ELASTOMER BASED COMPOSITES FILLED WITH

LAYERED FILLERS AND IONIC LIQUIDS

This thesis was focused on the preparation and the study of elastomer composites filled
with layered fillers (cationic clays, anionic clays and graphene-like platelets) with improved
mechanical properties, decreased swelling in solvents, increased UV stability and reduced gas
permeability. The use of layered minerals in rubber formulations has ecologic and economic
importance and offers the potential for environmentally friendly rubber products. Moreover,
the melt mixing method used in this work for the rubber/layered fillers composites preparation
is considered as a one of the most eco-friendly routes that excludes the use of organic solvents
and is the most suitable for an industrial scale production. In this work, the layered minerals
where investigated not only in terms of their use as reinforcing fillers for rubbers but also as
crosslinking agents, gas barrier and UV stability enhancers. The multifunctionality of these
fillers makes them interesting materials with broad potential applicability for the
manufacturing of high performance elastomers. The layered fillers tested belong to a class of
cationic clays (natural and synthetic hectorite), anionic clays (hydrotalcites or magnesium
aluminum layered double hydroxides MgAl-LDHs) and graphene-based materials. The first
part of thesis focused on the evaluation of morphological, structural, thermal and surface
characteristics of the layered minerals by following techniques: scanning electron microscopy
(SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR),
Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and inverse gas
chromatography (IGC). Subsequently, the rubber composites were prepared either by 1-step
mixing method in a laboratory two-roll mill or by 2-step method involving (1) processing in
an internal mixer and (2) milling in the two-roll mill. The influences of layered fillers in the
amounts form 2.5 40 phr (depending on the types of particulate filler) on the curing
behavior, crosslink density, tensile properties, mechano-dynamical properties, thermal
behavior and morphology of elastomer composites were investigated. The elastomer
composites containing increasing concentrations of imidazolium ionic liquids ILs, were
tested for their rheometric, mechanical, ionic conductivity and morphological properties. The
following techniques were used: DMA (dynamic-mechanical analysis), differential scanning
calorimetry (DSC), broadband dielectric spectroscopy (BDS), Fourier-transmission infrared
spectral analysis (FTIR), thermogravimetric analysis (TGA), X-ray analysis (XRD), scanning
electron microscopy (SEM).
Different structural and surface properties of layered fillers such as particles aspect ratio,
specific surface area and surface activity were investigated as factors impacting the
reinforcement of acrylonitrile-butadiene rubber (NBR) and carboxylated acrylonitrilebutadiene rubber (XNBR). The NBR was vulcanized with the use of conventional sulfur-base
cure system which leads to the formation sulfur bridges between rubber chains. The XNBR
was crosslinked by the metal ions-containing curatives (ZnO, MgAl-LDH) where ionic bonds
are generated through the reaction between carboxylic groups and metal ions. Special
attention has been devoted to the XNBR systems containing magnesium aluminum layered
double hydroxides (MgAl-LDHs) varying in Mg/Al ratios, layers aspect ratios and particles
morphologies. This thesis presented that the simultaneous application of MgAl-LDH as a

filler and as a crosslinking agent in XNBR provides not only environmentally friendly, zincoxide free product but also ionic elastomer composite with improved mechanical, barrier and
transparent properties. It was observed that the extent of the reinforcement and cure degree of
XNBR is strongly related to the content of magnesium ions in LDH crystalline structure and
the aspect ratio of layers. By conducting rheometric, dynamic mechanical (DMA) and Fourier
transform infrared spectroscopy (FTIR) studies it was demonstrated that improvements in
mechanical properties arise from the existence of ionic crosslinks via metal-carboxylate
crosslinking provided by MgAl-LDH. This thesis considers also the potential application of
hydrophilic and hydrophobic imidazolium ionic liquids which are characterized by high ionic
conductivities as multifunctional additives in rubber formulations. Such organic compounds
could serve simultaneous functions as dispersing agents in rubber matrix, plasticizers and
ionic conductivity enhancers. The optimal concentration and type of ionic liquids were
selected for obtaining a good compromise between mechanical and conductivity properties of
rubber composites. The rubber composite with improved mechanical, morphological
properties and increased ionic conductivity up to 10-7 S/cm was realized by the use of
hydrophobic 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic and 1butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids at low
concentrations from 5 to 10 parts per hundred rubber (phr). Increased length of alkyl chain to
1-hexyl-3-methylimidazolium or higher concentration of ionic liquid than 10 phr in rubber
matrix led to a decrease in mechanical properties due to the plasticizing effect of the excess of
ionic liquid in rubber composite material. Graphene fillers with various specific areas, surface
chemistry and particles morphology were also investigated as novel reinforcing fillers for
acrylonitrile-butadiene rubber (NBR) and carboxylated nitrile butadiene rubber (XNBR).
Both kinds of rubbers showed significantly improved UV stability in the presence of layered
carbon filler. A substantial improvement in mechanical properties of XNBR was observed
even at low filler concentration of 5 phr.