Novel nanocomposites for dielectric applications-based polypropylene/poly(ethylene-co-octene) (PP/POE) blends filled with nano silica are developed in the framework of the European ‘GRIDABLE’ project. A tailor-made low-pressure-plasma reactor was applied in this study for an organic surface modification of silica. Acetylene gas was used as the monomer for plasma polymerization in order to deposit a hydrocarbon layer onto the silica surface. The aim of this modification is to increase the compatibility between silica and the PP/POE blends matrix in order to improve the dispersion of the filler in the polymer matrix and to suppress the space charge accumulation by altering the charge trapping properties of these silica/PP/POE blends composites. The conditions for the deposition of the acetylene plasma-polymer onto the silica surface were optimized by analyzing the modification in terms of weight loss by thermogravimetry (TGA). X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray fluorescence spectroscopy (EDX) measurements confirmed the presence of hydrocarbon compounds on the silica surface after plasma modification. The acetylene plasma modified silica with the highest deposition level was selected to be incorporated into the PP/POE blends matrix. X-ray diffraction (XRD) showed that there is no new crystal phase formation in the PP/POE blends nanocomposites after addition of the acetylene plasma modified silica. Differential scanning calorimetry results (DSC) show two melting peaks and two crystallization peaks of the PP/POE blends nanocomposites corresponding to the PP and POE domains. The improved dispersion of the silica after acetylene plasma modification in the PP/POE blends matrix was shown by means of SEM–EDX mapping. Thermally stimulated depolarization current (TSDC) measurements confirm that addition of the acetylene plasma modified silica affects the charge trapping density and decreases the amount of injected charges into PP/POE blends nanocomposites. This work shows that acetylene plasma modification of the silica surface is a promising route to tune charge trapping properties of PP/POE blend-based nanocomposites.

We evaluated the significance of mechanical engagement and energetic interaction between a polymer and a filler as two reinforcing mechanisms in SBR composites containing silica modified by short- and long-chain silanes. To exclude mechanical contributions of reinforcement from that of energetic contributions, surface energy of silica particles was systematically adjusted to prepare fillers of identical and diverse surface energies. Having analyzed interactions using a temperature sweep in a small-strain oscillatory test and a uniaxial tension test, results indicated that the chain length of the silane has remarkable influence on energetic filler–filler and filler–polymer interactions, but no detectable difference associated with filler–polymer mechanical engagement was observed from these experiments. However, dynamic strain sweep experiments showed that the rate of breakage of the filler network (Payne effect) is less for the composite having long-chain silane compared to that having short-chain silane. It was hypothesized that this behavior could be correlated to mechanical engagements of long-chain silanes existing on the filler structure.

Functionalized nanoparticles have various applications, for which grafting of a chemical moiety onto the surface to induce/improve certain properties is needed. When incorporated in polymeric matrices, for instance, the modified nanoparticles can alter the interfacial characteristics leading to improvements ofthe macroscopic properties of the nanocomposites. The extent of these improvements is highly dependent on the thickness, morphology and conformity of the grafted layer. However, the common liquid-phase modification methods provide limited control over these factors. A novel gas-phase modification process was utilized, with 3-aminopropyltriethoxysilane (APTES) as precursor, to chemically deposit amino-terminated organic layers on fumed silica nanoparticles in a fluidized bed. A self-limiting surface saturation was achieved when the reaction was done at 200 °C. With this self-limiting feature, we were able to graft multiple layers of aminopropylsiloxane (APS) onto the silica nanoparticles using water as the coreactant. The feasibility of this process was analyzed using thermogravimetric analysis (TGA), diffuse reflectance IR Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and elemental analysis (EA). By altering the number of APTES/water cycles, it was possible to control the thickness and conformity of the deposited aminopropylsiloxane layer. This novel approach allows to engineer the surface of nanoparticles, by introducing versatile functionalized layers in a controlled manner.

The present study discusses that filler–filler mechanical engagement resulting from the grafted long-chain silanes on the silica surface is indeed a reinforcing mechanism in rubber composites, as already speculated by nonlinear viscoelastic properties in our previous study. The existence and severity of such a phenomenon are assessed purely by isolating the energetic contribution of reinforcement from interfering with filler mechanical engagement in the silica network formation and breakdown processes. In a novel approach, the driving force of fillers to flocculate energetically at elevated temperatures was defined using surface energy theories, and it was adjusted to be similar in two composites having silica treated by short- and long-chain silanes. Filler–filler mechanical engagement was monitored by tracking network formation (filler flocculation) in a matrix of styrene–butadiene rubber and also by conducting various dynamic viscoelastic experiments on liquid paraffin suspensions having short- and long-chain silica of similar surface energy. Results consistently confirmed the existence of mechanical engagement between silica particles having the long-chain silane in both rubber compounds and paraffin suspensions. The results may find applications in the rolling resistance of tires, for example, where stabilization of the filler network by displacing the peak energy dissipation of the network breakdown from applied service strains to larger values would be of technical importance.

Novel nanocomposites for dielectric applications based on a polypropylene (PP) blend filled with nanosilica are developed in the frame of the European `GRIDABLE' project. A systematic study of the influence of surface modification of the nanosilica on the dielectric properties of the PP/silica blend was performed. The main goal of this investigation was to modify the chemical composition of the silica surface, which is expected to improve the charge trapping properties of the nanocomposites. For the modification of the silica surface, a “green” approach was utilized: a dry silanization method, which is performed without the need of a solvent. Eight different silanes were investigated in this study, which are categorized into three different groups: I)Aliphatic silanes with a different number of alkoxy groups II)Hydrocarbon silanes containing delocalized electron clouds III)Polar silanes containing hetero elements (nitrogen, sulfur or oxygen) The results of the thermogravimetric analysis (TGA) show higher weight loss of the modified silicas in comparison to the unmodified one. This indicates that the dry process is an effective method to perform silica surface modification using alkoxysilanes. The charge trapping properties were studied by Thermally Stimulated Depolarization Current (TSDC) measurements. The obtained TSDC results show that the trap density peak is not significantly shifted in temperature when the silica is modified with functional groups elementally similar to the polymer matrix. However, their incorporation influences the traps density and suppress the deeper traps occurring near the range of the melting temperature of PP. When the silica surface is modified with a precursor containing a hetero element, it has an effect on both, trap level depth as well as density. Depending on the type of the hetero element (sulfur, nitrogen, oxygen), the trap depth shifted to higher temperatures, and the trap density decreased to significantly lower levels. Nitrogen appears to have the strongest effect on the charge trap properties. All these first stage of results show that incorporation of modified nanosilica into a PP matrix seems to be a promising approach to tailor its electric properties. Further development of these composites would lead to benefits for high-voltage cable and capacitors applications.