Molecular Layer Deposition of Polyurea on Silica Nanoparticles and Its Application in Dielectric Nanocomposites.

Polymer nanocomposites (NCs) offer outstanding potential for dielectric applications including insulation materials. The large interfacial area introduced by the nanoscale fillers plays a major role in improving the dielectric properties of NCs. Therefore, an effort to tailor the properties of these interfaces can lead to substantial improvement of the material's macroscopic dielectric response. Grafting electrically active functional groups to the surface of nanoparticles (NPs) in a controlled manner can yield reproducible alterations in charge trapping and transport as well as space charge phenomena in nanodielectrics. In the present study, fumed silica NPs are surface modified with polyurea from phenyl diisocyanate (PDIC) and ethylenediamine (ED) via molecular layer deposition (MLD) in a fluidized bed. The modified NPs are then incorporated into a polymer blend based on polypropylene (PP)/ethylene-octene-copolymer (EOC), and their morphological and dielectric properties are investigated. We demonstrate the alterations in the electronic structure of silica upon depositing urea units using density functional theory (DFT) calculations. Subsequently, the effect of urea functionalization on the dielectric properties of NCs is studied using thermally stimulated depolarization current (TSDC) and broadband dielectric spectroscopy (BDS) methods. The DFT calculations reveal the contribution of both shallow and deep traps upon deposition of urea units onto the NPs. It could be concluded that the deposition of polyurea on NPs results in a bi-modal distribution of trap depths that are related to each monomer in the urea units and can lead to a reduction of space charge formation at filler-polymer interfaces. MLD offers a promising tool for tailoring the interfacial interactions in dielectric NCs.

Fly Ash from Lignite Combustion as a Filler for Rubber Mixes-Part II: Chemical Valorisation of Fly Ash.

Fly ash (FA) fractions with a particle size of 63 µm < FA < 250 µm obtained by sieve fractionation were used as a partial carbon black (CB) replacement in a rubber mixture based on styrene-butadiene rubber (SBR). In order to improve the interactions at the interface between rubber and fractionated ash, at the stage of preparing the rubber mixtures, two different vinyl silanes were added to the system: Vinyltrimethoxysilane (U-611) or Vinyl-tris (2-methoxy-ethoxy) silane (LUVOMAXX VTMOEO DL50), silane with epoxy groups: 3-(glycidoxypropyl)trimethoxysilane (U-50) or sulfur functionalized silanes: containing sulfide bridges: Bis(triethoxysilylpropyl)polysulfide silane (Si-266) or mercapto groups: Mercaptopropyltrimethoxysilane (Dynaslan MTMO). The conducted research confirmed the effectiveness of silanization with selected functional silanes, from the point of view of improving the processing and operational properties of vulcanizates, in which CB is partially replaced with the finest fractions of fly ash. The silanization generally increased the interaction at the rubber−ash interface, while improving the degree of filler dispersion in the rubber mixture. The results of TGA and FTIR analyses confirmed the presence of silanes chemically bonded to the surface of fly ash particles. SEM tests and determination of the bound rubber (BdR) content show that the introduction of the silanes to the mixture increases the degree of ash dispersion (DI) and the Payne effect, which is the greatest when mercaptosilane was used for modification. The highest increase in torque, which was recorded in the case of rubber mixtures containing sulfur silanes and silane with epoxy groups, may be due to their participation in the vulcanization process, which is confirmed by the results of vulcametric studies. The lowest values of mechanical strength, elongation at break, and the highest hardness of vulcanizates obtained in this case may be the result of the over-crosslinking of the rubber. The addition of sulfur-containing silanes significantly slowed down the vulcanization process, which is particularly visible (up to three times extension of the t90 parameter, compared to mixtures without silane) in the case of Si-266. The addition of silanes, except for Si-266 (with a polysulfide fragment), generally improved the abrasion resistance of vulcanizates. The Dynaslan MTMO silane (with mercapto groups) performs best in this respect. Proper selection of silane for the finest fraction of fly ash in the rubber mixtures tested allows for an increase in the mechanical strength of their vulcanizates from 9.1 to 17 MPa, elongation at break from 290 to 500%, hardness from 68 to 74 °ShA, and reduction in abrasion from 171 to 147 mm3.

