Miroslav Mrlik

Electrorheological properties of suspensions of hollow globular titanium oxide/polypyrrole particles

Hollow globular clusters of titanium oxide (TiO2) nanoparticles were synthesized by a simple hydrothermal method. The prepared particles were consequently coated by in situ polymerization of conductive polymer polypyrrole (PPy) to obtain novel core–shell structured particles as a dispersed phase in electrorheological (ER) suspensions. The X-ray diffraction analysis and scanning electron microscopy provided information on particle composition and morphology. It appeared that PPy coating improved the compatibility of dispersed particles with silicone oil which results in higher sedimentation stability compared to that of mere TiO2 particles-based ER suspension. The ER properties were investigated under both steady and oscillatory shears. It was found that TiO2/PPy particles-based suspension showed higher ER activity than that of mere TiO2 hollow globular clusters. These observations were elucidated well in view of their dielectric spectra analysis; a larger dielectric loss enhancement and faster interfacial polarization were responsible for a higher ER activity of core–shell structured TiO2/PPy-based suspensions. Investigation of changes in ER properties of prepared suspensions as a function of particles concentration, viscosity of silicone oil used as a suspension medium, and electric field strength applied was also performed.

Improved thermooxidation and sedimentation stability of covalently-coated carbonyl iron particles with cholesteryl groups and their influence on magnetorheology

Sedimentation of particles in magnetorheological suspensions represents a crucial problem that concerns their efficient long-term application in practice. Prepared carbonyl iron (CI) microparticles coated with a low density substance, cholesteryl chloroformate, via a two-step reaction and immersed in silicone oil, exhibit three positive aspects: (1) the CI particle modification increased the compatibility between the particles and the silicone oil resulting in improved long-term stability (reduction in sedimentation); (2) the coating provided the particles with enhanced thermal stability in the oxygen atmosphere; and (3) rheological measurements proved a promising magnetorheological performance at different particle weight fractions.

The Electrorheological Behavior of Suspensions Based on Molten-Salt Synthesized Lithium Titanate Nanoparticles and Their Core–Shell Titanate/Urea Analogues

This paper concerns the preparation of novel electrorheological (ER) materials using microwave-assisted synthesis as well as utilizing a suitable shell-providing system with enhanced ER performance. Lithium titanate nanoparticles were successfully synthesized, and their composition was confirmed via X-ray diffraction. Rheological properties were investigated in the absence as well as in the presence of an external electric field. Dielectric properties clarified the response of the particles to the application of an electric field. The urea-coated lithium titanate nanoparticle-based suspension exhibits higher ER performance in comparison to suspensions based on bare particles.

Novel synthesis of core–shell urchin-like ZnO coated carbonyl iron microparticles and their magnetorheological activity

The overall stability (thermo-oxidation, sedimentation) of MR suspensions is a crucial problem decreasing their potential applicability in real life. In this study the unique functional coating of carbonyl iron (CI) particles with ZnO structures was presented in order to develop a new MR suspension based on the core–shell ZnO/CI urchin-like dispersed particles. The two-step synthesis provides the suitable core–shell particles with improved sedimentation and also thermo-oxidation stability. Moreover, due to the enhanced sedimentation stability core–shell based suspensions exhibit higher values of the yield stress than those of bare CI based suspensions at 20 wt% particle concentration. The suspension with 60 wt% particle concentration reaches values of the yield stress around 2.2 kPa at 272 mT. The excellent MR efficiency of the core–shell ZnO/CI based suspension at elevated temperatures was observed. Finally, the dimorphic particle based suspension was prepared when the ratio between the carbonyl iron and core–shell urchin-like particles was 1 : 1. The highest yield stress was obtained in the case of a dimorphic particle-based suspension due to the good magnetic properties of the bare carbonyl iron and mechanical gripping between core–shell ZnO/CI urchin-like particles.

A facile controllable coating of carbonyl iron particles with poly(glycidyl methacrylate): a tool for adjusting MR response and stability properties

This study is focused on the controllable coating of the carbonyl iron (CI) particles widely applied in magnetorheology. These particles were grafted with poly(glycidyl methacrylate) (PGMA) with narrow polydispersity via surface-initiated atom transfer radical polymerization. Two types of core–shell particles differing in molecular weights of grafted polymer chains were synthesized. The effect of shell thickness on the thermo-oxidation stability of particles as well as the sedimentation stability of their silicone oil suspensions was evaluated. The successful coating process was confirmed by Fourier transform infrared spectroscopy and energy-dispersive spectrometry. The differences in the magnetic properties of bare and coated CI particles were clarified through vibrating sample magnetometry. Due to the controllable length of the PGMA grafts, the magnetic properties remain almost the same as those for bare CI. The magnetorheological (MR) behavior of silicone oil suspensions containing 60 wt% of bare CI particles as well as PGMA-coated analogues was investigated in the absence and in the presence of various magnetic field strengths, demonstrating the negligible impact of surface modification on final MR performance. Thus, the grafting of the particles with PGMA negligibly affected magnetic properties but considerably enhanced thermo-oxidation and sedimentation stabilities. Finally, a novel tensiometric method for sedimentation stability measurements of MR suspensions was successfully implemented.

