Unmodified Silica Nanoparticles Research Articles

Mechanical properties of silica nanoparticle reinforced poly(ethylene 2, 6-naphthalate)

We added surface-modified silica nanoparticles to poly(ethylene 2,6-naphthalate) (PEN) to investigate their effect on the mechanical properties on the PEN nanocomposite material. The torque and total torque values of the composites decreased in the silica nanoparticle composites. The tensile modulus of the composites reinforced with unmodified silica nanoparticles increased upon increasing the silica content, while the tensile strength and elongation decreased accordingly. In contrast, stearic acid-modified, silica nanoparticle reinforced PEN composites exhibited an increase in elongation and a decrease in tensile modulus upon addition of the silica nanoparticles because the stearic acid that had adsorbed onto the surface of the silica nanoparticle in multilayers could act as a plasticizer during melt compounding. Stearic acid modification had a small effect on the crystallization behavior of the composites. We calculated theoretical values of the tensile modulus using the Einstein, Kerner, and Nielsen equations and compared these values with the experimental data obtained from the composites. The parameters calculated using the Nielsen equation and the Nicolais- Narkis model revealed that the interfacial adhesion between silica nanoparticles and the PEN matrix could be improved.

Fluorescence Anisotropy in Studies of Solute Interactions with Covalently Modified Colloidal Silica Nanoparticles

Time-resolved anisotropy decays of a fluorescent cationic solute, rhodamine 6G (R6G), in Ludox sols were measured to characterize the extent of the ionic binding of the probe to silica particles after modification of the surface with neutral or cationic silane coupling agents. The anisotropy decays provided direct evidence for distribution of the dye between the aqueous solution (picosecond decay component) and silica particles (nanosecond decay component and residual anisotropy component, which were attributed to the wobbling motion of dye on the silica surface and to the ionically bound probe, respectively). The dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Significant decreases in the degree of probe adsorption were obtained upon covalent modification of the silica with neutral or cationic silanes, with up to 80% of the probe being present in the aqueous solution in cases where the surface was coated with (3-aminopropyl)triethoxysilane. The addition of such agents also altered the fractional distribution between the nanosecond decay component and the residual anisotropy component in favor of the nanosecond component, indicative of weaker interactions between the dye and the modified surface (i.e., more wobbling motion). The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and should prove useful in characterization of new chromatographic stationary phases.

Monitoring Solute Interactions with Poly(ethylene oxide)-Modified Colloidal Silica Nanoparticles via Fluorescence Anisotropy Decay

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and suggest that this method should prove useful in characterization of new chromatographic stationary phases and nanocomposite materials.