Atom Transfer Radical Polymerization of Pyrrole-Bearing Methacrylate for Production of Carbonyl Iron Particles with Conducting Shell for Enhanced Electromagnetic Shielding.

The conducting polymer poly(2-(1H-pyrrole-1-yl)ethyl methacrylate (PPEMA) was synthesized by conventional atom transfer radical polymerization for the first time from free as well as surface-bonded alkyl bromide initiator. When grafted from the surface of carbonyl iron (CI) a substantial conducting shell on the magnetic core was obtained. Synthesis of the monomer as well as its polymer was confirmed using proton spectrum nuclear magnetic resonance (1H NMR). Polymers with various molar masses and low dispersity showed the variability of this approach, providing a system with a tailorable structure and brush-like morphology. Successful grafting from the CI surface was elucidate by transmission electron microscopy and Fourier-transform infrared spectroscopy. Very importantly, thanks to the targeted nanometer-scale shell thickness of the PPEMA coating, the magnetization properties of the particles were negligibly affected, as confirmed using vibration sample magnetometry. Smart elastomers (SE) consisting of bare CI or CI grafted with PPEMA chains (CI-PPEMA) and silicone elastomer were prepared and dynamic mechanical properties as well as interference shielding ones were investigated. It was found that short polymer chains grafted to the CI particles exhibited the plasticizing effect, which might be interesting from the magnetorheological point of view, and more interestingly, in comparison to the neat CI-based sample, it provided enhanced electromagnetic shielding of nearly 30 dB in thickness of 500 µm. Thus, SE containing the newly synthesized CI-PPEMA hybrid particles also exhibited considerably enhanced damping factor and proper mechanical performance, which make the material highly promising from various practical application points of view.

Magnetorheological fluids based on core-shell carbonyl iron particles modified by various organosilanes: synthesis, stability and performance.

Although smart materials, specifically magnetorheological (MR) fluids, have shown remarkable practical importance, their drawbacks such as an aggregation of magnetic fillers, insufficient compatibility with the carrier liquid, low resistance to corrosion and poor sedimentation stability still cause severe limitations for their broader utilization. To address this challenge, our study presents a facile concept for the coating of magnetic particles, leading to their enhanced utility properties and sufficient MR performance. This concentrates on the coating of magnetic carbonyl iron (CI) particles with a thin modifying layer as a surface shell utilizing four organosilanes; tetraethoxysilane, (3-aminopropyl)triethoxysilane, bis[3(trimethoxysilyl)propyl]amine and vinyltrimethoxysilane. Characterization of the modified particles and their suspensions was examined using various methods. XPS analysis confirmed the successful particle modification, while the surface free energy was evaluated by tensiometric measurements reflecting the better compatibility of particles with the dispersing medium. The lowest surface free energy possessed particles modified with (3-aminopropyl)triethoxysilane. The magnetization of the modified core-shell particles was not negatively affected by the organosilanes layer present on the particles resulting in comparable MR performance of the systems based on pure CI particles and their modified analogues as was proved by the fitting of the corresponding flow curves by the Robertson-Stiff model. Moreover, the modification of the particles improved their thermo-oxidation stability and chemical stability investigated via thermogravimetric analysis and acidic tests, respectively. Finally, the sedimentation stability of the modified particle-based systems expressed as a weight gain measured using a tensiometer device was enhanced in comparison with the pure CI particle-based system, which can be very positive in the intended applications.