Formation of Multiwall Carbon Nanotubes on Cylindrical Substrates in Synthesis by Metal-Organic Chemical Vapor Deposition

Processes of deposition of multiwall carbon nanotubes in the synthesis by metal-organic chemical vapor deposition on hollow cylindrical substrates and the effect of the substrate area on the yield of the target product were studied. Making larger the tubular deposition reactor and the area of the cylindrical substrate enabled a substantial increase in the yield of carbon nanotubes. The technological synthesis parameters of the carbon material were optimized. Methods were developed for purification of carbon nanotubes by annealing in air, and materials were obtained with purity of no less than 98%. Physicochemical analysis methods were used to examine the structure and properties of the materials.     

A study of the interaction between polyelectrolyte-coated nanostructured CaCO<Subscript>3</Subscript> particles and a stearic acid monolayer spread at the water/air interface

The influence of nanostructured CaCO₃ particles, both uncoated and coated with a polyelectrolyte (poly(diallyldimethylammonium chloride), polyethyleneimine, fluorescein-5-isothiocyanate-labeled poly(allylamine hydrochloride), or sodium polystyrene sulfonate), on a stearic acid monolayer spread on the surface of an aqueous subphase has been studied. The interaction of the particles present in the subphase with the monolayer as depending on the presence and composition of a polymer coating has been estimated with the help of compression isotherms and the Brewster angle microscopy. The monolayers were transferred from the aqueous subphase onto a solid substrate and studied by scanning electron microscopy. Strong interaction has been revealed between the calcium carbonate particles and the stearic acid monolayer. It has been shown that the transfer of the monolayer from the aqueous suspension surface onto the solid substrate may be accompanied by the detachment of the polymer coating from the surface of CaCO₃ particles or their transfer together with the monolayer.     

Comparative study on different carbon nanotube materials in terms of transparent conductive coatings

We compared conductive transparent carbon nanotube coatings on glass substrates made of differently produced single-wall (SWNT), double-wall, and multiwall carbon nanotubes. The airbrushing approach and the vacuum filtration method were utilized for the fabrication of carbon nanotube films. The optoelectronic performance of the carbon nanotube film was found to strongly depend on many effects including the ratio of metallic-to-semiconducting tubes, dispersion, length, diameter, chirality, wall number, structural defects, and the properties of substrates. The electronic transportability and optical properties of the SWNT network can be significantly altered by chemical doping with thionyl chloride. Hall effect measurements revealed that all of these thin carbon nanotube films are of p-type probably due to the acid reflux-based purification and atmospheric impurities. The competition between variable-range hoping and fluctuation-assisted tunneling in the functionized carbon nanotube system could lead to a crossover behavior in the temperature dependence of the network resistance.     

表面引发原子转移自由基聚合制备聚电解质修饰的碳纳米管

利用聚电解质对多壁碳纳米管(MWNT)的表面进行修饰,能有效改善碳纳米管在溶剂中的分散性.首先将经硝酸氧化的碳纳米管与二甲亚砜和乙二醇反应,得到羟基修饰的碳纳米管.然后利用羟基与α-溴异丁酰溴(或α-氯丙酰氯)的酯化反应,在碳纳米管的表面引入了原子转移自由基聚合(atom transfer radical polymerization,ATRP)引发基团,引发丙烯酸叔丁酯(tBA)或4-乙烯基吡啶(4VP)聚合,通过投料比的改变,得到接入量不同的聚合物修饰的碳纳米管.利用热重分析(TGA)和红外对聚合物修饰的碳纳米管进行表征.将聚合物修饰的碳纳米管进行水解(或季胺化),制备得到在水溶液中良好分散的聚电解质修饰的碳纳米管.     

