Polymer surfaces, inducing modification

This area of research is still at its beginning and many aspects are not resolved. This includes in particular the structure and conformation of polymers at an interface as well as the modification of polymer dynamics by the interface. We have given several examples of the potential of surface and interface analytical techniques. They provide information on surface roughness, surface composition, lateral structure, depth profiles, surface-induced order and interfacial mixing of polymers on a molecular and sometimes subnanometer scale. They thus offer a large variety of possible surface and interface studies which will help in the understanding of polymer structure and dynamics as it is modified by the influence... 

Radiation Treatment NVP, 2-hydroxyethylmethacrylate (HEMA), and acrylamide (AAm) have been grafted to the surface of ethylene-propylene-diene monomer (EPDM) rubber vulcanizates using the radiation method (from a Co 7 source) to alter surface properties such as wettability and therefore biocompatibility [197]. Poncin-Epaillard et al. [198] have reported the modification of isotactic PP surface by EB and grafting of AA onto the activated polymer. Radiation-induced grafting of acrylamide onto PE is very important... 

Laser ablation of polymer films has been extensively investigated, both for application to their surface modification and thin-film deposition and for elucidation of the mechanism [15]. Dopant-induced laser ablation of polymer films has also been investigated [16]. In this technique ablation is induced by excitation not of the target polymer film itself but of a small amount of the photosensitizer doped in the polymer film. When dye molecules are doped site-selectively into the nanoscale microdomain structures of diblock copolymer films, dopant-induced laser ablation is expected to create a change in the morphology of nanoscale structures on the polymer surface. 

Polymer films change their properties during ion implantation [25-29]. Carbonization mentioned above is one of the ion beam induced modification techniques for polymer surfaces. 

The materials analyzed were blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in various ratios. The two components are miscible in all proportions at ambient temperature. The photooxidation mechanisms of the homo-polymers PS and PVME have been studied previously [4,7,8]. PVME has been shown to be much more sensitive to oxidation than PS and the rate of photooxidation of PVME was found to be approximately 10 times higher than that of PS. The photoproducts formed were identified by spectroscopy combined with chemical and physical treatments. The rate of oxidation of each component in the blend has been compared with the oxidation rate of the homopolymers studied separately. Because photooxidative aging induces modifications of the surface aspect of the material, the spectroscopic analysis of the photochemical behavior of the blend has been completed by an analysis of the surface of the samples by atomic force microscopy (AFM). A tentative correlation between the evolution of the roughness measured by AFM and the chemical changes occurring in the PVME-PS samples throughout irradiation is presented. 

The variation of the chemical composition of the substrate (not realized in a continuous tunable fashion) leads to drastic modifications of surface fields exerted by the polymer/substrate (i.e.,II) interface [94,97, 111, 114,119]. The substrate may, for instance, change contact angles with the blend phase from zero to a finite value. As a result the final morphology changes from a layered structure of Fig. 5b into a column structure of Fig. 5c [94,114]. On the other hand our very recent experiment [16] has shown that the surface fields are temperature dependent. Therefore, although it has been shown that surface-induced spinodal decomposition yields coexisting bilayer structure (Fig. 5b) at a singular temperature [114,115], that in principle may not be necessary true for other temperatures. This motivated our comparative studies [107] on coexistence compositions determined with two techniques described above interfacial relaxation and spinodal decomposition. 

During the last decade, processing of polymers has become an important field of applied and fundamental research [48]. One of the most important fields is laser ablation involving various techniques and applications. Laser ablation is used as an analytical tool for MALDI (matrix-assisted laser de-sorption/ionization) [28, 29] and LIBS (laser-induced breakdown spectroscopy) [49] or as a preparative tool for PLD (pulsed laser deposition) of inorganic materials [37] and of synthetic polymer films [50, 51]. Another application is surface modification of polymers [52] if low fluences are applied, the polymer surface can be either chemically modified to improve adhesion... 

The previously discussed principles of grafting-to and grafting-from can also be applied for the modification of polymer surfaces with polymer brushes. However, the binding of linkers and polymerization initiators to polymer surfaces is not as straightforward as it is for oxidic inorganic materials. Thus, dedicated pretreatments are usually necessary. These may include rather harsh reaction conditions due to the chemical inertness of many polymers (see Chapter 3). Alternatively, radiation treatment of polymers (to form radicals) followed by exposure to air may be used to form peroxides and hydroperoxides, which can be directly used as initiators for thermally or ultraviolet-induced graft polymerizations [16,17] (see Chapter 2). 

As effective as these surface modification processes might be, they present limitations in terms of the extent to which the surfaces of polymers can be modified. Plasma-induced grafting offers another method by which chemical functional groups can be incorporated. In this process, free radicals are generated on the surface of a polymer through the use of an inert gas plasma. Because of the nonreactive nature of the inert gas plasma, surface chemical modification of the polymer does not occur. If the polymer surface that has been... 

A wide variety of natural and synthetic materials have been used for biomedical applications. These include polymers, ceramics, metals, carbons, natural tissues, and composite materials (1). Of these materials, polymers remain the most widely used biomaterials. Polymeric materials have several advantages which make them very attractive as biomaterials (2). They include their versatility, physical properties, ability to be fabricated into various shapes and structures, and ease in surface modification. The long-term use of polymeric biomaterials in blood is limited by surface-induced thrombosis and biomaterial-associated infections (3,4). Thrombus formation on biomaterial surface is initiated by plasma protein adsorption followed by adhesion and activation of platelets (5,6). Biomaterial-associated infections occur as a result of the adhesion of bacteria onto the surface (7). The biomaterial surface provides a site for bacterial attachment and proliferation. Adherent bacteria are covered by a biofilm which supports bacterial growth while protecting them from antibodies, phagocytes, and antibiotics (8). Infections of vascular grafts, for instance, are usually associated with Pseudomonas aeruginosa Escherichia coli. Staphylococcus aureus, and Staphyloccocus epidermidis (9). 

Opsonization-induced polyplex disassembly during systemic circulation also represents a barrier to efficient cellular targeting. The instability of electrostatic polyelectrolyte assemblies means polyplexes are susceptible to polyanion displacement after cellular or chemical interaction, such as with erythrocytes or heparin, respectively. Increased levels of free polycations in the blood, and in particular high MW and nondegradable polymers, could induce adverse effects if excreted or broken down. However, there are numerous reports where surface modification of the polyplex with hydrophilic polymers leads to steric stability with reduction in disassembly during systemic circulation. " ... 

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