Jacobus W.M. Noordermeer

Mechanistic aspects of the role of coupling agents in silica-rubber composites

Compared to carbon black, the use of silica as reinforcing filler for rubber results in lower hysteretic losses, for tyre applications leading to lower rolling resistance and consequently fuel savings. The compatibility of hydrophilic silica with a hydrophobic rubber polymer matrix is generally poor. Adding bi-functional coupling agents to the compounds, commonly bis(triethoxysilylpropyl) tetrasulphide (TESPT), enhances filler-matrix compatibility. The degree of hydrophobation of silica during rubber mixing then depends on many mutually interacting factors. Irreproducible conditions during mixing and vulcanisation are major causes of irreproducibility of silica-reinforced rubber compounds. Depending on the chemical composition of the coupling agent, the ultimate temperature obtained during the mixing process turns out to be the main factor governing the reactions of the coupling agent: the formation of a proper bond between the silica and the coupling agent, while avoiding a premature reaction with the rubber polymers, leading to premature scorch during mixing. Further, the mechanistic aspects of the reaction of various coupling agents, variants on TESPT, are covered, with silica as well as with the rubber. Of great importance are: the carbon and sulphur chain-lengths within the coupling agents, whether corrections are applied in the compound with elemental sulphur relative to the sulphur contained in the reference TESPT, and the moments the correcting amounts of sulphur are added to the compounds: during the first mixing stage, or together with the curing ingredients later-on in the process. The tensile properties of the vulcanised compounds are most prominently influenced. This is indicative of the dual role of sulphur: on the one hand as direct curative, on the other hand as part of the coupling agent becoming attached to the rubber polymers.

Effects of time and temperature on the reaction of TESPT silane coupling agent during mixing with silica filler and tire rubber

Abstract The addition of a coupling agent to silica-rubber compounds enhances the filler-matrix compatibility. Under certain mixing conditions the surface of the filler may be only partly activated...

Mechanisms Involved in the Recycling of NR and EPDM

Abstract The thermochemical recycling of natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) vulcanizates with disulfides was studied. NR sulfur vulcanizates were completely plasticized when heated with diphenyldisulfide at 200 °C. It could be concluded that both main chain scission and crosslink scission caused the network breakdown. NR peroxide vulcanizates were less reactive towards disulfide at 200 °C, and only reacted through main chain scission. For EPDM a temperature range of 200–275 °C was studied. In the presence of diphenyldisulfide at 200 °C there was almost no devulcanization of EPDM sulfur vulcanizates, and at 225 and 250 °C there was only slightly more devulcanization. A decrease in crosslink density of 90% was found when 2×10−4 mol diphenyldisulfide/cm3 vulcanizate was added and the EPDM sulfur vulcanizates were heated to 275 °C. EPDM peroxide vulcanizates showed a decrease in crosslink density of ca. 40% under the same conditions. The lower reactivity of EPDM towards disulfide c...

Flocculation in Silica Reinforced Rubber Compounds

Abstract Flocculation plays an important role in reinforcement of silica filled rubber compounds, even if coupling agents are applied. It is well known that silica tends to flocculate during the early stages of vulcanization, when no dense rubber network has been formed yet. In the present study, flocculation was monitored by following the change in storage modulus at low strain, the so-called Payne effect, using a RPA2000 dynamic mechanical tester. The kinetic parameters: the rate constant and the activation energy of the silica flocculation were calculated according to the well-known Arrhenius equation. On basis of the value of the activation energy obtained for flocculation, it can be concluded that the silica flocculation is a purely physical phenomenon. Bound rubber measurements were also done in order to estimate the interfacial interaction layer between silica and polymer resulting from the coupling agent. The silica flocculation rate decreases with increasing interfacial interaction layer on the s...

Dynamically vulcanized PP/EPDM blends: Effects of different types of peroxides on the properties

Abstract Thermoplastic vulcanizates (TPVs) or dynamic vulcanizates are thermoplastic elastomers produced by simultaneous mixing and crosslinking of a rubber and a thermoplastic. The effects of diff...

