Synthesis and Functionalization of Silver Nanoparticles for the Preparation of High Permittivity Nanocomposites

Over the last decade, a growing interest in nanochemistry has emerged due to the interesting features of nanomaterials that vary with size, shape and surface structure. In particular, metal nanoparticles have received much attention due to their properties that enable their use in various scientific disciplines. Although metal nanoparticles exhibit a number of properties that differ from bulk, some properties, such as their infinite permittivity, remain unchanged. As a result, metal nanoparticles have also been used to prepare nanocomposites with polymers in order to provide dielectric materials featuring high permittivities which can be used for applications such as energy storage (capacitors) or as materials for the conversion of electrical energy into mechanical motion (actuators). Despite the large number of publications on the preparation of nanocomposites exhibiting high permittivities which have emerged over the years, there is still room for further improvement in the current materials properties. For instance, dielectric losses are still quite high in some materials, and the use of certain types of filler lead to a large deterioration in the mechanical properties of the nanocomposites, especially with increasing filler content. In addition, a large number of the fillers used for the preparation of the nanocomposites feature poor size and shape control as well as poorly defined surface properties thus adding to the complexity of understanding the resulting material properties. This work tries to address some of the current issues concerning the preparation of dielectric materials. Therefore, silver nanoparticles (AgNPs) were used as filler, while polydimethylsiloxane (PDMS) was employed as the polymeric matrix. The advantages of using AgNPs as filler consist of their relative facile preparation, as well as the possibility of controlling their surface properties due to their resistance towards oxidation and corrosion. The possibility of preparing AgNPs in large amounts with control over the average size of the particles was realized by conducting the polyol synthesis of AgNPs in a Segmented Flow Tubular Reactor (SFTR). A SiO2 layer was grown around the AgNPs to prevent the loss of the insulating nature of the composite due to the formation of conductive pathways, and the thickness dependency of the dielectric properties of the core-shell particles was also investigated in this work. Furthermore, the SiO2 shell also provided the possibility of further surface functionalization, which was conducted in order to compatibilize the core-shell particles with the PDMS matrix. PDMS was chosen as the polymeric matrix due to its good electromechanical properties, which include high elasticity, low viscosity as well as low conductivity and low tangent losses (tan ÎŽ). The resulting nanocomposites featured enhanced permittivities compared to PDMS, while further optimization in the reaction conditions as well as in the processing procedure yielded nanocomposites with high flexibility that can undergo strains as high as 800 % at a silver content of 20 vol%. Other properties such as electric conductivity and the tan ÎŽ were kept low which emphasizes the potential of the nanocomposites to being used as flexible dielectric materials

Size Control and Enhanced Stability of Silver Nanoparticles by Cyclic Poly(ethylene glycol)

Silver nanoparticles (AgNPs) are used in a wide range of applications, and the size control and stability of the nanoparticles are crucial aspects in their applications. In the present study, cyclized poly(ethylene glycol) (c-PEG) with various molecular weights, along with linear PEG with hydroxy chain ends (HO-PEG-OH) and methoxy chain ends (MeO-PEG-OMe) were applied for the Tollens' synthesis of AgNPs. The particle size was significantly affected by the topology and end groups of PEG. For example, the size determined by TEM was 40 +/- 7 nm for HO-PEG(5k)-OH, 21 +/- 4 nm for c-PEG(5k), and 48 +/- 9 nm for MeO-PEG(5k)-OMe when the molar ratio of PEG to AgNO3 (omega) was 44. The stability of AgNPs was also drastically improved by cyclization; the relative UV-Vis absorption intensity (A/A(0) x 100%) at lambda(max) to determine the proportion of persisting AgNPs in an aqueous NaCl solution (37.5 mM) was 58% for HO-PEG(5k)-OH, 80% for c-PEG(5k), and 40% for MeO-PEG(5k)-OMe, despite the fact that AgNPs with c-PEG(5k) were much smaller than those with HO-PEG(5k)-OH and MeO-PEG(5k)-OMe