Fly Ash from Lignite Combustion as a Filler for Rubber Mixes. Part I: Physical Valorization of Fly Ash.

The potential use of fly ash (FA) originating from lignite combustion at the Belchatow Power Plant (Poland) as filler for rubber mixes was evaluated. Samples of fly ash collected from heaps created in different years were compared according to their chemical and phase composition, particle size distribution, and morphology. The sieve fractionation of fly ash results in size fractions of different chemical structures, phase compositions, and morphologies, reflected in changes to their specific surface area, surface energy, and activity in rubber mixes. Fractionation turned out to be more effective than grinding from the point of view of using ash as a filler for rubber mixes, because it results in higher specific surface area (SSA) and chemical composition differentiation. Carbon black can be replaced by up to 40% by weight with the fly ash fraction (FFA) of dimensions below 125 µm, without any significant deterioration in the mechanical properties of styrene butadiene rubber (SBR) vulcanizates filled with 50 phr of active carbon black (N 220). Despite the larger fly ash fraction of grain dimensions in the range between 125 and 250 µm presenting the highest specific surface area, the particle size adversely affects its strengthening effect in rubber. Taking into account all the tests performed, ranging from morphology, Payne effect and bound rubber, to mechanical and abrasion tests, the highest potential effectivity is presented by a sample containing 30 phr of N 220 and 20 phr of FFA of grain sizes from 63 to 125 µm. The obtained results indicate that fractionation seems to be an effective physical method of fly ash valorization.

Bitumen Binders Modified with Sulfur/Organic Copolymers.

With the continuing growth of waste sulfur production from the petroleum industry processes, its utilization for the production of useful, low-cost, and environmentally beneficial materials is of primary interest. Elemental sulfur has a significant and established history in the modification of bitumen binders, while the sulfur-containing high-molecular compounds are limited in this field. Herein, we report a novel possibility to utilize the sulfur/organic copolymers obtained via the inverse vulcanization process as modifiers for bitumen binders. Synthesis and thermal characterization (TGA-DSC) of polysulfides derived from elemental sulfur (S8) and unsaturated organic species (dicyclopentadiene, styrene, and limonene) have been carried out. The performance of modified bitumen binders has been studied by several mechanical measurements (softening point, ductility, penetration at 25 °C, frass breaking point, adhesion to glass and gravel) and compared to the unmodified bitumen from the perspective of normalized requirements concerning polymer-modified bitumen. The interaction of bitumen binder with sulfur/organic modifier has been studied by means of FTIR spectroscopy and DSC measurements. The impact of the modification on the performance properties of bitumen has been demonstrated. The bitumen binders modified with sulfur/organic copolymers are in general less sensitive to higher temperatures (higher softening point up to 7 °C), more resistant to permanent deformations (lower penetration depth), and more resistant to aging processes without intrusive deterioration of parameters at lower temperatures. What is more, the modification resulted in significantly higher adhesion of bitumen binders to both glass (from 25% up to 87%) and gravel surfaces in combination with a lower tendency to form permanent deformations (more elastic behavior of the modified materials).

Gas Phase Modification of Silica Nanoparticles in a Fluidized Bed: Tailored Deposition of Aminopropylsiloxane.

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.

Comparison between SBR Compounds Filled with In-Situ and Ex-Situ Silanized Silica.

The main advantages of the use of silica instead of carbon black in rubber compounds are based on the use of a silane coupling agent. The use of a coupling agent to modify the silica surface improves the compatibility between the silica and the rubber. There are two different possibilities of modifying the silica surface by silane: ex-situ and in-situ. The present work studies the differences between these processes and how they affect the in-rubber properties of silica filled SBR compounds.

Surface Modification of Fumed Silica by Plasma Polymerization of Acetylene for PP/POE Blends Dielectric Nanocomposites.

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.

New Sulfur Organic Polymer-Concrete Composites Containing Waste Materials: Mechanical Characteristics and Resistance to Biocorrosion.