Surface functionalization of multiwalled carbon nanotubes with poly(3,4-propylenedioxythiophene) and preparation of its random copolymers: new hybrid materials

Multiwalled carbon nanotubes (MWNTs) were functionalized with poly(3,4-propylenedioxythiophene) (PProDOT) using a simple “chemical grafting” approach. After the conventional acid oxidation (AO) process, the MWNT-COOH was converted to the acyl chloride functionalized MWNTs (MWNT-COCl) by treating them with thionyl chloride. The MWNT-COCl were further reacted with a functionalized monomer based on 3,4-propylenedioxythiophene (ProDOT-OH), followed by oxidative polymerization to prepare the MWNT-g-PProDOT hybrid. The monomer-functionalized MWNTs was further copolymerized with thiophene to prepare conducting copolymers on carbon nanotubes (CNTs). Fourier-transformed infrared spectrophotometry was employed to characterize the change in surface functionalities, which revealed that the PProDOT was covalently grafted to the MWNTs, while TGA was used to study the weight gain due to the functionalization. UV–Vis absorption spectra revealed the functionalization of the conjugated polymer by showing the typical absorption band. The morphology micrographs of the grafted PProDOT on MWNTs as evidenced by field emission scanning electron microscopy and transmission electron microscopy showed apparent effect on the structure and appearance of the MWNTs by growing thicker as expected from surface modification. Using the facile route developed in this study, CNTs can be easily fabricated with other types of polymers for several applications.     

Functionalized multiwall carbon nanotube/gold nanoparticle composites

Multiwall carbon nanotubes (MWCNTs) were chemically oxidized in a mixture of sulfuric acid and nitric acid (3:1) while being ultrasonicated. The effect of oxidative ultrasonication at room temperature on development of functional groups on the carbon nanotubes was investigated. The dispersability and the carboxylic acid group concentration of functionalized MWCNTs (fMWNTs) varied with reaction time. The concentration of carboxylic acid groups on fMWNTs increased from 4 x 10(-4) mol/g of fMWNTs to 1.1 x 10(-3) mol/g by doubling the treatment period from 4 to 8 h. The colloidal stability of aqueous fMWCNTs dispersions was enhanced through elongated oxidation. fMWCNTs that were reacted longer than 4 h did not precipitate in aqueous media for at least 24 h. The layer-by-layer self-assembly of polyelectrolytes on fMWCNTs was characterized by zeta potential measurements. The zeta potential of fMWCNTs changed from negative charge to positive charge when cationic polyelectrolytes were self-assembled on their surface. With addition of anionic polyelectrolytes, cationic polyelectrolyte coated fMWCNTs showed the expected charge reversal as expected for multilayer self-assembly. Complex formation of positively charged gold nanoparticles and negatively charged fMWCNTs was achieved with and without polyelectrolyte coatings by electrostatic interaction. The complex formation was characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The here found complex formation of positively charged colloidal gold and defect sites on fMWNTs indicates the location of functional groups on carbon nanotubes. It is suggested that positively charged colloids such as gold nanoparticles could be used for detection of defect sites on carbon nanotubes.     

Direct measurements of interactions between polypeptides and carbon nanotubes

The interactions of various polypeptides with individual carbon nanotubes (CNTs), both multiwall (MW) and single wall (SW), were investigated by atomic force microscopy (AFM). While adhesion forces arising from electrostatic attraction interactions between the protonated amine groups of polylysine and carboxylic groups on the acid-oxidized multi-wall carbon nanotubes (Ox-MWCNTs) dominate the interaction at a low pH, weaker adhesion forces via the hydrogen bonding between the neutral -NH2 groups of polylysine and -COO- groups of the Ox-MWCNTs were detected at a high pH. The adhesion force was further found to increase with the oxidation time for Ox-MWCNTs and to be negligible for oxidized single-wall carbon nanotubes (Ox-SWCNTs) because carboxylate groups were only attached onto the nanotube tips in the latter whereas onto both the nanotube tips and sidewall in the former. Furthermore, it was demonstrated that proteins containing aromatic moieties, such as polytryptophan, showed a stronger adhesion force with Ox-MWCNTs than that of polylysine because of the additional pi-pi stacking interaction between the polytryptophan chains and CNTs.     

