Over the past decades, increased scientific and research activity has been observed in the development of new, innovative materials for various end uses. This is mainly due to the growing ecological, environmental, and material awareness of many industries and societies. Equisteum arvense-horsetail is a plant that has demonstrated its properties in pharmacological and clinical aspects as well as in vitro and in vivo biological activity. This article presents a new method of using horsetail as a natural, lignocellulosic filler for a natural rubber matrix. In-depth characteristics of the applied bio-additive were prepared based on several research techniques and methods such as ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy with energy dispersive X-RAY spectroscopy, thermogravimetric analysis, and flame atomic absorption spectroscopy. Elastomer composites were prepared as a function of horsetail content. Then, an analysis of their main functional properties was performed, including mechanical properties and susceptibility to accelerated aging processes such as thermo-oxidative, ultraviolet radiation, and weathering. The research emphasizes the significant value of horsetail in its new role-as an active filler of elastomer biocomposites. The obtained results confirmed that horsetail is lignocellulosic material thermally stable up to 180 °C. Horsetail is an active filler to natural rubber, positively affecting mechanical strength. Due to the presence of flavonoids and phenolic acids in horsetail, it can be used as a polymer anti-aging agent.

https://www.mdpi.com/1996-1944/13/11/2526/pdf

Horsetail (Equisetum Arvense) as a Functional Filler for Natural Rubber Biocomposites.

The work was aimed at the investigation of influence of peroxide curing system on cross-linking and properties of rubber compounds based on SBR. First, the temperature of vulcanization and the amount of dicumyl peroxide on curing process and physical-mechanical properties were investigated. Then, co-agents Type I and Type II were added to the rubber formulations cured with peroxide. The results revealed that the increase in temperature leads to the acceleration of curing process while both, curing kinetics and physical-mechanical properties were influenced by the amount of peroxide. The application of Type I co-agents resulted in the acceleration of curing process and increase in cross-link density of vulcanizates, which was reflected in the increase of hardness and decrease of elongation at break. The influence of Type II co-agents on curing kinetics was negligible, while most of them caused the reduction in cross-linking degree of vulcanizates. Type I co-agents contributed to the improvement of tensile strength of vulcanizates, while the influence of Type II co-agents on tensile strength was of minor importance.

Peroxide curing systems applied for cross-linking of rubber compounds based on SBR

In this study, peppermint (Mentha piperita L.), German chamomile (Matricaria chamomilla L.) and yarrow (Achillea millefolium L.) were applied as natural fibrous fillers to create biocomposites containing substances of plant origin. The purpose of the work was to investigate the activity and effectiveness of selected plants as a material for the modification of natural rubber composites. This research was the first approach to examine the usefulness of peppermint, German chamomile and yarrow in the field of polymer technology. Dried and ground plant particles were subjected to Fourier transmission infrared spectroscopy (FTIR) and UV–Vis spectroscopy, thermogravimetric analysis (TGA), goniometric measurements (contact angle) and scanning electron microscopy (SEM). The characterization of natural rubber composites filled with bio-additives was performed including rheometric measurements, FTIR, TGA, cross-linking density, mechanical properties and colour change after simulated aging processes. Composites filled with natural fillers showed improved barrier properties and mechanical strength. Moreover, an increase in the cross-linking density of the materials before and after the simulated aging processes, compared to the reference sample, was observed.

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Potential Application of Peppermint (Mentha piperita L.), German Chamomile (Matricaria chamomilla L.) and Yarrow (Achillea millefolium L.) as Active Fillers in Natural Rubber Biocomposites.

Common nettle (Urtica Dioica L.), as a natural fibrous filler, may be part of the global trend of producing biocomposites with the addition of substances of plant origin. The aim of the work was to investigate and explain the effectiveness of common nettle as a source of active functional compounds for the modification of elastomer composites based on natural rubber. The conducted studies constitute a scientific novelty in the field of polymer technology, as there is no research on the physico-chemical characteristics of nettle bio-components and vulcanizates filled with them. Separation and mechanical modification of seeds, leaves, branches and roots of dried nettle were carried out. Characterization of the ground plant particles was performed using goniometric measurements (contact angle), Fourier transmission infrared spectroscopy (FTIR), themogravimetric analysis (TGA) and scanning electron microscopy (SEM). The obtained natural rubber composites with different bio-filler content were also tested in terms of rheological, static and dynamic mechanical properties, cross-linking density, color change and resistance to simulated aging processes. Composites with the addition of a filler obtained from nettle roots and stems showed the highest mechanical strength. For the sample containing leaves and branches, an increase in resistance to simulated ultraviolet and thermo-oxidative aging processes was observed. This phenomenon can be attributed to the activity of ingredients with high antioxidant potential contained in the plant.

https://www.mdpi.com/1996-1944/14/7/1616/pdf

Common Nettle (Urtica dioica L.) as an Active Filler of Natural Rubber Biocomposites.

Zinc oxide nanoparticles (N-ZnO) and zinc complexes with 1,3-diketones of different structures were applied instead of microsized zinc oxide (M-ZnO) to activate the sulfur vulcanization of styrene-butadiene rubber (SBR). The influence of vulcanization activators on the cure characteristics of rubber compounds, as well as crosslink density and functional properties of SBR vulcanizates, such as tensile properties, hardness, damping behavior, thermal stability and resistance to thermo-oxidative aging was explored. Applying N-ZnO allowed to reduce the content of zinc by 40% compared to M-ZnO without detrimental influence on the cure characteristic and performance of SBR composites. The activity of zinc complexes in vulcanization seems to strongly depend on their structure, i.e., availability of zinc to react with curatives. The lower the steric hindrance of the substituents and thus the better the availability of zinc ions, the greater was the activity of the zinc complex and consequently the higher the crosslink density of the vulcanizates. Zinc complexes had no detrimental effect on the time and temperature of SBR vulcanization. Despite lower crosslink density, most vulcanizates with zinc complexes demonstrated similar or improved functional properties in comparison with SBR containing M-ZnO. Most importantly, zinc complexes allowed the content of zinc in SBR compounds to be reduced by approximately 90% compared to M-ZnO.

https://www.mdpi.com/1996-1944/14/14/3804/pdf

Zinc Complexes with 1,3-Diketones as Activators for Sulfur Vulcanization of Styrene-Butadiene Elastomer Filled with Carbon Black.

Organic zinc salts and complexes were applied as activators for sulfur vulcanization of styrene-butadiene elastomer (SBR) in order to reduce the content of zinc ions in rubber compounds as compared with conventionally used zinc oxide. In this article, the effects of different organic zinc activators on the curing characteristics, crosslink densities, and mechanical properties of SBR as well as the aging resistance and thermal behavior of vulcanizates are discussed. Organic zinc salts seem to be good substitutes for zinc oxide as activators for sulfur vulcanization of SBR rubber, without detrimental effects to the vulcanization time and temperature. Moreover, vulcanizates containing organic zinc salts exhibit higher tensile strength and better damping properties than vulcanizate crosslinked with zinc oxide. The application of organic zinc activators allows the amount of zinc ions in SBR compounds to be reduced by 70-90 wt % compared to vulcanizate with zinc oxide. This is very important for ecological reasons, since zinc oxide is classified as being toxic to aquatic species.

https://www.mdpi.com/2073-4360/11/10/1723/pdf

Judyta Kucharska

Papers

Organic Zinc Salts as Pro-Ecological Activators for Sulfur Vulcanization of Styrene–Butadiene Rubber