Effect of grafted polymer species on particle monolayer structure at the air-water interface.

We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass substrate.

Colloidal crystallization of colloidal silica modified with ferrocenyl group-contained polymers in organic solvents.

Surface modification of colloidal silica with ferrocenyl-grafted polymer and colloidal crystallization of the particles in organic solvent were studied. Poly(methyl methacrylate-co-vinylferrocene)-grafted silica never formed colloidal crystals in polar solvent, such as acetone, acetonitrile, ethanol and N,N-dimethylformamide (DMF), while poly(methyl methacrylate-co-ferrocenyl acrylate)-grafted silica gave colloidal crystallization in DMF. The particles prepared by grafting of poly(N,N-dimethylacrylamide-co-vinylferrocene), with vinylferrocene (Vfc) mole fraction of 1/13 and 1/23, were observed to give the crystallization in ethanol and DMF over particle volume fraction of 0.058. Further, silica modified with copolymer of Vfc and N-vinyl-2-pyrrolidone, N-vinylcarbazole or N-isopropylacrylamide formed colloidal crystals in ethanol and DMF. Especially, poly(N-isopropylacrylamide-co-Vfc)-grafted silica, which was composed of the highest mole fraction of vinylferrocene, 1/3, afforded colloidal crystallization in ethanol over particle volume fraction of 0.053. Relatively high polar vinylferrocene copolymer grafting of silica resulted in colloidal polymerization in organic solvents.