The aim of this study was to develop new sulfur-copolymer concrete composites using waste compounds that have good mechanical characteristics and show a resistance to biocorrosion. The comonomers used to synthesize the sulfur-organic copolymers were-90 wt. % sulfur; 5 wt. % dicyclopentadiene (DCPD); 5 wt. % organic monomers, styrene (SDS), 1-decene (SDD), turpentine (SDT), and furfural (SDF). The concrete composites based on sulfur-organic copolymers were filled with aggregates, sand, gravel, as well as additives and industrial waste such as fly ash or phosphogypsum. The sulfur-organic copolymers were found to be chemically stable (softening temperature, thermal stability, melting temperature, amount of recrystallized sulfur, and shore D hardness). Partial replacement of DCPD with other organic comonomers did not change the thermal stability markedly but did make the copolymers more elastic. However, the materials became significantly stiffer after repeated melting. All the tested copolymers were found to be resistant to microbial corrosion. The highest resistance was exhibited by the SDS-containing polymer, while the SDF polymer exhibited the greatest change due to the activity of the microorganisms (FTIR analysis and sulfur crystallization). The concrete composites with sulfur-organic copolymers containing DCPD, SDS, SDF, fly ash, and phosphogypsum were mechanically resistant to compression and stretching, had low water absorbance, and were resistant to factors, such as temperature and salt. Resistance to freezing and thawing (150 cycles) was not confirmed. The concrete composites with sulfur-organic copolymers showed resistance to bacterial growth and acid activity during 8 weeks of incubation with microorganisms. No significant structural changes were observed in the SDS composites after incubation with bacteria, whereas composites containing SDF showed slight changes (FTIR and microscopic analysis). The concrete composite containing sulfur, DCPD, SDS, sand, gravel, and fly ash was the most resistant to microbiological corrosion, based on the metabolic activity of the bacteria and the production of ergosterol by the molds after eight weeks of incubation. It was found that Thiobacillus thioparus was the first of the acidifying bacteria to colonize the sulfur concrete, decreasing the pH of the environment. The molds Penicillium chrysogenum, Aspergillus versicolor and Cladosporium herbarum were able to grow on the surface of the tested composites only in the presence of an organic carbon source (glucose). During incubation, they produced organic acids and acidified the environment. However, no morphological changes in the concretes were observed suggesting that sulfur-organic copolymers containing styrene could be used as engineering materials or be applied as binders in sulfur-concretes.

Impact of Basalt Filler on Thermal and Mechanical Properties, as Well as Fire Hazard, of Silicone Rubber Composites, Including Ceramizable Composites.

This article illustrates the impact of basalt filler, both in the form of basalt flakes and basalt fibers, on thermal and mechanical properties, as well as on the fire hazard, of silicone rubber (SR) composites, including ceramizable composites. In addition to basalt filler, ceramizable composites contain mineral fillers in their composition in the form of silica and calcium carbonate, inorganic fluxes such as zinc borate and glass frit, and melamine cyanurate as a flame retardant. The obtained composites were analyzed from the point of view of their morphology, rheological and thermal properties, flammability, and mechanical properties before and after the ceramization process. The obtained research results indicate that the basalt filler has an unambiguous impact on the improvement of thermal properties and the reduction of flammability in the analyzed composites. The results of morphological analyses of ceramizable composites before and after the process of their ceramization indicate a definite impact of the basalt filler on the structure of the formed ceramic layer. An increase in its homogeneity exerts a direct impact on the improvement of its mechanical parameters.

Influence of Surface Modified Nanodiamonds on Dielectric and Mechanical Properties of Silicone Composites.

