Jacques W.M. Noordermeer

Activators in Accelerated Sulfur Vulcanization

Abstract 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 syst...

Effect of zinc complexes as activator for sulfur vulcanization in various rubbers

Abstract 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.

Zinc loaded clay as activator in sulfur vulcanization: A new route for zinc oxide reduction in rubber compounds

Abstract Concern about the release of eco-toxic zinc species from rubbers into the environment leads to an increasing interest in potential substitutes. Although alternative metal oxides and zinc compounds as activators for sulfur vulcanization have been studied thoroughly, at present no viable alternative has been found to eliminate ZnO completely from rubber compounds, without significantly jeopardizing processing as well as performance characteristics. In this paper, the application of a new activator for sulfur vulcanization will be discussed. This activator is developed based on the assumption that an increase in the availability of Zn2+-ions could lead to a considerable reduction of ZnO in rubber compounds. Montmorillonite clay was used as carrier material and loaded with Zn2+-ions via an ion-exchange process. Application in a wide range of natural and synthetic rubbers has been explored. Results clearly demonstrate that this Zn-Clay can substitute conventional ZnO, retaining the curing and physical...

Multifunctional Additives as Zinc-Free Curatives for Sulfur Vulcanization

Abstract Concern about the release of eco-toxic zinc species from rubbers into the environment leads to an increasing interest in potential substitutes. This investigation reports on the applicatio...

Existence of a Tribo-Modified Surface Layer on SBR Elastomers: Balance between Formation and Wear of the Modified Layer

In most of the tribological contacts, the composition and tribological properties of the original interface will change during use. The tribo-films, with modified properties compared to the bulk, are dynamic structures that play a significant role in friction. The existence of a tribo-modified surface layer and its importance on the overall friction of elastomers has been shown both theoretically and experimentally before. The characteristics of the modified surface layer deserve specific attention since the tribological properties of elastomers in contact with a rough counter-surface are determined by these modified surfaces together with the properties of bulk of the material. Both the formation of the modified layer and the break down (wear) of it are of importance in determining the existence and thickness of the tribo-modified layer. In this study, the importance of the wear is emphasized by comparing two styrene butadiene rubber-based elastomers in contact with a granite sphere. A current status of perception of the removal and the stability of the modified surface layers on rubbers is introduced as well as experimental work related to this matter and discussion within literature. Pin-on-disk friction tests are performed on two SBR-based samples in contact with a granite sphere under controlled environmental conditions to form the modified surface layer. Although the hysteresis part of the friction force which has a minor contribution in the overall friction is not markedly different, the total measured friction coefficient differs significantly. Mechanical changes both inside and outside the wear track are determined by atomic force microscope nano-indentations at different timescales to examine the modified surface layer on the test samples. The specific wear rates of the two tribo-systems are compared, and the existence of the modified surface layer, the different measured friction coefficient and the running-in distances toward steady-state friction are explained considering different wear rates. A conceptual model is presented, correlating the energy input into the tribo-system and the existence of a modified surface layer.

MIXING, CURING AND REINFORCEMENT OF NR/BR/EPDM BLENDS FOR TIRE SIDEWALL APPLICATIONS

Abstract Tire sidewalls generally consist of blends of natural rubber (NR) and butadiene rubber (BR), containing a high concentration of antiozonants to provide ozone resistance. However, the most widely used antiozonant, N-(1, 3-dimethyl-butyl)-N-phenyl-p-phenylenediamine (6PPD), is a staining, toxic and environmentally unfriendly substance. Incorporation of Ethylene-Propylene-Diene rubber (EPDM) into NR/BR is a way of achieving non-staining ozone resistance. But blending of dissimilar rubbers is severely restricted due to viscosity mismatch, thermodynamic incompatibility, cure incompatibility and heterogeneous filler distribution. This chapter gives an overview of the various research approaches in the field of blending dissimilar rubbers so far, as well as the mechanism of ozone protection by incorporation of EPDM in tire sidewall applications.

Compatibilization of silica-filled natural rubber compounds by combined effects of functionalized low molecular weight rubber and silane