Thermal behavior of multiwall carbon nanotube/zeolite nanocomposites

Summary In this study we report the synthesis and thermal characterization of multiwall carbon nanotubes containing zeolite based nanocomposites. Three different zeolites (LTA, FAU and MFI) were used in this study and it was observed that the morphologies of the synthesized nanocomposites were significantly different. For FAU zeolite nanocrystals with a few nm in diameter were nucleated on the nanotubes covering their surface, however, for LTA and MFI zeolites bulky crystals with nanotubes crossing them were observed by transmission electron microscopy. One of the most important results of our study was the generation of secondary mesoporosity in the zeolites after removing the carbon nanotubes.     

Effects of carbon nanotube functionalization on the agglomeration and sintering of supported Pd nanoparticles

The size of carbon nanotube supported Pd and PdO nanoparticles was investigated on oxidatively functionalized multiwall carbon nanotubes. All samples were characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy and Raman spectroscopy. The average particle diameter calculated from TEM image analysis was found to be inversely proportional with the duration of the oxidation in nitric acid. Crystallite sizes determined from XRD patterns confirmed this general tendency.     

Layer-by-layer self-assembly of multiwalled carbon nanotube polyelectrolytes prepared by in situ radical polymerization

Anionic and cationic multiwalled carbon nanotube polyelectrolytes, prepared by covalent modification of multiwalled carbon nanotubes (MWCNTs) with poly(acrylic acid) and poly(acrylamide), were used for the layer-by-layer (LBL) self-assembly of MWCNTs on different substrates with polyelectrolytes, such as poly(diallyldimethylammonium chloride) and sodium poly(styrenesulfonate). Thermogravimetric analysis, Raman spectroscopy, and scanning electron microscopy (SEM) were used to demonstrate the modification of MWCNTs. Investigations using Fourier transform infrared spectroscopy, atomic force microscopy, SEM, and ultraviolet-visible spectroscopy proved this method to be practicable for preparing LBL films.     

Controlling growth of aligned carbon nanotubes from porous silicon templates

Fabricating well-aligned carbon nanotubes, especially, on a silicon substrate is very important for their applications. In this paper, an aligned carbon nanotube array has been prepared by pyrolysis of hydrocarbons catalyzed by nickel nanoparticles embedded in porous silicon (PS) templates. High-magnification transmission electron microscopy images confirm that the nanotubes are well graphitized. The PS substrates with pore sizes between 10 and 100 nm play a control role on the growth of carbon nanotubes and the diameters of the tubes increase with the enlargement of the pores of the substrates. However, such a control role cannot be found in the macro-PS substrates.     

Nanotubes as polymer composite reinforcing additive materials – A comparative study

Nitrogen-doped bamboo-shaped carbon nanotubes (N-BCNTs) and their non-doped conventional counterparts, multiwalled carbon nanotubes (MWCNTs) were compared as polymer reinforcing additives in polyvinyl chloride (PVC) matrix. The nanotubes were synthetized by catalytic chemical vapor deposition (CCVD) method. The purity of both nanotubes was measured by thermogravimetric analysis (TGA) and found to be >91%. Further analysis on the morphology and size of the carbon nanotubes (CNTs) were performed by transmission electron microscopy (TEM). The PVC powder was impregnated with CNTs in ethanol by using tip ultrasonicator. The dispersion media was evaporated, and the CNT/PVC powder was used to produce polymer fibers. The orientation of carbon nanotubes in the PVC matrix was characterized by scanning electron microscopy (SEM), and the presence of nanotubes were confirmed in case of all PVC samples. It can be observed on the SEM images that the nanotubes are fully covered with PVC. The tensile strength of the nanotube containing samples was tested and the N-BCNT/PVC composite was found to be better in this sense, thanks to the extraordinary structure of the nanotube. In case of the N-BCNT/PVC composite the measured young modulus was 39.7% higher, while the elongation at brake decreased by 33.6% compare to the MWCNT/PVC composite. These significant differences in the mechanical properties of the composites can be explained with the stronger interaction between N-BCNTs and PVC.     

