Gr-F). The effectiveness of this counter electrode on the reduction of the triiodide in the iodide/triiodide redox (I(-)/I(3)(-)) redox reaction was studied in parallel with the use of the dry spun carbon MWNT sheets alone and graphene flakes used independent of each other. This nanocomposite deposited onto fluorinated tin-oxide-coated glass showed improved catalytic behavior and power conversion efficiency (7.55%) beyond the use of the MWNTs alone (6.62%) or graphene alone (4.65%) for the triiodide reduction reaction in DSSC. We also compare the use of the carbon MWNT/Gr-F composite counter electrode with a DSSC using the standard Pt counter electrode (8.8%). The details of increased performance of graphene/MWNT composite electrodes as studied are discussed in terms of increased catalytic activity permitted by sharp atomic edges that arise from the structure of graphene flakes or the defect sites in the carbon MWNT and increased electrical conductivity between the carbon MWNT bundles by the graphene flakes.     

多壁碳纳米管填充丁苯橡胶复合材料的研究

采用浓硝酸(HNO3)氧化处理后的多壁碳纳米管(MWNTs)与丁苯橡胶(SBR)及其他配合剂在开炼机上进行混炼加工制备MWNTs／橡胶复合材料，并与炭黑补强橡胶体系进行对比，进而研究了MWNTs／橡胶复合材料的物理性能，并初步探讨了该材料微观结构与性能之间的关系。结果表明：随着MWNTs质量百分含量的增加，橡胶复合材料的力学性能也随之增高；MWNTs／橡胶复合材料的抗撕裂强度(25．9kN／m)、硬度(58)、磨耗(0．22mL/1．61km)性能较炭黑／橡胶体系要好。由MWNTs补强的橡胶对开发具有低滚动滞后性和抗疲劳损失的轮胎胎面胶将有很大的实用潜力。     

Enhanced mechanical properties of polyacrylonitrile/multiwall carbon nanotube composite fibers

The use of multiwall carbon nanotubes (MWNTs) as a reinforcing phase in a polyacrylonitrile (PAN) fiber matrix was investigated with the goal of producing a PAN-derived carbon/MWNT composite fiber with enhanced physical properties. MWNTs were dispersed in a PAN/DMAc (dimethylacetamide) solution and spun into composite fibers containing up to 5 wt.% MWNTs, with the use of a lab-scale dry-jet wet spinline. The spinning process resulted in alignment of the MWNTs parallel with the fiber axis. Three types of chemical vapor deposition (CVD)-derived, high-purity MWNTs were used: as produced, graphitized (heat treated to 2800 degrees C), and NaCN-treated (chemically treated to attach CN groups to the nanotube surface). Tensile tests were performed to measure yield stress/strain, initial modulus, break stress/strain, and energy to yield and energy to break. Significant mechanical property increases were recorded for the composite fibers compared with the control samples with no MWNT reinforcement: break strength +31%, initial modulus +36%, yield strength +46%, energy to yield +80%, and energy to break +83%.     

混杂功能化碳纳米管/聚氨酯复合材料的制备及性能

以多壁碳纳米管（MWNTs）为原料,采用不同改性方法制得了羧化碳纳米管（MWNTs-COOH）、共价功能化碳纳米管（MWNTs-NH₂）、非共价功能化碳纳米管（MWNTs-PPA）和混杂功能化碳纳米管（MWNTs-COOH-PPA）,将这4种改性碳纳米管按不同质量分数分别加入聚氨酯（PU）中制备了复合材料。使用万能材料试验机和热失重分析仪测试了复合材料的力学和热学性能,研究了碳纳米管对复合材料性能的影响。结果表明:通过在碳纳米管表面接枝少量的共价官能团防止非共价包覆的剥离,混杂功能化方法既能够改善碳纳米管在基体中的分散性,又能够保持其与基体界面间结合力,复合材料增强效果最明显。耐热性良好的碳纳米管的添加提高了PU基体的热分解温度,提高程度由于其功能化方式的不同而稍有差别。MWNTs-COOH-PPA/PU复合材料的力学性能最优,当碳纳米管含量（质量分数,下同）为0.3%时,其拉伸强度与纯PU相比提高104%,其热分解温度与MWNTs-COOH/PU相当,优于纯PU,但低于MWNT8-NH₂/PU和MWNTs-PPA/PU。     

Spark Plasma Sintered Hydroxyapatite/Graphite Nanosheet and Hydroxyapatite/Multiwalled Carbon Nanotube Composites: Mechanical and in Vitro Cellular Properties

Hyroxyapatite (HA) and its nanocomposites reinforced with 0.5, 1, 1.5, and 2 wt% graphite nanosheets (GNs) and multi‐walled carbon nanotubes (MWNTs) are fabricated by means of spark plasma sintering (SPS) process. The effects of MWNT and GN additions on the morphology, mechanical behavior, cell adhesion, and biocompatibility of HA were studied. Three‐point‐bending test shows that the bending strength of MWNT/HA nanocomposites increases with increasing MWNT content. However, the bending strength of GN/HA nanocomposites initially increases by adding 0.5 wt% GN, and then decreases markedly as the filler content increases. Cell culture and viability test results demonstrate that the GNs with diameters of several micrometers retard osteoblast cell adhesion and proliferation on the GN/HA nanocomposite. In contrast, the addition of 2 wt% MWNT to HA is beneficial to promote osteoblast adhesion and proliferation, thereby enhancing the biocompatibility of MWNT/HA nanocomposite.     