Detonation nanodiamonds, also known as ultradispersed diamonds, possess versatile chemically active surfaces, which can be adjusted to improve their interaction with elastomers. Such improvements can result in decreased dielectric and viscous losses of the composites without compromising other in-rubber properties, thus making the composites suitable for new demanding applications, such as energy harvesting. However, in most cases, surface modification of nanodiamonds requires the use of strong chemicals and high temperatures. The present study offers a less time-consuming functionalization method at 40 °C via reaction between the epoxy-rings of the modifier and carboxylic groups at the nanodiamond surface. This allows decorating the nanodiamond surface with chemical groups that are able to participate in the crosslinking reaction, thus creating strong interaction between filler and elastomer. Addition of 0.1 phr (parts per hundred rubber) of modified nanodiamonds into the silicone matrix results in about fivefold decreased electric losses at 1 Hz due to a reduced conductivity. Moreover, the mechanical hysteresis loss is reduced more than 50% and dynamic loss tangent at ambient temperature is lowered. Therefore, such materials are recommended for the dielectric energy harvesting application, and they are expected to increase its efficiency.

Sulfur/Organic Copolymers as Curing Agents for Rubber.

It is widely acknowledged that waste sulfur generated from the petroleum industry creates huge storage and ecological problems. Therefore, the various methods of utilization are becoming increasingly attractive research topics worldwide. The thermal ability of elemental sulfur to homolytic cleavage of S8 rings enables its free radical copolymerization with unsaturated organic species and the obtaining of chemically stable polymeric materials. Here we report a novel possibility to use sulfur/organic copolymers obtained via "inverse vulcanization" as curatives for rubber. For this purpose, several various sulfur/organic copolymers were synthesized and analyzed from the point of view of their performance as rubber crosslinking agents. Solvent extraction was used to purify sulfur/organic copolymers from unreacted (elemental) sulfur. Thermal properties of the prepared copolymers were characterized by thermogravimetric analysis and differential scanning calorimetry (TGA⁻DSC). Crosslink density and structure of cured elastomers was studied by equilibrium swelling, thiol-amine analysis and freezing point depression. Mechanical properties of the vulcanizates were determined under static and dynamic conditions (DMA-dynamic mechanical analysis). It is proved that the utilization of sulfur/organic copolymers as curatives enables an effective crosslinking process of rubbers. Taking into account the results of a crosslink density analysis and mechanical properties of the vulcanizates cured with purified copolymers, it is evident that relatively long copolymer macromolecules are also involved in the formation of chemical bonds between unsaturated rubber macromolecules.

Thermal Stability and Flammability of Styrene-Butadiene Rubber-Based (SBR) Ceramifiable Composites.

Ceramifiable styrene-butadiene (SBR)-based composites containing low-softening-point-temperature glassy frit promoting ceramification, precipitated silica, one of four thermally stable refractory fillers (halloysite, calcined kaolin, mica or wollastonite) and a sulfur-based curing system were prepared. Kinetics of vulcanization and basic mechanical properties were analyzed and added as Supplementary Materials. Combustibility of the composites was measured by means of cone calorimetry. Their thermal properties were analyzed by means of thermogravimetry and specific heat capacity determination. Activation energy of thermal decomposition was calculated using the Flynn-Wall-Ozawa method. Finally, compression strength of the composites after ceramification was measured and their micromorphology was studied by scanning electron microscopy. The addition of a ceramification-facilitating system resulted in the lowering of combustibility and significant improvement of the thermal stability of the composites. Moreover, the compression strength of the mineral structure formed after ceramification is considerably high. The most promising refractory fillers for SBR-based ceramifiable composites are mica and halloysite.

Thermal behavior of silicone rubber-based ceramizable composites characterized by Fourier transform infrared (FT-IR) spectroscopy and microcalorimetry.

Ceramizable (ceramifiable) silicone rubber-based composites are commonly used for cable insulation. These materials are able to create a protective ceramic layer during fire due to the ceramization process, which occurs at high temperature. When the temperature is increased, the polymer matrix is degraded and filler particles stick together by the fluxing agent, producing a solid, continuous ceramic phase that protects the copper wire from heat and mechanical stress. Despite increasing interest in these materials that has resulted in growing applications in the cable industry, their thermal behavior and ceramization process are still insufficiently described in the literature. In this paper, the thermal behavior of ceramizable silicone rubber-based composites is studied using microcalorimetry and Fourier transform infrared spectroscopy. The analysis of the experimental data made it possible to develop complete information on the mechanism of composite ceramization.