Ferronematic Co(II) Complex: An Active Filler for Magnetically Actuated Soft Materials.

Ferronematics that are generally based on nematic liquid crystals (LCs) doped with magnetic nanoparticles, synergistically taking advantage of the anisotropic and flow characteristics of the nematic host and the magnetic susceptibility of the dopant, have powerful applications as magnetically actuated soft materials. In this work, a Co(II) complex, which alone presents both characteristics, is built with a salen-type ligand 3,5-dichlorosubstituted at the aromatic nuclei and has a tetramethyldisiloxane spacer, which makes it one of the few metallomesogens containing this structural motif. Paramagnetic crystals, through heat treatment above 110 °C, change into magnetic nematic LCs. Applying a perpendicular magnetic field of 50 mT, the nematic droplets align two by two through dipole-dipole interactions. By incorporating it into a silicone matrix consisting mainly of polydimethylsiloxane, a 3D printable ink is formulated and crosslinked under various shapes. In this environment, the cobalt complex is stabilized in an LC state at room temperature and, due to its anisotropy, facilitates the mechanical response to magnetic stimuli. The resulting objects can be easily manipulated on fluid or rough surfaces using external magnetic fields, behave like magnets by themselves, and show reversible locomotion.

All-Polymer Piezo-Composites for Scalable Energy Harvesting and Sensing Devices.

Silicone elastomer composites with piezoelectric properties, conferred by incorporated polyimide copolymers, with pressure sensors similar to human skin and kinetic energy harvester capabilities, were developed as thin film (<100 micron thick) layered architecture. They are based on polymer materials which can be produced in industrial amounts and are scalable for large areas (m2). The piezoelectric properties of the tested materials were determined using a dynamic mode of piezoelectric force microscopy. These composite materials bring together polydimethylsiloxane polymers with customized poly(siloxane-imide) copolymers (2−20 wt% relative to siloxanes), with siloxane segments inserted into the structure to ensure the compatibility of the components. The morphology of the materials as free-standing films was studied by SEM and AFM, revealing separated phases for higher polyimide concentration (10, 20 wt%). The composites show dielectric behavior with a low loss (<10−1) and a relative permittivity superior (3−4) to pure siloxane within a 0.1−106 Hz range. The composite in the form of a thin film can generate up to 750 mV under contact with a 30 g steel ball dropped from 10 cm high. This capability to convert a pressure signal into a direct current for the tested device has potential for applications in self-powered sensors and kinetic energy-harvesting applications. Furthermore, the materials preserve the known electromechanical properties of pure polysiloxane, with lateral strain actuation values of up to 6.2% at 28.9 V/µm.

From Amorphous Silicones to Si-Containing Highly Ordered Polymers: Some Romanian Contributions in the Field.

Polydimethylsiloxane (PDMS), in spite of its well-defined helical structure, is an amorphous fluid even at extremely high molecular weights. The cause of this behavior is the high flexibility of the siloxane backbone and the lack of intermolecular interactions attributed to the presence of methyl groups. These make PDMS incompatible with almost any organic or inorganic component leading to phase separation in siloxane-siloxane copolymers containing blocks with polar organic groups and in siloxane-organic copolymers, where dimethylsiloxane segments co-exist with organic ones. Self-assembly at the micro- or nanometric scale is common in certain mixed structures, including micelles, vesicles, et cetera, manifesting reversibly in response to an external stimulus. Polymers with a very high degree of ordering in the form of high-quality crystals were obtained when siloxane/silane segments co-exist with coordinated metal blocks in the polymer chain. While in the case of coordination of secondary building units (SBUs) with siloxane ligands 1D chains are formed; when coordination is achieved in the presence of a mixture of ligands, siloxane and organic, 2D structures are formed in most cases. The Romanian research group's results regarding these aspects are reviewed: from the synthesis of classic, amorphous silicone products, to their adaptation for use in emerging fields and to new self-assembled or highly ordered structures with properties that create perspectives for the use of silicones in hitherto unexpected areas.

From iron coordination compounds to metal oxide nanoparticles.

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), µ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.