A tertiary amine in two competitive processes: reduction of graphene oxide vs. catalysis of atom transfer radical polymerization

Electrically conductive graphene oxide–polystyrene hybrids (GO–PS) were prepared by reduction of graphene oxide (GO) in one step during covalent modification of graphene oxide surface using surface-initiated atom transfer radical polymerization (SI-ATRP) of styrene. The reduction of the GO surface was proven by Raman spectroscopy, electrical conductivity measurements, thermogravimetric analysis and X-ray photoelectron spectroscopy. Electrical conductivity of the synthesized GO–PS particles increased in eight orders of magnitude, depending on the polymerization period. Detailed studies were performed to determine that the tertiary amine, such as N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA), used in SI-ATRP as a ligand complexing copper catalyst, was responsible for the GO surface reduction. It was shown that due to participation of PMDETA in reduction of graphene oxide, the ATRP in the presence of GO can proceed only above a certain PMDETA–GO ratio.

The chemical stability and cytotoxicity of carbonyl iron particles grafted with poly(glycidyl methacrylate) and the magnetorheological activity of their suspensions

Carbonyl iron (CI) particles were grafted with poly(glycidyl methacrylate) (PGMA) using atom transfer radical polymerization. Compact coating of PGMA largely improved the chemical stability of the particles in an acid environment and thus reduced the common drawback of bare CI particles. Furthermore, due to possible medical applications of CI-polymer systems for magnetic drug targeting, an in vitro cytotoxicity test was performed using an NIH/3T3 cell line. The cell viability was evaluated by spectrometric assay (MTT). The results show that the prepared particles are not cytotoxic. Moreover, bare CI particles as well as synthesized core–shell particles were suspended in silicone oil, and the rheological behavior of MR suspensions was investigated in controlled shear rate mode under various magnetic field strengths. Dynamic yield stress as a measure of the rigidity of the created internal structures of the suspensions was determined using the Herschel–Bulkley model, which provided a reasonably good fit for rheological data. MR suspensions of PGMA-coated particles exhibited only slightly decreased yield stresses due to their negligibly-affected magnetic performance.

A rheological evaluation of steady shear magnetorheological flow behavior using three-parameter viscoplastic models

Knowledge of the complicated flow characteristics of magnetorheological (MR) suspensions is necessary for simulations, calculations in engineering processes, or designing new devices utilizing these systems. In this study, we employed three constitutive equations (three-parameter models) for an evaluation of steady shear behavior of MR suspensions. The predictive/fitting capabilities of the Robertson–Stiff (R–S) model were compared with the commonly used Herschel–Bulkley (as a reference) and the Mizrahi–Berk models. The appropriateness of the models was examined using rheological data for diluted as well as concentrated MR systems. The effect of magnetic field strength on model fitting capabilities was also investigated. The suitability of the individual models was evaluated by observing correlation coefficient, sum of square errors, and root mean square errors. A statistical analysis demonstrated that the best fitting capabilities were exhibited by the R–S model, while others provided less accurate fits ...

Magnetorheological suspensions based on modified carbonyl iron particles with an extremely thin poly(n-butyl acrylate) layer and their enhanced stability properties

This study is focused on the modification of magnetic carbonyl iron (CI) particles with a thin polymer shell utilizing the atom-transfer radical polymerization (ATRP) technique, enabling control of the molecular weight and polydispersity of the final grafted polymer chains on the surface of CI particles and therefore also allowing tuning of the magnetorheological (MR) performance as well as stability properties (chemical, sedimentation). Hence, the bare CI particles were coated with a poly(butyl acrylate) (PBA) shell by the ATRP technique. The polymerization procedure of polymer grafting on the surface of the CI particles was characterized by gel permeation chromatography and nuclear magnetic resonance. The presence of the PBA chain on the CI particles was confirmed by Fourier infrared spectroscopy and energy dispersive spectroscopy. A saturation magnetization analysis using vibrating sample magnetometer proved that a thin polymer shell negligibly affects their magnetic properties, and data fit into the Jiles–Atherton model allowed the finite magnetization saturation for both bare CI and CI-PBA particles to be obtained. Furthermore, it was proved that a thin PBA coating provides sufficiently enhanced chemical and sedimentation stability properties for such a system, while the MR performance investigated using a rotational rheometer was affected negligibly. Finally it can be stated that a controllable coating performed via the ATRP technique is a useful tool to significantly improve stability properties, while the MR performance maintains values suitable for real-life applications.

The Impact of Polymer Grafting from a Graphene Oxide Surface on Its Compatibility with a PDMS Matrix and the Light-Induced Actuation of the Composites

Poly(dimethyl siloxane) (PDMS)-based materials with improved photoactuation properties were prepared by the incorporation of polymer-grafted graphene oxide particles. The modification of the graphene oxide (GO) surface was achieved via a surface initiated atom transfer radical polymerization (SI ATRP) of methyl methacrylate and butyl methacrylate. The modification was confirmed by thermogravimetric analysis, infrared spectroscopy and electron microscopy. The GO surface reduction during the SI ATRP was investigated using Raman spectroscopy and conductivity measurements. Contact angle measurements, dielectric spectroscopy and dynamic mechanical analyses were used to investigate the compatibility of the GO filler with the PDMS matrix and the influence of the GO surface modification on its physical properties and the interactions with the matrix. Finally, the thermal conductivity and photoactuation properties of the PDMS matrix and composites were compared. The incorporation of GO with grafted polymer chains, especially poly(n-butyl methacrylate), into the PDMS matrix improved the compatibility of the GO filler with the matrix, increased the energy dissipation due to the improved flexibility of the PDMS chains, enhanced the damping behavior and increased the thermal conductivity. All the changes in the properties positively affected the photoactuation behavior of the PDMS composites containing polymer-grafted GO.