Surface-guided self-assembly of silver nanoparticles on edges of heterogeneous surfaces

A general method for the generation of two-dimensional (2D) ordered silver nanoparticles (av 45 nm) ring array has been demonstrated via controllable self-assembly. The selective self-assembly is conducted on the edges of a gold coated polyelectrolyte film. This film is fabricated using the monolayer polystyrene (PS) spheres (av 600 nm) on a substrate as template, followed by depositing a positively charged polyelectrolyte and gold colloids (av 17 nm) via the layer-by-layer (LbL) self-assembly technique, and finally by eliminating the PS monolayer. This gold coated polyelectrolyte film has a regular pattern of sharp edges, and those edges are composed of abundant polyelectrolyte. This heterogeneous surface is easily prepared and universal for site-selective absorption of nanoparticles (silver nanoparticles in this paper, av 45 nm). This surface-guided self-assembly is powerful for fabricating micro/nanostructures on the edges of prepatterns. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the products.     

Immobilizing shortened single-walled carbon nanotubes (SWNTs) on gold using a surface condensation method

We propose a surface condensation method for assembling single-walled carbon nanotubes (SWNTs) on gold. The as-prepared long and randomly tangled SWNTs were cut into short pipes by chemical oxidation, allowing the nanotubes to be terminated by carboxyl functionalities. A surface condensation reaction was then performed by immersing an amino self-assembled monolayer (SAM)-modified gold substrate into the dimethylformamide suspension of carboxylic nanotubes with the aid of dicyclohexylcarbodiimide condensation agent. Raman spectroscopy and atomic force microscopy (AFM) results show that a highly aligned assembly of SWNTs has been formed on gold, with the nanotubes standing on the surface stable enough for a long ultrasonication. In combination with the microcontact printing (muCP) technique, we have fabricated patterned nanotube assemblies using this surface condensation method. Moreover, we found that the "giant" carbon nanotubes tend to form bundles on an amino-terminating surface, likely following a nucleation-growth model.     

聚氨酯接枝多壁碳纳米管的制备及表征

采用两步法成功地将聚氨酯分子链以共价键连接到碳纳米管表面. 首先将聚丙烯酰氯通过与强酸氧化后多壁碳纳米管表面产生的羟基及少量羧基之间的化学反应共价接枝到碳纳米管表面; 然后将接枝到碳纳米管表面的聚丙烯酰氯与端羟基聚氨酯发生酯化反应, 实现了聚氨酯对碳纳米管的表面共价接枝. 采用傅里叶变换红外光谱(FTIR)、透射电镜(TEM)、扫描电镜(SEM) 和热重分析(TGA)等对接枝后的产物进行了表征, 结果表明, 聚氨酯已共价接枝到碳纳米管表面, 被接枝的聚合物的含量接近90%.     

Formation of the pore structure in xerogel films based on ultra-high-molecular-weight polyethylene and multiwall carbon nanotubes

The fundamental aspect of the pore structure formation in composite films based on ultra-high-molecular-weight polyethylene and multiwall carbon nanotubes were studied by IR spectroscopy, mercury porosimetry, scanning electron microscopy, and differential scanning calorimetry in relation to the degree of filling.     

Modification of multiwall carbon nanotubes by grafting from controlled polymerization of styrene: Effect of the characteristics of the nanotubes

