Abstract
In modern polymer industry, there still is a room for new generations of fillers capable of enhancing the performance of composite materials. Currently, much effort is being put into a process of improving mechanical properties of elastomer materials. In this work, multiwalled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GnPs) were modified with silane, titanate, or zirconate using plasma treatment, in order to apply them as fillers for styrene/butadiene rubber. Following its modification, filler surface was analyzed: Surface free energy (SFE) was measured with tensiometry, and micromorphology and chemical composition were studied with scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), while elemental composition and bonding were assessed with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Low-temperature oxygen plasma activation of MWCNT fillers leads to a significant increase in the SFE polar component, with the same effect being much weaker for GnP fillers. Grafting silanes, zirconates, and titanates on activated filler surface results in a decrease in SFE polar component—surface oxygen-containing active groups react with silane/zirconate/titanate molecules. Fillers modified in this way exhibit different micromorphology and surface chemical composition what is revealed with the SEM–EDS, ToF-SIMS, and XPS techniques. As the ultimate step, either MWCNT or GnP rubber nanocomposites were manufactured using the modified fillers with their mechanical properties and cross-link density being studied. Filler modification resulted in substantial changes both in composite performance, and in its cross-linking density. In the case of modified filler containing composites, improved tensile strength and elongation at break were observed.
Highlights
The filler most commonly used in rubber technology is carbon black, in this dynamically developing industry, there is still a lot of room for new generations of carbon fillers that can improve performance or introduce novel functions to rubber vulcanizates
A reference sample (MWCNTs before treatment) exhibited a substantially high Surface free energy (SFE) polar component, what could be attributed to a partial oxidization of a residual amorphous carbon layer
The maximum of SFE was attained after 32 min of activation (28.1 mJ/ m2) with an intermediate value of 25.5 mJ/m2 acquired for 16 min activation
Summary
The filler most commonly used in rubber technology is carbon black, in this dynamically developing industry, there is still a lot of room for new generations of carbon fillers that can improve performance or introduce novel functions to rubber vulcanizates Due to their extraordinary properties and thanks to current prices that are much more acceptable than those of the last decade, such advanced powder fillers as carbon nanotubes (CNT) or graphene nanoplatelets (GnP) are more and more often applied in the rubber industry. Since their discovery, these forms of carbon have focused scientific interest of research workers representing different fields [1]. In order to improve a strengthening effect of the filler, a formation of large secondary filler structures should be avoided [3, 4]—especially when nanoparticles such as CNTs or GnPs are considered
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