Effects of particle size on the molecular orientation and birefringence of magnetic nanoparticles/polyimide composites

Size dependency of nanoparticles for birefringence and molecular orientation of nanocomposite films have been studied using a prism coupler and near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS). We synthesized two different sizes of magnetic nanoparticles, Ni0.6Zn0.4Fe2O4. The smaller ones were 6.1 ± 1.3 nm‐diameter nanoparticles showing superparamagnetism and the larger ones were 20.7 ± 6.1 nm‐diameter nanoparticles showing ferrimagnetism. To make nanocomposites, we incorporated these particles into poly(N,N′‐bis(phenoxyphenyl)pyromellitimide) (PMDA‐ODA PI). From the prism coupler study, pristine PI without nanoparticles had higher out‐of‐plane birefringence, which indicated high in‐plane orientation of polyimide. However, the birefringence of PI nanocomposites decreased with the increase of particle content. The birefringence of PI nanocomposite with small nanoparticles was smaller than that of PI nanocomposite with large nanoparticles. The birefringence of PI nanocomposite with 1 wt % of small nanoparticles was reduced to almost half of that of pristine PI due to the decreased orientation of PI molecules. NEXAFS spectra of N K‐edge were the same as the birefringence results. Imide and phenyl rings of pristine PI aligned more parallel to the in‐plane direction, but those of PI with nanoparticles aligned less parallel to the in‐plane direction.