Raman spectroscopy of fullerenes and fullerene-nanotube composites

The discovery of fullerenes in 1985 opened a completely new field of materials research. Together with the single-wall carbon nanotubes (SWCNTs) discovered later, these curved carbon networks are a playground for pure as well as applied science. We present a review of Raman spectroscopy of fullerenes, SWCNTs and composite materials. Beginning with pristine C(60), we discuss intercalated C(60) compounds and polymerized C(60), as well as higher and endohedral fullerenes. Concerning SWCNTs, we show how the diameter distribution can be obtained from the Raman spectra and how doping modifies the spectra. Finally, the Raman response of C(60) encapsulated into SWCNTs (C(60) peapods) is discussed.     

Phase behavior and shear alignment in SWNT-surfactant dispersions

The effect of single-walled carbon nanotubes (SWNT) on the phase behavior of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous solutions is investigated at room temperature. Small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM) are used for characterization of bulk dispersions and nanometrically thin films. Additional carbonaceous additives (fullerenes, multi-walled carbon nanotubes, and carbon black) serve as reference systems. It is found that dispersions of carbonaceous additive (excluding fullerenes) at intermediate surfactant concentrations (below the liquid-crystalline region of the native surfactant) induce demixing and macroscopic phase separation in otherwise homogeneous solutions of CTAB. Two coexisting liquid phases of similar CTAB concentrations are observed, with the carbonaceous species residing within the lower phase. At high CTAB concentrations (liquid-crystal region) the SWNTs are found to incorporate into the ordered lyotropic liquid-crystalline phase while preserving the native d-spacing. Investigation of nanometrically thin films at intermediate surfactant concentrations under external shear reveals shear-induced structure (SIS) in the presence of minute amounts of SWNTs. The effect is found to be exclusive to SWNT and does not occur in dispersions of other carbonaceous additives.     

不同碳纳米管对壳聚糖膜性能的影响研究

目的研究普通碳纳米管(MWNT)与羧基化碳纳米管(MWNT-COOH)对壳聚糖复合膜性能的影响。方法将质量分数不同的MWNT与MWNT-COOH分别添加到壳聚糖基材中,采用溶液共混法制得纳米复合膜,并对复合膜的溶胀性能、透湿性能、力学性能、表面形貌和抑菌性能等进行表征。结果当MWNT和MWNT-COOH的质量分数均为1%时,2种复合膜的阻湿性能和拉伸性能相对于纯壳聚糖膜有明显改善,尤其是MWNT-COOH,2种碳纳米管的加入均可增强复合膜对大肠杆菌的抑制效果。结论浓度相同时,与MWNT相比,MWNT-COOH与壳聚糖间具有更强的结合力,它的加入能更有效地改善壳聚糖膜的性能。     

Nanostructured Carbon Films

By periodic variation of the deposition conditions nanometer multilayers of amorphous carbon films of varying density are deposited. Such carbon–carbon multilayers can be used for the preparation of X‐ray mirrors of extreme irradiation stability and the optimization of tribological carbon coatings. Combining these techniques with concepts demonstrated in the preparation of fullerenes and nanotubes leads to graphitic films of very high hardness. Potential applications involve such different fields as field emission cathodes for flat panel displays and low‐friction wear‐protecting films.     

Polymer Nanocomposites for Aerospace Applications: Fabrication

Nanocomposite polymers have tremendous potential to enhance the performance of macromolecular materials used for composite matrices. Effective utilization of carbon nanotubes in composite applications depends strongly on the ability to homogeneously disperse them throughout the matrix without destroying their integrity. This work looks at the fabrication for montmorillonite, fullerenes and nanotubes polymer/nanocomposites tailored to fit aerospace needs. Further insight is also given on developments in nanofibers and nanotubes production for good load transfer on the composite systems.     

A New Molecular Mechanics Computer Program for Giant Fullerenes and Nanotubes

The molecular mechanics computer program is designed to study the structure of fullerenes with icosahedral symmetry and carbon nanotubes. The program takes full advantage of symmetry. The program predicts meaningful conformations, energies of formation for symmetrical fullerenes as well as for the carbon nanotubes for which also the elastic properties are calculated.

The systematic IUPAC nomenclature of fullerenes and fullerenes derivatives is discussed. Comments are made on terminology questions and on the chemical non-aromaticity of fullerenes.     

The photoluminescence of amorphous carbon in a-C:C<Subscript>60</Subscript> films obtained by fullerene C<Subscript>60</Subscript> deposition

The results of experimental investigations of the carbon deposits obtained in the course of fullerene C₆₀ sublimation are presented. It is shown that the films formed at a high deposition rate possess a composite structure representing a mixture of fullerenes and an amorphous carbon phase with a graphitelike short-range order. The films containing amorphous nonhydrogenated carbon possess photoluminescent properties analogous to those of hydrogenated amorphous carbon films with a high hydrogen content. The possible mechanism of photoluminescence of the composite carbon films is discussed.     