Dynamically vulcanized PP/EPDM blends: Multifunctional peroxides as crosslinking agents. Part I

Abstract Thermoplastic vulcanizates (TPVs) or dynamic vulcanizates are a special class of thermoplastic elastomers, produced by mixing and crosslinking of a rubber and a thermoplastic polymer simultaneously. In a previous study, it was demonstrated that the use of dicumyl peroxide in combination with triallyl cyanurate as crosslinking agents provides a good overall balance of physical properties of PP/EPDM TPVs. Commonly used peroxides like dicumyl peroxide generally produce volatile decomposition products, which sometimes provide a typical smell or show a blooming effect. In this paper multifunctional peroxides are described, which reduce the above-mentioned problems. They consist of a peroxide and co-agent-functionality combined in a single molecule. The multifunctional peroxides provide properties of TPVs, which are comparable with commonly employed co-agent assisted peroxides. The solubility and kinetic aspects of the various peroxides are highlighted, as well as the decomposition products of the mult...

Effect of Methacrylate Co-Agents on Peroxide Cured PP/EPDM Thermoplastic Vulcanizates

Abstract Thermoplastic vulcanizates (TPVs) have gained large technical and economic importance. TPVs are characterized by a chemically crosslinked rubber phase, embedded in a thermoplastic matrix, produced by dynamic vulcanization during mixing with the thermoplastic in its molten state. Methacrylate species are investigated as co-agents for peroxide vulcanization of polypropylene/ethylene-propylene-diene-rubber (PP/EPDM) TPVs, whereby the weight fraction of the EPDM is varied from 30, 50 to 70%. Ethylene glycol dimethacrylate (EDMA), trimethylol propane trimethacrylate (TMPTMA, often referred to as TRIM) and zinc dimethacrylate (ZDMA) are tested. A fixed amount of dicumyl peroxide as crosslinker and varying contents of co-agents are employed, the latter to boost EPDM-crosslinking and prevent degradation of the PP by β-scission. Differences observed in mechanical properties point to diverse structures of the crosslink networks of the TPVs. Of the three co-agents, TMPTMA gives the best overall balance of p...

Effects of composition and processing conditions on morphology and properties of thermoplastic elastomer blends of SEBS-PP-Oil and dynamically vulcanized EPDM-PP-Oil

This work presents a comparative study of the morphology and structure-related properties of thermoplastic elastomer blends based on SEBS-PP-oil and dynamically vulcanized EPDM-PP-oil prepared under identical conditions. Compositions of each blend type with three different SEBS-PP and EPDM-PP ratios by weight were made in a co-rotating twin-screw extruder and a Brabender internal mixer. A comparative study of different electron microscopic techniques for studying the morphology of these oil-extended blends is reported. Morphological characterization using different microscopic techniques showed a co-continuous morphology for the SEBS-PP-oil blends and droplet-matrix morphology for the thermoplastic vulcanizate (TPV) blends. The particle size distribution of the EPDM-phases in the TPVs prepared in the twin-screw extruder was wider than for the Brabender mixer. No difference in the morphology was observed for the SEBS-PP-oil blends prepared in the twin-screw extruder and Brabender, except for the blend with the highest PP content. The elongation-at-break values were significantly higher for the SEBS-PP-oil blends as compared to the TPV blends. The gel content of the TPVs was the main factor determining the stress-strain properties, as influenced by the preparation method. Also the crystallinity of the PP-phase for both SEBS-PP-oil and TPV blends was investigated and, although being dependent on the preparation method for the SEBS-PP-oil blends, did not reflect in the stress-strain properties.

Atomic Force Microscopy of Elastomers: Morphology, Distribution of Filler Particles, and Adhesion Using Chemically Modified Tips

Abstract The microdispersion of silica and carbon black-based filler particles in unvulcanized and vulcanized ethylene-propylene-diene terpolymer (EPDM) rubbers was investigated by atomic force microscopy (AFM). Tapping mode phase imaging was found to be particularly useful for imaging of the filler aggregates and for the visualization of single primary filler particles. It was demonstrated that the use of silane coupling agents significantly improves the microdispersion of silica filler in the rubber matrix, as compared to (a) silica without coupling agent, and (b) to carbon black. These results correlate very well with the observed mechanical properties of the materials. In addition, adhesion imaging and the analysis of measured pull-off forces allowed us to differentiate between the filler particles and the rubber matrix, as well as between different types of filler particles. The application of chemically modified AFM tips in pull-off force measurements allowed us to monitor the increase of the hydrop...

Fiber Adhesion to Rubber Compounds

Abstract The present paper provides an overview of literature published on fiber-rubber composites. A brief history of Fibers used in rubber applications is given. The emphasis is on the adhesion b...