Linear polystyrene chains were grown from the convex surface of two commercially available multiwall carbon nanotubes (MWCNTs) with similar diameter but different lengths. The MWCNTs were supplied from Bayer Material Science® (purity >95%, external diameter = 13–16 nm, length = 1–10 μm, denoted MWCNT_BMS⁹⁵) and FutureCarbon GmbH (purity >99%, external diameter = 15 nm, length = 5–50 μm, denoted MWCNT_FC⁹⁹). The MWCNTs were oxidized with nitric acid, consecutively reacted with thionyl chloride, glycol or poly(ethylene glycol), 2‐bromo‐2‐methylpropionyl bromide and finally with styrene under atom transfer radical polymerization (ATRP) conditions. The content of polystyrene grafted from the surface of the MWCNTs can be controlled by adjusting the molecular weight of the poly(ethylene glycol), the initiator concentration and the monomer to carbon nanotube weight ratio. Under comparable experimental conditions, a higher amount of polystyrene is grafted from the MWCNT_BMS⁹⁵ than from MWCNT_FC⁹⁹. The difference in dimensions and the state of aggregation of the carbon nanotubes influence the grafting from polymerization reactions, where relative shorter and tightly aggregated carbon nanotubes promote higher polymerizations yields than longer and less aggregated carbon nanotubes. The increase of the viscosity of the carbon nanotube dispersion decreases the polymer grafting content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1035–1046, 2010     

Adhesion of spherical polyelectrolyte brushes on mica: an in situ AFM investigation

We demonstrate that the adsorption of cationic spherical polyelectrolyte brushes (SPB) on negatively charged mica substrates can be controlled in situ by the ionic strength of the suspension. The SPB used in our experiments consist of colloidal core particles made of polystyrene. Long cationic polyelectrolyte chains are grafted onto these cores that have diameters in the range of 100 nm. These particles are suspended in aqueous solution with a fixed ionic strength. Atomic force microscopy (AFM) in suspension as well as in air was used for surface characterization. In pure water the polymer particles exhibit a strong adhesion to the mica surface. AFM investigations of the dry samples show that the particles occupy the identical positions as they did in liquid. They were not removed by the capillary forces within the receding water front during the drying process. The strong interaction between the particles and the mica surface is corroborated by testing the adhesion of individual particles on the dried surface by means of the AFM tip: after a stepwise increase of the force applied to the surface by the AFM tip, the polymer particles still were not removed from the surface, but they were cut through and remained on the substrate. Moreover, in situ AFM measurements showed that particles which adsorb under liquid in a stable manner are easily desorbed from the surface after electrolyte is added to the suspension. This finding is explained by a decreasing attractive particle-substrate interaction, and the removal of the particles from the surface is due to the significant reduction of the activation barrier of the particle desorption. All findings can be explained in terms of the counterion release force.     

Layer-by-Layer electrostatic self-assembly of polyelectrolyte nanoshells on individual carbon nanotube templates

Carbon nanotubes have been featured prominently in the nanotechnology research for some time, yet robust strategies for noncovalent chemical modification of the nanotube surface are still missing. Such strategies are essential for the creation of functional device architectures. Here, we present a new general procedure for carbon nanotube modification based on polyelectrolyte layer-by-layer assembly. We have built multilayer structures around individual carbon nanotube bridges by first modifying the nanotube surface with a pyrene derivative followed by layer-by-layer deposition of polyelectrolyte macroions on the nanotube. Transmission electron microscopy and scanning confocal fluorescence microscopy images confirm the formation of nanometer-thick amorphous polymer nanoshells around the nanotubes. These multilayer polyelectrolyte shells on individual carbon nanotubes introduce nearly unlimited opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent structures.     

Templating silica nanostructures on rationally designed self-assembled peptide fibers

Nature presents exquisite examples of templating hard, functional inorganic materials on soft, self-assembled organic substrates. An ability to mimic and control similar processes in the laboratory would increase our understanding of fundamental science, and may lead to potential applications in the broad arena of bionanotechnology. Here we describe how self-assembled, alpha-helix-based peptide fibers of de novo design can promote and direct the deposition of silica from silicic acid solutions. The peptide substrate can be removed readily through proteolysis, or other facile means to render silica nanotubes. Furthermore, the resulting silica structures, which span the nanometer to micrometer range, can themselves be used to template the deposition of the cationic polyelectrolyte, poly-(diallyldimethylammonium chloride). Finally, the peptide-based substrates can be engineered prior to silicification to alter the morphology and mechanical properties of the resulting hybrid and tubular materials.