聚吡咯／多壁碳纳米管的合成及电化学行为

在含有多壁碳纳米管(MWCNT)的十二烷基苯磺酸钠(SDBS)溶液中电化学氧化吡咯(Py)制得聚吡咯/多壁碳纳米管(PPy/MWCNT)导电复合膜。研究了聚合温度、电流密度、吡咯浓度对PPy/MWC-NT复合膜沉积量的影响,采用交流阻抗谱(EIS)法研究了该导电复合膜的电化学行为,并用扫描电子显微镜对其表面形貌进行了观察。实验结果表明,随着温度的降低、电流密度及吡咯浓度的增大,复合膜沉积量变大。与纯PPy膜相比,PPy/MWCNT复合膜有更好的电子传递行为,而复合膜表面更加粗糙、疏松。     

Laser-induced processes in the IR range in nanocomposites with fullerenes and carbon nanotubes

Laser-induced processes in the IR spectral range, which are related to manifestations of the optical limiting in composite systems containing fullerenes and carbon nanotubes (CNTs), have been studied. Organic materials based on polyimides (PIs), 2-cyclooctylamine-5-nitropyridine (COANP), polyanilines, and dispersed liquid crystal (LC) structures were used as nanoparticle-sensitized matrices. Manifestations of optical limiting in the IR range at 1047, 1080, 1315, and 2940 nm are demonstrated and the position of composites studied among other systems used for optical limiting in the IR range is determined. The optical limiting at 1080 nm in CNT-containing solutions and LC cells was studied and the levels of limiting in thin-film PI-based nanocomposites with CNTs are established. A microscopic examination of thin PI films with CNTs revealed the structure of quasi-photonic crystals formed in these systems.     

Alignment of muscle precursor cells on the vertical edges of thick carbon nanotube films

The development of scaffolds and templates is an essential aspect of tissue engineering. We show that thick (> 0.5 mm) vertically aligned carbon nanotube films, made by chemical vapour deposition, can be used as biocompatible substrates for the directional alignment of mouse muscle cells where the cells grow on the exposed sides of the films. Ultra high resolution scanning electron microscopy reveals that the films themselves consist mostly of small diameter (10 nm) multi-wall carbon nanotubes of wavy morphology with some single wall carbon nanotubes. Our findings show that for this alignment to occur the nanotubes must be in pristine condition. Mechanical wiping of the films to create directional alignment is detrimental to directional bioactivity. Larger areas for study have been formed from a composite of multiply stacked narrow strips of nanotubes wipe-transferred onto elastomer supports. These composite substrates appear to show a useful degree of alignment of the cells.     

镍基碳纳米管复合电沉积薄膜的制备和机械性能分析

采用直径为10～20nm的碳纳米管作为增强相材料,采用间歇超声复合空气搅拌,通过复合电沉积技术,制备了碳管均匀分散,表面平整连续的镍基碳纳米管复合薄膜.通过扫描电子显微镜(SEM),对镀层的表面形貌进行了观察,并用表面轮廓仪,对镀层的粗糙度进行了测量.通过显微硬度计和纳米硬度计对镀层的硬度分别进行了测量,采用一种新型的微拉伸器件对复合薄膜的拉伸性能进行了测量.通过实验发现,采用间歇超声复合空气搅拌方式在镍镀层中复合碳纳米管,可以明显的提高镀层的硬度,并且当镀层中碳纳米管体积百分比在4%左右时,镀层硬度最大.同时镀层的抗拉强度也有所提高,通过用SEM对镀层断裂处观测,验证了碳纳米管的增强效应.     

Simulation of novel superhard carbon materials based on fullerenes and nanotubes

The state-of-the-art in theoretical research directed at the search for superhard materials based on carbon fullerenes and nanotubes has been briefly reviewed. The data available on elastic properties of the main groups of condensed phases that form due to the interaction of fullerenes or (and) nanotubes because of both weak (of the van der Waals type) bonds and polymerization to form strong covalent sp3 bonds have been considered. Models for new hypothetical carbon nanostructured materials (the so-called autointercalated hyperdiamonds, covalently bonded lattices of nanotubes, tubular cubic crystals, etc.) are discussed, and elastic properties of them are considered as related to their atomic structure, special features of their electronic structure and chemical bond have been discussed. The problems of synthesis of these systems are briefly considered.     

Formation and conversion of carbon nanostructures under radiation

Consideration has been given to the current status of research on the use of radiation techniques for synthesizing new carbon nanomaterials based on fullerenes, carbon nanotubes, and graphene sheets and their derivatives, which are promising for practical application due to their unique properties. An analysis has been made of the existing experimental and theoretical works on studying different processes induced by the action of radiation on carbon nanostructures (melting of cross-linking carbon nanotubes and formation of molecular junctions between them, polymerization of fullerene layers, formation of new structures, radiation chemistry of fullerenes, and others).     

