Rubber recycling is a major environmental challenge, as their covalently crosslinked structure makes it impossible to reprocess via conventional polymer processing technologies. Devulcanization of rubber waste, whereby crosslinks are selectively broken, may provide a solution, as it allows it to be remolded into new shapes. We used two types of ground tire rubbers (GTRs) for this study; mechanically ground and waterjet‐milled GTRs with different particle sizes. First, we revealed the effects of GTR particle size on the devulcanization process. We examined the sol content of the samples before and after devulcanization with two different microwave ovens, a power‐controlled conventional one, and a temperature‐controlled laboratory oven. In the latter one, heating rate and maximum temperature were controlled. We studied the effects of temperature, atmosphere in which the rubber was treated, heating rate, and holding time at maximum temperature. We prepared styrene‐butadiene rubber‐based rubber compounds containing GTR and optimally devulcanized GTR (dGTR_WJ). The physical and mechanical properties of the samples were assessed. The results indicate that both GTR_WJ and dGTR_WJ have an accelerating and a mildly softening effect on curing and dGTR_WJ has a less significant negative effect on mechanical properties: 15 phr GTR_WJ has the same effect as 45 phr dGTR_WJ. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48351.

No abstract

We devulcanized ground tire rubber (GTR) in a laboratory microwave oven and an internal mixer, measured the soluble content and the cross-link density of the samples, and then used Horikx’s analysis. The results showed that microwave treatment caused severe degradation of the polymer chains, while in the case of thermomechanical devulcanization, the selective scission of covalent cross-links is more common. Four devulcanized ground tire rubber (dGTR) samples were chosen for further study and three groups of samples were produced: dGTR samples containing vulcanizing agents and different amounts of paraffin oil (dGTR-based mixtures), natural rubber-based rubber mixtures with different dGTR contents and reference rubber mixtures with dGTR-based mixtures (increased vulcanizing agent contents). Cure characteristics showed a plasticizer-like effect of dGTR. Tensile and tear strength decreased drastically with increasing dGTR content; however, elongation at break values did not follow such a trend. Mechanical properties improved with increased vulcanizing agent contents. The examined properties of the samples improved even further with the use of thermomechanically devulcanized samples. Horikx’s analysis showed that this is attributable to moderate polymer chain scission.

Abstract:The flame retardant synergism between highly stretched polymer fibres and intumescent flame retardant systems was investigated in self-reinforced polypropylene composites. It was found that the structure of reinforcement, such as degree of molecular orientation, fibre alignment and weave type, has a particular effect on the fire performance of the intumescent system. As little as 7.2 wt % additive content, one third of the amount needed in non-reinforced polypropylene matrix, was sufficient to reach a UL-94 V-0 rating. The best result was found in self-reinforced polypropylene composites reinforced with unidirectional fibres. In addition to the fire retardant performance, the mechanical properties were also evaluated. The maximum was found at optimal consolidation temperature, while the flame retardant additive in the matrix did not influence the mechanical performance up to the investigated 13 wt % concentration.

Because of the chemically crosslinked 3D molecular structure of rubbers, their recycling is a challenging task, especially when cost efficiency is also considered. One of the most straightforward procedures is the grinding of discarded rubber products with subsequent devulcanization. The devulcanized rubber can be used as a feedstock for fresh rubber compounds or can be blended with uncured virgin rubber and thermoplastic polymers to form thermoplastic dynamic vulcanizates (TDVs). TDVs combine the beneficial (re)processability of thermoplastics and the elastic properties of rubbers. Our current work focuses on the development of polypropylene (PP)-based TDVs with the use of a tire model rubber (MR) composed of natural rubber (NR) and styrene-butadiene rubber (SBR) in a ratio of 70/30. The research target was the partial substitution of the above fresh MR by microwave devulcanized crumb rubber (dCR). TDVs were produced by continuous extrusion, and the effects of composition (PP/MR/dCR = 40/60/0…50/35/15) and processing parameters (different screw configurations, temperature profiles, the feeding method of PP) were investigated. Results showed that the fresh rubber compound can be replaced up to 10 wt % without compromising the mechanical properties of the resulting TDV.

We devulcanized ground tire rubber (GTR) with microwaves at different temperatures (140−200 °C) and heating rates (2−18 °C/min). We measured the soluble content and the cross-link density of the samples, and then evaluated them by Horikx's analysis and determined the specific microwave energy during devulcanization and the selectivity parameter of the treatments. We also introduced the K•D number that can be calculated as the product of the selectivity parameter (K) and the relative decrease in the cross-link density (D). The results showed that GTR devulcanized at lower temperatures, selectivity was very high, and the degree of devulcanization was adequate. At higher temperatures (180−200 °C), the degree of devulcanization reached 85%, but the selectivity parameter was low, which indicates severe degradation at this temperature range. At lower temperatures (140−160 °C) and decreasing heating rate, i.e., increasing residence time, the degree of devulcanization showed an increase, but at higher temperatures, the heating rate had no significant effect on the degree of devulcanization. We introduced different devulcanized GTRs (dGTRs) to natural rubber-based mixtures and produced samples with two different mixing methods: conventional mixing and so-called two-step mixing. In the latter one, in the first mixing step, we added vulcanizing agents to the dGTR, and in the second mixing step, we added this mixture to the reference mixture. Two-step mixing helped recover mechanical properties, especially tear strength. Scanning electron microscopy− energy-dispersive spectroscopy and atomic force microscopy showed that microwave devulcanization and the vulcanizing agents mixed with dGTR acted in the cross-section of dGTR.

No abstract

In our current paper the preparation and properties of thermoplastic elastomer produced by dynamic vulcanization is presented and discussed. We dynamically vulcanized natural and styrene butadiene rubber (NR/SBR) phase by continuous extrusion. Dispersion and in-situ vulcanization of the rubber phase occurred simultaneously in a co-rotating twin screw extruder. We used a random polypropylene copolymer (rPP) as the thermoplastic matrix and untreated crumb rubber (CR) to partially substitute the neat fresh rubber in order to check whether this is a potential recycling route for waste rubber products. We studied the effect of various rubber formulations, various processing conditions (screw speed and configuration) and various CR particle size distributions by characterizing the mechanical performance of the thermoplastic dynamic vulcanizates (TDVs) with tensile and hardness tests and their morphology by evaluating SEM micrographs taken from the fracture surfaces of the tensile specimens. The results showed that increasing screw speed and more high-shear elements in the screw setup led to a finer dispersion of the rubber phase, resulting in improved mechanical properties. The ultimate tensile properties of the best TDVs reached 20.5 MPa in tensile strength and 550 % in strain at break. However, partial replacement of the fresh rubber with untreated CR caused a significant deterioration in mechanical properties, due to poor adhesion between the CR particles and the matrix and rubber. This suggests that some kind of pre-treatment (e.g. by microwave or other devulcanization techniques) is necessary to enhance the surface activity of the CR particles.