Epoxidized low molecular weight natural rubber (ELMWNR) with 28 mol% epoxide groups and weight average molecular weight of 49,000 g mol−1 was prepared by oxidative degradation of epoxidized natural rubber (NR) using periodic acid in the latex state. ELMWNR-28 was used at 10 parts per hundred parts of rubber (phr) loading in combination with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) as the silane coupling agent in the range of 0–4.5 phr in silica-reinforced NR compounds. The use of TESPT in combination with ELMWNR-28 gives lower mixing torques and compound viscosities compared with the use of TESPT alone and the system without any compatibilizer. The bound rubber content, modulus, and tensile strength of the compounds with only TESPT strongly depend on the TESPT loading. The use of ELMWNR-28 as a compatibilizer clearly improves such properties compared with the non-compatibilized systems. By adding TESPT into the compound with ELMWNR-28, the properties further improve with increasing TESPT loading. The combined effect of ELMWNR-28 at 10 phr with a small amount of TESPT at 1.5 phr results in compounds with superior processability (i.e. low Mooney viscosity and Payne effect), and only slightly lower modulus and reinforcement index (M300/M100) compared with the use of the optimum content of TESPT. This compatibilizer/TESPT combination has the environmental benefits that the ELMWNR is a naturally based product, and that the reduced amount of TESPT silane coupling agent emits a greatly reduced amount of ethanol during processing.

Property enhancement of silica-filled natural rubber compatibilized with epoxidized low molecular weight rubber by extra sulfur

The properties of both compounds and vulcanizates of silica-filled natural rubber (NR) compatibilized with epoxidized low molecular weight natural rubbers (ELMWNRs) consisting of 12 and 28 mol% epoxide are investigated. The ELMWNRs with a molecular weight range of 50,000 to 60,000 g/mol are produced by depolymerization of epoxidized natural rubber (ENR) latex using periodic acid, and then used as compatibilizer in a range of 0 to 15 phr in virgin NR. The compounds with LMWNR without epoxide groups, and with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) coupling agent are also prepared for comparison purpose. Incorporation of ELMWNRs lowers Mooney viscosity and Payne effect to the level closed to that of silica/TESPT compound, and clearly enhances the modulus and tensile strength of vulcanizates compared to the compounds with no compatibilizer and LMWNR. The higher epoxide groups content results in the better tensile properties but somewhat less than the compound with TESPT. Addition of extra sulfur into the compounds with LMWNR and ELMWNRs to compensate for the sulfur released from silane molecule in the silica/TESPT system shows small influence on Mooney viscosity, but remarkably enhances 300% modulus, tensile strength and loss tangent at 60°C as a result of the better network formation.

Silica-Reinforced Natural Rubber Compounds Compatibilized through the Use of Epoxide Functional Groups and TESPT Combination

Epoxidized natural rubber (ENR) and bis-(3-triethoxysilylpropyl) tetrasulfide (TESPT) were used to improve the properties of silica-filled NR. The use of ENR containing 51 mol% epoxide groups (ENR-51) as a compatibilizer without TESPT was optimized at 7.5 phr, based on the results of Payne effect and tensile strength. By using 7.5 phr of ENR-51 with varying amounts of TESPT in a range of 2 to 5 wt% relative to the silica, the properties of compounds were compared to those of the ones with optimum TESPT content (i.e. 8.6 wt% relative to the silica) and without. The addition of TESPT to the ENR-51 compatibilized silica-filled NR compound had no effect on Mooney viscosity but lowered the Payne effect to the same level as that of the silica/TESPT compound, and significantly decreased both scorch and optimum cure times. The silica-filled NR with ENR and the small amount of TESPT combination showed a further increase in tensile strength to match that of the optimized silica/TESPT system, while maintained the elongation at break. This work demonstrates that the use of ENR as compatibilizer clearly enhances the properties of silica-filled NR compounds, and that such properties can be further improved by adding TESPT at a half or less amount of TESPT normally needed for silica-filled compounds.

Effect of chlorinated polyethylene on dynamic mechanical and thermal properties of SAN/EPDM blends in dependence of mixing conditions

The effect of chlorinated polyethylene (CPE) on the compatibilization and thermal properties of styrene-acrylonitrile copolymers (SAN)/Ethylele-Propylene-Diene-polyMethylene rubber (EPDM) blends (80/20) was investigated. Two different mixing procedures were employed, that is, single- and two-step blending. In the single-step process, EPDM was melt blended with CPE and SAN simultaneously, which led to a droplet morphology. In the two-step process, first, a masterbatch of EPDM and CPE in SAN was prepared, and then mixed with further amounts of SAN and CPE in order to reach the same fixed blend ratio of 80/20 for SAN/EPDM. The morphology changed from EPDM droplets for the one-step mixing to co-continuous for the two-step blending process. This morphological change was reflected in a change of the complex modulus. The characteristics of thermogravimetric analysis (TGA) curves (T1%, T5%, T30%, and T50%) were examined, as indicators for improved thermal stability of the blends. The intermolecular interaction characterized by the Kwei equation showed higher values for the blends prepared by the two-step mixing procedure. The dynamic mechanical analysis supported the occurrence of chain scission in the SAN phase at the beginning of aging and cross-linking of SAN at higher temperatures and longer times as a result of cyclization of CN groups in SAN.