Magnetic field induced uniaxial alignment of the lyotropic liquid-crystalline PMMA-grafted Fe3O4 nanoplates with controllable interparticle interaction

Abstract

Magnetite (Fe₃O₄) nanoplates with a hexagonal platelet shape were synthesized by two steps: hydrothermal synthesis of iron(III) oxide (α-Fe₂O₃) nanoplates followed by wet chemical reduction of the α-Fe₂O₃ nanoplates. Then, poly(methyl methacrylate) (PMMA) chains were grafted onto the surface of the hexagonal Fe₃O₄ nanoplates (F) via surface-initiated atom transfer radical polymerization (SI-ATRP), which ensures dispersion stability in organic solvents and ionic liquids. After mixing with 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Emim⁺][NTf₂⁻]), a representative ionic liquid, the resulting PMMA-modified F were found to show good lyotropic liquid-crystalline (LC) behaviour in [Emim⁺][NTf₂⁻] and to exhibit a fast response to the application of an external magnetic field. Ultrasmall-angle synchrotron X-ray scattering (USAXS) measurements verified that the PMMA chain length, the weight ratio of the ionic liquid and the external magnetic field could significantly influence the interparticle distance (I_D) of the PMMA-modified F in [Emim⁺][NTf₂⁻]. In particular, the lyotropic LC phase could be assigned as a nematic phase with a columnar alignment. In addition, the PMMA-modified F maintained a uniaxially aligned nematic columnar structure along the magnetic field direction. Our study also determined the mechanism for the special alignment of the PMMA-modified F under an external magnetic field by analysing the growth axis, the easy magnetic axes, and the interparticle distance of F. The results suggested that the special alignment of the PMMA-modified F was affected by the interparticle interaction caused by the PMMA long chains on F under the magnetic field. Furthermore, the present study revealed that PMMA-modified F exhibited a new magnetic field responsive behaviour that led not only to the formation of a uniaxial alignment structure but also to control of I_D with the help of the PMMA soft corona under the application of a magnetic field. These features could prove to be a promising advance towards novel applications of magnetic nanoparticles (NPs), such as functional magnetic fluids, rewritable magnetic switching devices, and smart magneto-electrochemical nanosensors.