A novel hybrid carbon material

Both fullerenes and single-walled carbon nanotubes (SWNTs) exhibit many advantageous properties. Despite the similarities between these two forms of carbon, there have been very few attempts to physically merge them. We have discovered a novel hybrid material that combines fullerenes and SWNTs into a single structure in which the fullerenes are covalently bonded to the outer surface of the SWNTs. These fullerene-functionalized SWNTs, which we have termed NanoBuds, were selectively synthesized in two different one-step continuous methods, during which fullerenes were formed on iron-catalyst particles together with SWNTs during CO disproportionation. The field-emission characteristics of NanoBuds suggest that they may possess advantageous properties compared with single-walled nanotubes or fullerenes alone, or in their non-bonded configurations.     

Carbon fibers modified with carbon nanotubes

Carbon nanotubes were used to modify a polyacrylonitrile (PAN) polymer solution before the manufacture of the carbon fiber precursor. The modified PAN fibers were spun from a dimethylformamide solution containing a small amount of single-walled carbon nanotubes. The fibers were characterized by thermogravimetry and optical and scanning electron microscopy. Structure, morphology, and selected properties of the composite polymeric fibers and the fibers after carbonization are characterized. The mechanical properties of the fibers are examined. It is found that nanotubes in the PAN solution have a strong tendency to form agglomerates that inhibit suitable macromolecular chain orientation of the carbon fiber precursor. Fibers manufactured from such a solution have similar mechanical properties to those from a pure PAN precursor, and after carbonization the resultant carbon fibers are very weak. A comparison of pure carbon fibers and those containing nanotubes reveals slight differences in their structural ordering.     

Shape and complexity at the atomic scale: the case of layered nanomaterials

In nature there are numerous layered compounds, some of which could be curved so as to form fascinating nanoshapes with novel properties. Graphite is at present the main example of a very flexible layered structure, which is able to form cylinders (nanotubes) and cages (fullerenes), but there are others. While fullerenes possess positive curvature due to pentagonal rings of carbon, there are other structures which could include heptagonal or higher membered rings. In fact, fullerenes and nanotubes could display negative curvature, thus forming nanomaterials possessing unexpected electronic and mechanical properties. The effect of curvature in other nano-architectures, such as in boron nitride and metal dichalcogenides, is also discussed in this account. Electron irradiation is a tool able to increase the structural complexity of layered materials. In this context, we describe the coalescence of carbon nanotubes and C(60) molecules. The latter results now open up an alternative approach to producing and manipulating novel nanomaterials in the twenty-first century.     

Mechanical Characteristics and Preparation of Carbon Nanotube Fiber‐Reinforced Ti Composite

Carbon nanotubes, a kind of high order fullerenes, offers remarkable electronic as well as mechanical properties, e.g., an extremely high Young’s modulus of TPa order has been reported. This suggests the suitability of carbon nanotubes as novel fiber materials for metal matrix composites. The authors demonstrate that Ti/ nanotube composites show a large increase in hardness and Young’s modulus as compared to pure Ti. This makes the composite an attractive advanced material for future applications.     

Ferroelectric ordering in ice nanotubes confined in carbon nanotubes

The ice nanotubes with odd number of side faces formed inside carbon nanotubes (CNTs) are found to exhibit spontaneous electric polarizations along their tube axes by means of molecular dynamics simulations. The physical mechanism underlying the quasi-one-dimensional (Q1D) ferroelectricity is an interplay between the Q1D geometrical confinement of CNTs and the distinct orientational ordering of the hydrogen bonds dictated by the "ice rule". This mechanism is fundamentally different from the conventional one seen in three-dimensional ferroelectric (FE) materials or in two-dimensional FE ice films. In addition, it is found that vacancies in the ice nanotubes can induce a net polarization normal to the tube axis.     

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.     

Electromagnetic shielding effectiveness of thin film with composite carbon nanotubes and stainless steel fibers

Using the polymer blending method, conductive materials and waterborne polyurethane (WPU) were mixed to fabricate conductive composite films for application in electromagnetic shielding. First, nitric acid was used to purify the multi-walled carbon nanotubes (MWCNT). Second, sodium dodecyl sulfate (SDS) was utilized to disperse the carbon nanotubes, and then they were mixed with 8 microm diameter and 2 mm long stainless steel fibers (SSF) in the WPU by the polymer blending method. Finally, the thickness of 0.25 mm of conductive composite film was fabricated by means of coating. According to the ASTM D4935-99 standard, a coaxial transmission line was used to measure the electromagnetic shielding effectiveness (EMSE) of conductive composite film within the range of 50 MHz approximately 3.0 GHz. Moreover, the influence of the prior and posterior dispersion of carbon nanotubes dispersed on electromagnetic shielding was dealt with in the paper. Results demonstrated that the conductive composite film, within 50 MHz approximately 3.0 GHz, fabricated by the 15 wt% of the multi-walled carbon nanotubes and 30 wt% of the stainless steel fibers can achieve the maximum of the electromagnetic shielding effectiveness, 34.86 dB, and its shielding effect, 99.9%.