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<p> A recently developed surface grafting technique, surface-initiated atom transfer radical polymerization (ATRP), has the ability to directly graft polymer chains with controllable chain lengths, densities and functionalities from various kinds of surfaces. This thesis has two main focuses. First is to study the use of this technique in grafting monomers with special structures and functionalities. The other is to apply this technique to the modification of reactive metal surfaces. </p> <p> Both of fluorinated polymers and polyhedral oligomeric silsesquioxane (POSS)-containing polymers have very interesting properties. In this thesis, for the first time, a highly fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEMA) and a POSS-containing monomer, POSS-MA were successfully polymerized from silicon wafers by surface-initiated ATRP. This is also the first work to use this technique to graft polymers with bulky, rigid side groups. </p> <p> To achieve very high grafting density is a big challenge for surface-initiated ATRP. We designed a novel surface-attachable difunctional initiator, 11-(2,2-bis(2bromo-2-methylpropionyloxy methyl)propionyloxy) undecyltrichlorosilane. With its help, the grafting density of PTFEMA was almost doubled, from 0.48 to 0.86chains/nm2. This is so far the most effective method to increase the grafting density. </p> <p> Unlike other kinds of materials, the surfaces of metals are active in electrochemical and acid/base reactions and this reactivity complicates A TRP reactions. With the help of triethoxysilane-based initiator and mild Fe(II)/Fe(III) catalyst system, various acrylic polymers were successfully grafted from flat nickel and copper surfaces by surface-initiated ATRP. This work provided a convenient method to prepare functional polymer coatings with very stable adhesions to the metal surfaces. The same strategy can be extended to the surface modification of a shape-memory-alloy, nitinol. </p> <p> Metal nanoparticles were also modified by this technique. Polymer shells were grafted from nickel nanoparticles surfaces. After the polymer grafting, both of the dispersibility and dispersion stability of nickel nanoparticles in appropriate solvents were greatly improved. </p> / Thesis / Doctor of Philosophy (PhD)