Ryosuke Matsuno

Precise surface structure control of inorganic solid and metal oxide nanoparticles through surface-initiated radical polymerization

Abstract Surface-initiated radical polymerization was carried out in order to modify the surface of inorganic solid and metal oxide nanoparticles. Novel (inorganic nanoparticles/polymer) nanocomposites were prepared through a direct polymer grafting reaction from the surfaces of magnetite (Fe3O4) (d ¼ 10 and 25 nm) and titanium oxide (TiO2) (d ¼ 15 nm) nanoparticles. The initiator for nitroxide-mediated radical polymerization with a phosphoric acid group was chemisorbed onto the nanoparticles and gave controlled polystyrene (PS) and poly(3-vinylpyridine) (P3VP) graft layers on their surfaces. The PS- and P3VP-modified nanoparticles were finely dispersed in organic solvents, whereas protonated P3VP-modified magnetite nanoparticles were dispersed in aqueous phase. The fine dispersion of nanoparticles in the polymer matrix was confirmed by microscopic observation. In order to realize tribological control, atom transfer radical polymerization of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate was also carried out from an immobilized initiator on a flat silicon wafer, resulting in a high-density polymer brush that was subsequently converted to a hydrophilic polymer brush consisting of 2,3-dihyroxypropyl methacrylate units. The poly(2,3-dihydroxypropyl methacrylate) brush-immobilized surface showed a low dynamic friction coefficient in water due to the highly stable hydrophilicity.

Phase selective preparations and surface modifications of spherical hollow nanomagnets

We carried out the phase selective preparations of hollow spheres of ccp- and hcp-Co, Co3O4, α-Fe, Fe3O4 and α-Fe2O3 with a diameter of ca. 600 nm and a shell thickness of 40 nm, using polystyrene (PS)-bead templates. The 600 nm PS beads were uniformly coated with cobalt or iron hydroxides by means of a homogeneous precipitation method. These cobalt-salt/PS hybrid particles were calcined in air at 400 °C and were transformed into Co3O4 hollow spheres. The hcp-Co hollow spheres were obtained by a reduction reaction of the Co3O4 particles under a stream of a 1 ∶ 1 mixed gas of H2 and N2 at 400 °C; in contrast, the ccp-Co hollow spheres were obtained by the calcination of the parent cobalt-salt/PS particles under H2–N2 at 400 °C. Hollow spheres of Fe3O4 and α-Fe2O3 were selectively prepared by calcination of iron-salt/PS particles at 400–500 °C in two different atmospheres, namely under H2–N2 and in air, respectively. Furthermore, the α-Fe2O3 particles were reduced into α-Fe under H2–N2 at 350 °C without any changes in morphology. These spheres were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) analyses. Magnetic measurements revealed a significant temperature dependence of the coercive field for the Fe3O4 (magnetite) particles, whereas the magnetic properties of the other particles were generally similar to those of the corresponding bulk samples. Surface chemical modifications were carried out on the Fe3O4 hollow spheres; the surfaces were grafted with poly(4-N-methylvinylpyridinium) brushes. This treatment was found to induce good dispersibility in water.