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.

Siloxane Matrix Molecular Weight Influences the Properties of Nanocomposites Based on Metal Complexes and Dielectric Elastomer.

Siloxane-based elastomers are some of the most sought-after materials for the construction of actuators and equipment for energy harvesting devices. This article focuses on changes of the mechanical (breaking stress, breaking strain, Young's modulus) and dielectric properties for elastomers prepared with silicones, induced by the variation of molecular weight of the matrix, with three different silicone polymers having 60,000 g/mol, 150,000 g/mol, and 450,000 g/mol (from GPC measurements). Multiple siloxane elastomers were crosslinked with methyltriacetoxysilane using the sol-gel route. The dielectric permittivity values of the elastomers were also enhanced with two different complex structures containing siloxane bond and 3d transition metals as filler materials for polydimethylsiloxane polymers with various molecular weights. The dielectric spectroscopy tests demonstrated a small decrease (5%) for the values of the dielectric permittivity in relation to increased molecular weight of the siloxane polymer, both for samples prepared with pure polymer and for samples with metal complexes. The samples of nanocomposites showed a >50% increase of dielectric permittivity values relative to samples prepared of pure siloxane elastomer. The thermal tests demonstrated that the nanocomposites retained thermal stability similar with samples prepared of pure siloxane elastomer. The behavior under controlled conditions of humidity showed a trend of increased water vapor sorption with increasing molecular weight but an overall hydrophobic stable character of nanocomposites.

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.

A dynamic thermoregulatory material inspired by squid skin.

Effective thermal management is critical for the operation of many modern technologies, such as electronic circuits, smart clothing, and building environment control systems. By leveraging the static infrared-reflecting design of the space blanket and drawing inspiration from the dynamic color-changing ability of squid skin, we have developed a composite material with tunable thermoregulatory properties. Our material demonstrates an on/off switching ratio of ~25 for the transmittance, regulates a heat flux of ~36 W/m2 with an estimated mechanical power input of ~3 W/m2, and features a dynamic environmental setpoint temperature window of ~8 °C. Moreover, the composite can manage one fourth of the metabolic heat flux expected for a sedentary individual and can also modulate localized changes in a wearer's body temperature by nearly 10-fold. Due to such functionality and associated figures of merit, our material may substantially reduce building energy consumption upon widespread deployment and adoption.

Adaptive infrared-reflecting systems inspired by cephalopods.

Materials and systems that statically reflect radiation in the infrared region of the electromagnetic spectrum underpin the performance of many entrenched technologies, including building insulation, energy-conserving windows, spacecraft components, electronics shielding, container packaging, protective clothing, and camouflage platforms. The development of their adaptive variants, in which the infrared-reflecting properties dynamically change in response to external stimuli, has emerged as an important unmet scientific challenge. By drawing inspiration from cephalopod skin, we developed adaptive infrared-reflecting platforms that feature a simple actuation mechanism, low working temperature, tunable spectral range, weak angular dependence, fast response, stability to repeated cycling, amenability to patterning and multiplexing, autonomous operation, robust mechanical properties, and straightforward manufacturability. Our findings may open opportunities for infrared camouflage and other technologies that regulate infrared radiation.

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.