Multi-walled carbon nanotubes-supported Fe(naph)3 nanoparticles to prepare polyacetylene/multi-walled carbon nanotubes nanocomposites

Carbon nanotubes (CNTs) are a promising candidate for preparing conductive polymer/CNT nanocomposites. CNTs are also an alternative to conventional catalyst support. This report studies multi-walled carbon nanotubes (MWNTs) supported-Fe(naph)₃ nanoparticles to prepare polyacetylene (PA)/MWNT nanocomposites with core–shell structure. The XPS spectra and HRTEM images demonstrate the Fe(naph)₃ nanoparticles successfully deposited on the walls of MWNTs and partially transformed to γ-Fe₂O₃ nanoparticles after heated at 100 °C for 2 h. XRD analysis indicates the formation of PA on the walls of MWNTs. Structural analysis using HRTEM shows that PA/MWNT nanocomposites exhibit core–shell structure. TGA data reveals the stability of PA grown on the exterior walls of MWNTs has been improved. The growth mechanism of PA/MWNT nanocomposites can be explained by a heterogeneous process. The conductivity of the nanocomposites was studied by a four-probe approach and a relatively high conductivity was observed.     

Effect of dispersion condition of multi-walled carbon nanotube (MWNT) on bonding properties of solderable isotropic conductive adhesives (ICAs)

Carbon nanotubes have been considered as reinforcements in composite materials because of their exceptional mechanical, electrical, and thermal properties. In this paper, the effect of dispersion conditions of multi-walled carbon nanotubes (MWNTs) on bonding properties of solderable isotropic conductive adhesives (ICA) was investigated. Two types of ICAs, untreated pristine MWNT-filled ICAs and acid-treated MWNT (a-MWNT)-filled ICAs were formulated with 1 wt% MWNTs and 83 wt% low-melting-point alloy (LMPA) fillers. X-ray photoelectron spectroscopy analysis was conducted to characterize the surface chemical states of pristine and a-MWNTs and verify the effectiveness of a-MWNTs. The fracture surface of the polymer matrix and solderable ICAs with a-MWNTs showed good dispersion conditions through field-emission scanning electron microscope. After the interconnection process, the a-MWNT-filled solderable ICA showed uniform dispersion of MWNTs in the polymer matrix and formed a stable metallurgical conduction path because of the good rheology-coalescence-wetting behavior of LMPA. Alternatively, pristine MWNT-filled ICA showed poor dispersion and an unstable conduction path formed by aggregated MWNTs.     

Synthesis and characterization of processable multi-walled carbon nanotubes-sulfonated polydiphenylamine graft copolymers

Water soluble and processable nanocomposites composed of multi-walled carbon nanotubes (MWNTs) and poly(diphenylamine sulfonic acid) (PDPASA) are synthesized and characterized. Two types of methodologies are adopted. MWNTs are covalently functionalized with 2,5-diaminobenzene sulfonic acid (DABSA) and further in situ polymerized with diphenylamine-4-sulfonic acid (DPASA). This results in the formation of nanocomposites, MWNT(DABSA)-g-PDPASA, in which PDPASA is presented as the graft chains onto MWNTs. In another approach, DPASA is in situ polymerized in presence of unfunctionalized MWNTs, results in a nanocomposite in which MWNTs are present as entrapped mass in PDPASA matrix. Both nanocomposites are found to be water soluble and can form free standing films. The conductivity of MWNT(DABSA)-g-PDPASA and MWNT/PDPASA is found to be 1.25 mS x cm(-1) and 0.65 mS x cm(-1), respectively, which is higher than that of pristine PDPASA (0.25 x 10(-5) S x cm(-1)). The nanocomposites are characterized for their structure, morphology, optical and thermal properties.     

