Thermoreversible Hydroferrogels with Tunable Mechanical Properties Utilizing Block Copolymer Mesophases As Template

Abstract

Thermoreversible hydroferrogels (FGs) have been prepared via gelation of aqueous maghemite ferrofluids (FFs) using the triblock copolymer Pluronic P123 as gelator. In the investigated concentration range of 28-42 wt % P123, long-term stable homogeneous FGs can be prepared from FFs with a maximum maghemite content of 14 wt %. For higher FF concentrations up to 29 wt %, however, homogeneous FGs were formed only for gelator contents up to ca. 33 wt %. A combination of rheology and μ-DSC was applied as an alternative method to construct the P123 phase diagram, without the need for visual methods or scattering techniques. Using this procedure, we could show that maghemite nanoparticles can be effectively templated by the cubic and hexagonal P123 mesophases in a concentration range of 33-38 wt % P123 and FF concentrations up to 14 wt %, respectively. Most importantly, the phase behavior and the corresponding phase-transition temperatures of P123 were not significantly altered. As a result, the FGs show a reversible temperature-triggered transition from a cubic hard gel to a hexagonal gel, which is linked with a softening of the gel. Furthermore, this concept can be applied to template cobalt ferrite nanoparticle effectively, too. Magnetization experiments revealed that the superparamagnetic behavior of the maghemite nanoparticles, which show a Néel type relaxation, is not altered in the corresponding FGs. In contrast, FGs based on blocked cobalt ferrite nanoparticles show a hysteretic behavior, which indicates a strong mechanical coupling between the P123 mesophase and the magnetic nanoparticles.