Effects of organic polymer addition in magnetite synthesis on the crystalline structure

Magnetite (Fe3O4) nanoparticles and magnetite-based inorganic-organic hybrids are attracting attention in biomedical fields as thermoseeds for hyperthermia and a contrast medium in magnetic resonance imaging. Size control of Fe3O4 thermoseeds is important as the particle size affects the heat generation properties. Fe3O4 can be easily synthesized via aqueous processes and the presence of organic substances during synthesis can affect the size and crystalline phase of the Fe3O4 formed. In this study, various polymers with different functional groups and surface charges were added to the precursor solution of Fe3O4 to clarify the relationship between the chemical structure of the organic substances and the crystal structure of Fe3O4. At first, coexistence effects of the organic substances in the solutions were clarified. As a result, crystalline Fe3O4 was precipitated even after addition of neutral polyethylene glycol and cationic poly(diallyldimethylammonium chloride). The poly(sodium-4-styrene sulfonate) addition significantly decreased the particle size, while polyacrylic acid addition inhibited Fe3O4 nucleation to afford an amorphous phase. These differences were related to the ease of complex formation from iron ions and coexisting organic polymers. In order to clarify this assumption, a modified experimental procedure was applied for the polyacrylic acid. Namely, the iron oxide precipitation by the NaOH solution was followed by the polyacrylic acid addition. Notably, Fe3O4 nucleation was not inhibited. Hence, the size and crystalline phase of the iron oxide prepared by the aqueous process were drastically affected by organic polymers.