Physical surface modification interactions

Surfaces are investigated with surface-sensitive teclmiques in order to elucidate fiindamental infonnation. The approach most often used is to employ a variety of techniques to investigate a particular materials system. As each teclmique provides only a limited amount of infonnation, results from many teclmiques must be correlated in order to obtain a comprehensive understanding of surface properties. In section A 1.7.5. methods for the experimental analysis of surfaces in vacuum are outlined. Note that the interactions of various kinds of particles with surfaces are a critical component of these teclmiques. In addition, one of the more mteresting aspects of surface science is to use the tools available, such as electron, ion or laser beams, or even the tip of a scaiming probe instrument, to modify a surface at the atomic scale. The physics of the interactions of particles with surfaces and the kinds of modifications that can be made to surfaces are an integral part of this section. 

Energetic particles interacting can also modify the structure and/or stimulate chemical processes on a surface. Absorbed particles excite electronic and/or vibrational (phonon) states in the near-surface region. Some surface scientists investigate the fiindamental details of particle-surface interactions, while others are concerned about monitormg the changes to the surface induced by such interactions. Because of the importance of these interactions, the physics involved in both surface analysis and surface modification are discussed in this section. 

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. 

In most practical uses of polymeric particles, their surfaces play a very important role by taking part in interfacial interactions such as recognition, adsorption, catalytic reactions, etc. When we want to use polymer particles, we first check whether the chemical and physical structures of the surfaces meet the purpose. If some of them do not satisfy the criteria, we may seek other particles or try to modify the existing particles. This chapter mainly deals with the modification of surface of existing particles. In addition to chemical modification of particle surfaces, modification of the morphology of particles is also described. 

There are two types of surface modifications for CNTs noncovalent interactions (Figure 6.54) and covalent sidewall (Figure 6.55) or defect-sitet (Figure 6.56) functionalization.Both methods, as well as physical techniques such as sonica-tion, are successful in separating individual SWNTs from bundles - a process known as exfoliation. In general, it is most desirable to incorporate isolated SWNTs in a composite rather than bundles, since the latter features poor intertube interactions resulting in a lower overall strength - especially at low CNT concentrations. 

Surface thermodynamic considerations can be helpful in an understanding of the complex phenomena which occur in supported metal catalysts. Indeed, the physical and chemical interactions between metal, substrate and atmosphere lead to wetting and spreading phenomena (of the active catalyst over the substrate and of the substrate over the metal) which are relevant for the physical (sintering, redispersion) as well as chemical (suppression of chemisorption, modification of selectivity, enhanced activity) manifestations of supported metal catalysts. 

Due to the nature of carbon materials, the presentation of representative methods for surface derivatization will follow an approach different from that described in the preceding section, which is based on the spatial target site where physical-chemical modification can take place (1) immobilization performed at edges and/or ends and defects of graphitic sheets, (2) immobilization onto the graphene sheets, and (3) exclusively for CNTs we present some examples of endohedral encapsulation of metal complexes. For the first two cases, covalent bonding and noncovalent interactions can occur directly between the transition metal complex and carbon supports or via spacers grafted to the carbon surface. 

Bioactive molecules can be immobilized on polymeric surfaces by covalent chemical attachment or physical adsorption [251]. Solid polymer surfaces with reactive functional groups (OH, NH, COOH, SH, and CHCH ) present an opportunity for covEdent conjugation with biomolecules either directly or via a spacer linker [251]. Relatively inert polymers can also be treated with surface modification techniques to introduce reactive functional groups and allow chemical functionalization with desired biochemical moieties [251], Alternatively, biomolecules can also be physically immobilized on polymeric surfaces via van der Waal forces, affinity binding, or electrostatic interaction [251]. Notably, these biomolecules must be presented on the material surfaces with stabilized conformations and correct orientations to preserve their bioactivity [252-255]. 

---