Highly dense and uniformly dispersed platinum nanoparticles on poly(acrylic acid) modified multi-walled carbon nanotubes for methanol oxidation

Poly(acrylic acid) modified multi-walled carbon nanotubes (PAA-MWNTs) were synthesized through in situ radical polymerization in acetone and the PAA-MWNTs were used as supporting material for platinum nanoparticles. Platinum nanoparticles were deposited on the surface of PAA-MWNTs with high loading and high dispersion through ethylene glycol reduction. The size of Pt nanoparticles on PAA-MWNTs can be tuned by the water content in the reaction system and the loading amount can be adjusted by the mass ratio of H₂PtCl₆ to PAA-MWNTs. The electrocatalytic properties of the Pt/PAA-MWNTs catalyst were evaluated by methanol oxidation. The results of cyclic voltammetry show that the Pt/PAA-MWNTs composite possesses high electrocatalytic activity, good long-term stability and storage property, which can be attributed to the small particle size and high dispersion of Pt nanoparticles as well as the nature of MWNTs.     

Facile preparation and characterization of free-standing stiff carbon-based composite films with excellent performance

Novel free-standing stiff all carbon films based on multi-walled carbon nanotube (MWNT)/glassy carbon (GC) with excellent performance were fabricated. MWNTs, as excellent reinforcing materials, were successfully dispersed in polyimide (PI) matrix by in situ polymerization. The resultant MWNT/PI nanocomoposite films were used as precursors and underwent carbonization process. As a result, all carbon constituted MWNT/GC composite films were obtained. Mechanical results showed the maximum 3-point bending strength and modulus reached 575.5 MPa and 7.7 GPa respectively, improved by 54% and 78% compared to those of neat GC films. This method is simple, and the free-standing composite films can be prepared in large scales, which hold great potential in many applications.     

Variability of the elastic properties of multiwalled carbon nanotubes

The results of numerous experimental investigations of carbon nanotubes show evidence of a considerable variability in their mechanical properties. Based on the common features of the structures of graphite and multiwalled carbon nanotubes (MWNTs), it is demonstrated that structural polytype transitions are among the probable factors responsible for this variability. Analysis of the MWNT behavior under torsion shows that the torsional stiffness of MWNTs depends on the elastic moduli, the number and magnitudes of which vary with the local symmetry of the MWNT structure (on the transition from rhombohedral to hexagonal and turbostratic modifications). The effect of structural transformations on the Young modulus in stretched MWNTs is evaluated.     

Polyazomethine/carbon nanotube composites

Composites were synthesized by “in-situ” polymerization of polyazomethine, a liquid crystal polymer (LCP), in presence of multi-walled carbon nanotubes (MWNTs) previously dispersed in one of the employed monomers. Fiber processing was carried out by extrusion from the composites containing 1 and 10 wt.% of MWNTs at the mesophase temperature. We have observed that the typical highly oriented internal fibrillar structure can be significantly disrupted by increasing the nanotube content in the composite fibers. Evidences of MWNT alignment were found in the studied LCP/MWNT composites.     

Poly(vinylidene fluoride)-assisted melt-blending of multi-walled carbon nanotube/poly(methyl methacrylate) composites

Multi-walled carbon nanotubes (MWNTs) were sonicated in the dimethylformamide solution of poly(vinylidene fluoride) (PVDF). The PVDF-covered MWNTs were then melt-blended with poly(methyl methacrylate) (PMMA). The dynamic mechanical behavior of various composites was studied. The presence of a small amount of PVDF leads to a significant improvement in the storage moduli of the MWNT/PMMA composites at low temperatures. The storage modulus of a PVDF/MWNT/PMMA composite containing 0.5 wt.% PVDF is almost twice as that of a MWNT/PMMA composite at 50°C. However, a further increase in the PVDF content leads to a reduction of the storage modulus. The beneficial effect of PVDF diminishes at higher temperatures.     

Controlling bubble density in MWNT/polymer nanocomposite foams by MWNT surface modification

Polymer nanocomposite foams are promising substitutes for polymeric foams. Carbon nanotube/polymer nanocomposite foams possess high strength, low density, and can be made conductive. Creating polymer foams with controlled foam morphology is of great importance for controlling foam properties. The foam morphology is influenced by the foaming conditions and filler properties. For carbon nanotube/polymer composite foams, dispersion state and aspect ratio of the carbon nanotubes have been shown to influence the bubble density and bubble size. In the current study, the influence of carbon nanotube surface chemistry on the bubble density of multi-walled carbon nanotube/poly(methyl methacrylate), MWNT/PMMA, nanocomposite foams was investigated. The surface of the MWNTs with controlled aspect ratio was covalently modified with glycidyl phenyl ether (GPE). Surface modified MWNT/PMMA nanocomposite foams were produced using a supercritical carbon dioxide foaming process. At constant MWNT concentration, the bubble density of polymer nanocomposite foams filled with GPE surface modified MWNT was found to be several times higher than that of polymer nanocomposite foams filled with nitric acid treated MWNT. After the MWNTs were modified with GPE, the surface chemistry of the MWNT became the dominant factor in determining the bubble density while the MWNT aspect ratio became less influential.