This review provides relevant background information about the vulcanization process, as well as the chemistry of thiuram- and sulfenamide-accelerated sulfur vulcanization with emphasis on the role of activators, to lay a base for further research. It commences with an introduction of sulfur vulcanization and a summary of the reaction mechanisms as described in literature, followed by the role of activators, particularly ZnO. The various possibilities to reduce ZnO levels in rubber compounding, that have been proposed in literature, are reviewed. A totally different approach to reduce ZnO is described in the paragraphs about the various possible roles of multifunctional additives (MFA) in rubber vulcanization. Another paragraph is dedicated to the role of amines in rubber vulcanization, in order to provide some insight in the underlying chemical mechanisms of MFA systems. Furthermore, an overview of Model Compound Vulcanization (MCV) with respect to different models and activator/accelerator systems is given. In the last part of this review, the various functions of ZnO in rubber are summarized. It clearly reveals that the role of ZnO and zinc compounds is very complex and still deserves further clarification.

The addition of zinc oxide (ZnO) as an activator for the sulfur vulcanization of rubbers enhances the vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. The first part of this article deals with the reduction and optimization of the amount of ZnO. Two different rubbers, solution-styrene-butadiene rubber and ethylene-propylene-diene rubber, have been selected for this study. The results demonstrate that the curing and physical properties can be retained when the level of ZnO (Red Seal) is reduced to 1 or 2 phr, respectively. Of particular interest is nano-ZnO, characterized by a nanoscale particle distribution. The cure characteristics indicate that with nano-ZnO, a reduction of zinc by a factor of 10 can be obtained. In the second part, model compound vulcanization is introduced to investigate the effects of ZnO during the different stages of vulcanization. Experiments are described with two models, squalene and 2,3-dimethyl-2-butene, both with benzothiazolesulfenamide-accelerated vulcanization systems. The results demonstrate the influence of ZnO during the different stages of the vulcanization. With ZnO present, a marked decrease can be observed in the sulfur concentration during an early stage of vulcanization, along with a slight delay in the disappearance of the crosslink precursor. The crosslinked product distribution is influenced as well.

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 silica surface. This indicates that the decrease of the flocculation rate is due to the shielding effect of the coupling agent. It is argued that the attractive flux from forces related to polarity differences between the silica and the rubber is the determining factor for silica flocculation.

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Because of environmental concerns, the zinc content in rubber compounds has come under scrutiny; therefore it is necessary to explore possibilities to reduce this zinc content. In this article the application of several zinc complexes as activator for sulfur vulcanization are discussed, in order to find alternatives for the conventionally used ZnO and fatty acid activator system. The effects of different zinc complexes on the cure and physical properties of two widely different rubbers, viz. EPDM and s-SBR, are studied. It can be concluded that zinc-m-glycerolate is a good substitute for ZnO as activator for sulfur vulcanization, in EPDM as well as in s-SBR rubber, without detrimental effects on the cure and physical properties. Furthermore, the results indicate that, dependent on the intended applications, zinc-2-ethylhexanoate represents a substitute for the commonly used ZnO. Zinc stearate is considerably less active as activator in sulfur vulcanization.

The developments on long-term protection of rubber against aerobic aging are reviewed. Although conventional antidegradants such as N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) are still the most widely used antidegradants in rubber, there is a trend and demand for longer-lasting and non-staining products. The relatively low molecular weight (MW) antioxidants have undergone an evolutionary change towards higher molecular weight products with the objective to achieve permanence in the rubber polymer, without loss of antioxidant activity. In the last two decades, several approaches have been evaluated in order to achieve this objective: attachment of hydrocarbon chains to conventional antioxidants in order to increase the MW and compatibility with the rubber matrix; oligomeric or polymeric antioxidants; and polymer bound or covulcanizable antioxidants. The disadvantage of polymer bound antioxidants was tackled by grafting antioxidants on low MW polysiloxanes, which are compatible with many polymers. New developments on antiozonants have focused on non-staining and slow migrating products, which last longer in rubber compounds. Several new types of non-staining antiozonants have been developed, but none of them appeared to be as efficient as the chemically substituted p-phenylenediamines. The most prevalent approach to achieve non-staining ozone protection of rubber compounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The disadvantage of this approach, however, is the complicated mixing procedure needed to ensure that the required small polymer domain size is achieved.

Migration of compounding ingredients is an important factor in the overall properties and performance of rubber articles containing a number of layers for example, a tire, a hose or a conveyor belt. In certain cases, migration of compounding ingredients before, during and after vulcanization in rubber compounds can be of benefit. For example, waxes and p-phenylenediamines antiozonants rely heavily on the migration mechanism to provide optimum protection of rubber products during service against degradation by ozone. In addition, the dispersion of compounding ingredients such as oil, curatives, and antidegradants can be enhanced by diffusion within rubber. In other cases, however, diffusion across a rubber-to-rubber interface can be detrimental to performance. Diffusion will change the distribution of materials which in turn may result in changes in mechanical properties, loss in adhesion or antidegradant protection, and staining of light-colored products. Thus, a better understanding of the migration of chemical additives in rubber could provide the desired distribution of ingredients for obtaining the optimum compound performance.

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