Carbon covalent functionalization

Figure 5.10 Raman spectra (Kexc= 1064 nm) of PANI/SWNT composites obtained by electrochemical polymerization of aniline on a SWNT film in HCI 0.5 M. Curve 1 corresponds to the SWNT film Raman spectrum. Curves 2-4 and 6-8 show the evolution of the Raman spectrum after 25, 50, 75, 100, 150, and 300 cycles, respectively, carried out in the potential range (-200 +700) mV vs. SCE with a sweep rate of 100 mV s The dedoping of the PANI-salt-functionalized SWNT films (curves 4 and 8), as a result of the chemical reaction with NH4OH 1M solution, is illustrated in curves 5 and 9. (Reprinted with permission from Carbon, Covalent functionalization of single-walled carbon nanotubes by aniline electrochemical polymerization by M. Baibarac, I. Baltog, S. Lefrant et ah, 42, 15, 3143-3152. Copyright (2004) Elsevier Ltd)...

Direct consumption sugar, 23 450-451 Direct contact heat exchangers, 13 268 Direct cooler evaporators, 21 537 Direct-coupled plasma (DCF), 25 370 Direct covalent carbon nanotube functionalization, 17 54-55 Direct current (dc) diode sputtering, 24 730-731. See also dc sensing current... 

From an atomic configuration point of view, a nanotube can be divided into two parts that are generated by curvatures the end caps and sidewall. The end caps are close to the hemispherical fullerene and are curved in 2D, and the sidewall contains less-distorted carbon atoms and is curved in ID (Polizu et al., 2006). Owing to their specific curvatures, the chemical reactivity at the sidewall is significantly lower than that at the end caps The sidewall is thought to be inert and highly reactive agents are required for the covalent functionalization of CNT sidewalls (Wei et al., 2007). 

In order to overcome this drawback, there are two main approaches for the surface modification of carbon nanostructures that reoccur in the literature. The first one is covalent functionalization, mainly by chemical bonding of functional groups and the second one is noncovalent functionalization, mainly by physical interactions with other molecules or particles. Both strategies have been used to provide different physical and chemical properties to the carbon nanostructures. Those that will be presented here are only a few examples of the modifications that can be achieved in carbon nanostructure surfaces and composite fabrication. 

When the formation of covalent bonds is established between functional groups and a surface, a covalent or chemical functionalization is reached. The main characteristic of this type of functionalization is the change in the carbon hybridization from sp2 to sp3 [104]. Although this covalent functionalization provides the possibility to obtain a... 

Although there have been great advances in covalent functionalization of fullerenes to obtain surface-modified fullerene derivatives or fullerene polymers, the application of these compounds in composites still remains unexplored, basically because of the low availability of these compounds [132]. However, until now, modified fullerene derivatives have been used to prepare composites with different polymers, including acrylic [133,134] or vinyl polymers [135], polystyrene [136], polyethylene [137], and polyimide [138,139], amongst others. These composite materials have found applications especially in the field of optoelectronics [140] in which the most important applications of the fullerene-polymer composites have been in the field of photovoltaic and optical-limiting materials [141]. The methods to covalently functionalize fullerenes and their application for composites or hybrid materials are very well established and they have set the foundations that later were applied to the covalent functionalization of other carbon nanostructures including CNTs and graphene. 

A. Ghosh, K.V. Rao, R. Voggu, S. J. George, Non-covalent functionalization, solubilization of graphene and single-walled carbon nanotubes with aromatic donor and acceptor molecules, Chemical Physics Letters, vol. 488, pp. 198-201, 2010. 

A. 1.1. Covalently Functionalized Dendrimers Applied in a CFMR The palladium-catalyzed allylic substitution reaction has been investigated extensively in the preceding decades and provides an important tool for the formation of carbon—carbon and carbon—heteroatom bonds 14). The product is formed after attack of a nucleophile to an (f/ -allyl)Pd(II) species, formed by oxidative addition of the unsaturated substrate to palladium(0) (Scheme 1). To date several nucleophiles have been used, mostly resulting in the formation of carbon—carbon and... 

In many cases the potential application of single-walled carbon nanotubes is associated with solubility of this nanomaterial in different solvents. Unfortunately, nanotubes are poorly soluble in the most of organic solvents and are insoluble in water, and this fact especially hinders biological using SWNT. Weak solubility of SWNT is a result of substantial van der Waals attractions between nanotubes aggregated in bundles. To solve nanotubes in water without any covalent functionalization, a surfactant would be added into aqueous solution, and then this mixture is suspended by sonication. It is supposed that the sound wave splits bundles in aqueous solution. A surfactant in suspension adsorbed onto the nanotube surfaces precludes aggregation of nanotubes in bundles. 

Besides covalent functionalization of carbon nanotubes, non-covalent interaction between CNTs and polyurethane can also help fabricate uniform CNT dispersion nanocomposites. A dominant improvement in the dispersion of MWNTs in hyperbranched polyurethane (HBPU) matrix was found, and good solubility of... 

Another approach to covalently attach carbon nanotubes is based on the chemical modification of a PEEK matrix which allows further covalent interaction with functionalized carbon nanotubes. In 2007 Babaa et al. (40) proposed a route to covalently graft commercial MWCNTs by using this approach. The process initiates by dissolution of PEEK in concentrated H2S04, leading to functionalization yields of 70%. MWCNTs covalently functionalized with... 

Most of PVA/CNT composites are processed under the form of films. Generally, films are casted and dried from water-based PVA and nanotube dispersions. Different types of water-based dispersions have been used. Carbon nanotubes come from various production sources and can be covalently functionalized. The PVA molecular weight and hydrolysis rate can also be varied as well as the nanotube fraction. This is why comparisons between all the contributions in the literature can sometimes be difficult. Nevertheless some general and important features can still be deduced from all the studies reported on this topic. 

Figure 31 Representative reaction products obtained in the covalent functionalization of the carbon nanotubes. The preciusor acid functionality is distributed all around the tubes and concentrated at the open ends ( 1 - 3 mol%). For clarity, one substitution with n multiples is illustrated...

Secondly, however, the carbon nanotube may be covalently functionalized with monomer units, initiator molecules or crosslinking groups, which leads to a significantly better interaction with the matrix. 

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