No 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, which may have an adverse effect on the properties in the final product. Some coupling agents may also act as sulfur donor. The dump temperature employed during mixing and the length of time the compound is exposed to that temperature govern the reaction mechanisms of the coupling agent and determine whether the agent leads to the formation of a silica-rubber bond or acts as a curing agent. A temperature of at least 130 °C is necessary to ensure that the reaction between the coupling agent and the silica proceeds, whereas the coupling agent starts to react with the rubber or to donate sulfur, resulting in scorching, at temperatures above 160 °C. An increase in the 300% modulus and/or G' at 100% strain above 150 °C is an indication of scorching caused by the sulfur in the coupling agent. No scorching is observed when a coupling agent without sulfur is used. Another important parameter is the mixing time. It was observed that the coupling agent must be mixed with the silica for at least 10 minutes at 150 °C to obtain a sufficient degree of coupling.

It is generally believed that only intermolecular, elastically-effective crosslinks influence elastomer properties. The role of the intramolecular modifications of the polymer chains is marginalized. The aim of our study was the characterization of the structural parameters of cured elastomers, and determination of their influence on the behavior of the polymer network. For this purpose, styrene-butadiene rubbers (SBR), cured with various curatives, such as DCP, TMTD, TBzTD, Vulcuren®, DPG/S8, CBS/S8, MBTS/S8 and ZDT/S8, were investigated. In every series of samples a broad range of crosslink density was obtained, in addition to diverse crosslink structures, as determined by equilibrium swelling and thiol-amine analysis. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the glass transition process, and positron annihilation lifetime spectroscopy (PALS) to investigate the size of the free volumes. For all samples, the values of the glass transition temperature (Tg) increased with a rise in crosslink density. At the same time, the free volume size proportionally decreased. The changes in Tg and free volume size show significant differences between the series crosslinked with various curatives. These variations are explained on the basis of the curatives’ structure effect. Furthermore, basic structure-property relationships are provided. They enable the prediction of the effect of curatives on the structural parameters of the network, and some of the resulting properties. It is proved that the applied techniques—DSC, DMA, and PALS—can serve to provide information about the modifications to the polymer chains. Moreover, on the basis of the obtained results and considering the diversified curatives available nowadays, the usability of “part per hundred rubber” (phr) unit is questioned.

The partial replacement of silica by high specific surface area and high structure Carbon Black (CB) N134 as secondary filler, keeping the same total filler content at 55 phr, shows a clear synergistic effect on overall performance. At low content of CB, i.e. in the range of 0-36 wt% of CB relative to total filler amount, the Payne effect and tan delta at both 0 � C and 60 � C change marginally, but thereafter gradually increase. Cure times are shortened in the presence of CB, facilitating an increase of productivity. Bound rubber content and mechanical properties show an optimum at 18 wt% of CB relative to total filler amount or at a ratio of silica/CB 45/10 phr. With regard to tire performance as indicated by the laboratory test results, the abrasion resistance, wet grip and ice traction can therefore be enhanced while maintaining the tire rolling resistance at the optimum level for this silica/CB ratio.

Diphenyl guanidine (DPG) is an essential ingredient in silica-reinforced rubber compounds for low rolling resistance tires, as it not only acts as a secondary accelerator, but also as a catalyst for the silanization reaction. However, because of concern over the toxicity of DPG that liberates aniline during high-temperature processing, safe alternatives are required. The present work studies several amines as potential alternatives for DPG. Different amines (i.e., hexylamine, decylamine, octadecylamine, cyclohexylamine, dicyclohexylamine, and quinuclidine) are investigated in a model system, as well as in a practical rubber compound by taking the ones with DPG and without amine as references. The kinetics of the silanization reaction of the silica/silane mixtures are evaluated using model compounds. The mixtures with amines show up to 3.7 times higher rate constants of the primary silanization reaction compared to the compound without amine. Linear aliphatic amines promote the rate constant of the primary silanization reaction to a greater extent compared to amines with a cyclic structure. The amines with short-alkyl chains that provide better accessibility towards the silica surface, enhance the primary silanization reaction more than the ones with long-alkyl chains. The different amines have no significant influence on the rate constant of the secondary silanization reaction. The amine types that give a higher primary silanization reaction rate constant show a lower flocculation rate in the practical compounds. For the systems with a bit lower primary silanization reaction rate, but higher extent of shielding or physical adsorption that still promotes higher interfacial compatibility between the elastomer and the filler surface, the rubber compounds show a lower Payne effect which would indicate lower filler-filler interaction. However, the flocculation rate constant remained high.

