Monitoring colloidal stability of polymer-coated magnetic nanoparticles using AC susceptibility measurements

Abstract

The application of the response of magnetic nanoparticles to oscillating magnetic fields to probe transitions in colloidal state and structure of polymer-coated nanoparticles is demonstrated. Cobalt ferrite nanoparticles with narrow size distribution were prepared and shown to respond to oscillating magnetic fields through a Brownian relaxation mechanism, which is dependent on the mechanical coupling between the particle dipoles and the surrounding matrix. These nanoparticles were coated with covalently-attached poly(N-isopropylacrylamide) (pNIPAM) or poly(N-isopropylmethacrylamide) (pNIPMAM) through free radical polymerization. The temperature induced transitions of colloidal suspensions of these nanoparticles were studied through a combination of differential scanning calorimetry (DSC), dynamic light scattering (DLS), and AC susceptibility measurements. In the pNIPAM coated nanoparticles excellent agreement was found for a transition temperature of ∼30 °C by all three methods, although the AC susceptibility measurements indicated aggregation which was not evident from the DLS results. Small-angle neutron scattering (SANS) results obtained for pNIPAM coated nanoparticles confirmed that aggregation indeed occurs above the lower critical transition temperature of pNIPAM. For the pNIPMAM coated nanoparticles DLS and AC susceptibility measurements indicated aggregation at a temperature of ∼33–35 °C, much lower than the transition temperature peak at 40 °C observed by DSC. However, the transition observed by DSC is very broad, hence it is possible that aggregation begins to occur at temperatures lower than the peak, as indicated by the AC susceptibility and DLS results. These experiments and observations demonstrate the possibility of using AC susceptibility measurements to probe transitions in colloidal suspensions induced by external stimuli. Because magnetic measurements do not require optical transparency, these methods could be applied even in concentrated or opaque systems, in which light scattering techniques encounter technical problems.