The feasibility of the use of epoxidized palm oil (EPO) and amine-modified epoxidized palm oil (mEPO) as process oils in silica-reinforced natural rubber compounds is studied. The chemical structures of EPO and mEPO are characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy (1H-NMR). Amine modification for 3 and 5 h leads to mEPOs with 0.03 and 0.04 mmol of amine in 1 g of oil, referred to as 0.03 mEPO and 0.04 mEPO, respectively. The properties of rubber compounds containing modified palm oils are investigated by taking those with TDAE oil and those without oil as references. The use of process oils clearly enhances the processibility (i.e., lower mixing torque and complex viscosity) and mechanical and dynamic mechanical properties of the rubber compounds as compared with compounds without oil. The rubber compounds with EPO and 0.03 mEPO show a lower Payne effect (i.e., less filler–filler interaction) than the rubber compound with TDAE because of the shielding effect of the oils on the silica surface. The use of mEPO boosts the vulcanization reaction, resulting in much better cure torque difference, which indicates a higher crosslink density due to the amino groups present in mEPO as compared with TDAE. Therefore, rubber compounds with mEPOs have better mechanical properties (i.e., reinforcement index, tensile strength, and elongation at break) and better elastic response under dynamic deformation, as indicated by a lower loss tangent at 60 °C as compared with the mix with TDAE.

The effect of the sulfur rank (4-0) and of the carbon rank (2-10) of equivalents of bis(triethoxysilylpropyl)tetrasulphide TESPT as coupling agents for silica-reinforced tire tread compounds, is the subject of this study. The coupling agents are added in quantities equimolar to TESPT. Sulfur correction for lower sulfur ranks than TESPT is performed either in the final mixing step or in the first mixing step in an internal mixer. Without sulfur correction the silanes studied show a marked difference in processing as well as in the final properties of the rubber. When sulfur correction is made in the final mix together with the addition of vulcanization ingredients, all sulfur-containing silanes behave more like TESPT. The disulphide (TESPD) shows final properties similar to those of TESPT; the mixing behavior shows improved scorch safety. This is lost when sulfur correction is applied in the first mix. Sulfur-free silanes do not react on sulfur correction during processing and show only a slight improvement in mechanical properties. A silane without sulfur, having a carbon rank of 10 (DTES) shows the best processing, although final mechanical properties are inferior to TESPT.

The addition of a coupling agent to silica-rubber compounds enhances filler-matrix compatibility. The coupling agent under study, TESPT, can also act as a sulfur donor, which leads to premature scorch in the mixer. The effect of the presence of zinc oxide in the internal mixer at higher dump temperatures was demonstrated by dynamic mechanical testing. A lower tendency to scorch was seen when zinc oxide was omitted during the internal mixing stage and added only later together with the curing additives on a two roll mill. Zinc oxide primarily interferes with the reaction between the coupling agent and the silica surface, as shown by the reaction rate constants obtained with rheological experiments. Further confirmation was obtained by HPLC-experiments: the reaction rate constants of TESPT with silica for the samples with zinc oxide present, were lower at higher temperatures in comparison with samples without zinc oxide. XPS data confirmed that zinc oxide can indeed react with the silica surface. When zinc oxide is included in the internal mixer stage, shorter scorch times are obtained for curing when compared to compounds where no zinc oxide is included during mixing and only added later on. These shorter scorch times are the result of filler flocculation of the silica during the curing stage.