FTIR spectroscopic and thermogravimetric characterization of ground tyre rubber devulcanized by microwave treatment

In this work the phenomena involved with the microwave devulcanization of ground tyre rubber (GTR) were investigated. During studies three types of GTR characterized by different content of organic compounds (elastomers, plasticizers, etc..), carbon black and ash have been analyzed. The chemical structure of GTR before and after microwave devulcanization process was studied by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Furthermore, efficiency of microwave devulcanization conducted at different time was evaluated based on the crosslinking density and sol content values. FTIR spectroscopy results shown that devulcanization of GTR causes a decrease in carbon black with generation of CO2 due to its thermo oxidation, a decrease in structural groups of elastomeric components (mainly methylene and methine) and a breaking of C-S groups and S-S bridges. The presented results indicate the strong correlation between content of SiO2 in GTR and its degree of devulcanization. It was observed that GTR with a high content of SiO2 are easier devulcanized than samples with low content of SiO2, which suggest the presence of silica fillers improve microwave devulcanization efficiencyPostprint (author's final draft

Processing and structure-property relationships of natural rubber/wheat bran biocomposites

In this work, wheat bran was used as cellulosic filler in biocomposites based on natural rubber. The impact of wheat bran content [ranging from 10 to 50 parts per hundred rubber (phr)] on processing, structure, dynamic mechanical properties, thermal properties, physico-mechanical properties and morphology of resulting biocomposites was investigated. For better characterization of interfacial interactions between natural rubber and wheat bran, achieved results were compared with properties of biocomposites filled with commercially available cellulosic fillers—wood flour and microcellulose. It was observed that wheat bran, unlike commercial cellulosic fillers, contains high amount of proteins, which act like plasticizers having profitable impact on processing, physical, thermo-mechanical and morphological properties of biocomposites. This is due to better dispersion and distribution of wheat bran particles in natural rubber, which results in reduction of stiffness and porosity of the biocomposites. Regardless of cellulosic filler type, Wolff activity coefficient was positive for all studied biocomposites implying reinforcing effect of the applied fillers, while tensile strength and elongation at break decreased with increasing filler content. This phenomenon is related to restricted strain-induced crystallization of NR matrix due to limited mobility of polymer chains in the biocomposites. Furthermore, this explains negligible impact of particle size distribution, chemical composition and crystallinity degree of applied cellulosic filler on static mechanical properties of highly-filled NR biocomposites. The conducted investigations show that wheat bran presents interesting alternative for commercially available cellulosic fillers and could be successfully applied as a low-cost filler in polymer compositesPostprint (author's final draft

Preparation and characterization of natural rubber composites highly filled with brewers' spent grain/ground tire rubber hybrid reinforcement

Brewers' spent grain (BSG) and ground tire rubber (GTR) were applied as low-cost hybrid reinforcement natural rubber (NR). The impact of BSG/GTR ratio (in range: 100/0, 75/25, 50/50, 25/75 and 0/100 phr) on processing and performance properties of highly filled natural rubber composites was evaluated by oscillating disc rheometer, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, swelling behavior, tensile tests and impedance tube measurements. It was found that increasing content of GTR in NR/BSG/GTR composites accelerate cross-linking reactions during their preparation, which resulted in decrease of scorch time and optimal cure time. Simultaneously, higher content of GTR filler in NR/BSG/GTR composites significantly improved their physico-mechanical, thermal, morphological and acoustical properties. This indicates better compatibility between natural rubber matrix and GTR than with BSG, which is related to correlation between two factors. First factor is obvious differences in particles size and polarity of GTR and BSG, which affected physical interactions into phase boundary between NR matrix and BSG/GTR hybrid reinforcement. Second factor is possible migration of unreacted curing additives and carbon black particles from GTR filler to NR matrix, which played a significant role on processing and final properties of NR/BSG/GTR compositesPostprint (author's final draft

Structural and physico-mechanical properties of natural rubber/GTR composites devulcanized by microwaves: influence of GTR source and irradiation time

Ground tire rubber from car and truck was modified using microwave irradiation at variable time. The irradiated ground tire rubber was used as filler in composites based on natural rubber. The composites, with high content of ground tire rubber, were prepared using an internal batch mixer and subsequently cross-linked at 160¿. The influence of the ground tire rubber source (car/truck) and irradiation time on structure, physico-mechanical behaviour, thermal properties and morphology of natural rubber/ground tire rubber composites was studied. The interfacial interactions between ground tire rubber and natural rubber as function of ground tire rubber source and irradiation time were evaluated by Fourier transform infrared spectroscopy, thermogravimetric analysis, tensile tests, swelling measurements and scanning electron microscopy. The results showed that irradiation of ground tire rubber slightly enhanced tensile properties and cross-link density of natural rubber/ground tire rubber composites. This effect was more evident in the case of ground tire rubbertruck because of its higher content of natural rubber and was reflected in changes in the interfacial adhesion, which were confirmed by the results of Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy analysisPostprint (author's final draft

Investigating the impact of curing system on structure-property relationship of natural rubber modified with brewery by-product and ground tire rubber

The application of wastes as a filler/reinforcement phase in polymers is a new strategy to modify the performance properties and reduce the price of biocomposites. The use of these fillers, coming from agricultural waste (cellulose/lignocellulose-based fillers) and waste rubbers, constitutes a method for the management of post-consumer waste. In this paper, highly-filled biocomposites based on natural rubber (NR) and ground tire rubber (GTR)/brewers’ spent grain (BSG) hybrid reinforcements, were prepared using two different curing systems: (i) sulfur-based and (ii) dicumyl peroxide (DCP). The influence of the amount of fillers (in 100/0, 50/50, and 0/100 ratios in parts per hundred of rubber) and type of curing system on the final properties of biocomposites was evaluated by the oscillating disc rheometer, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, swelling behavior, tensile testing, and impedance tube measurements. The results show, that the scorch time and the optimum curing time values of sulfur cured biocomposites are affected by the change of the hybrid filler ratio while using the DCP curing system, and the obtained values do not show significant variations. The results conclude that the biocomposites cured with sulfur have better physico-mechanical and acoustic absorption, and that the type of curing system does not influence their thermal stability. The overall analysis indicates that the difference in final properties of highly filled biocomposites cured with two different systems is mainly affected by the: (i) cross-linking efficiency, (ii) partial absorption and reactions between fillers and used additives, and (iii) affinity of additives to applied fillersPostprint (published version

Preliminary investigation on auto-thermal extrusion of ground tire rubber

Ground tire rubber (GTR) was processed using an auto-thermal extrusion as prerequisite to green reclaiming of GTR. The reclaimed GTR underwent a series of tests: thermogravimetric analysis combined with Fourier-transform infrared spectroscopy (TGA-FTIR), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and static headspace and gas chromatography-mass spectrometry (SHS-GC-MS) in order to evaluate the impact of barrel heating solution (with/without external barrel heating) on reclaiming process of GTR. Moreover, samples were cured to assess the impact of reclaiming heating solution on curing characteristics and physico-mechanical properties. Detailed analysis of the results indicated that the heat supplied by the machinery was replaced by energy generated due to the high shearing phenomenon, what significantly influenced energy consumption and hereby lowered processing costPostprint (published version

Morphology, Thermo-Mechanical Properties and Biodegradibility of PCL/PLA Blends Reactively Compatibilized by Different Organic Peroxides

Reactive blending is a promising approach for the sustainable development of bio-based polymer blends and composites, which currently is gaining more and more attention. In this paper, biodegradable blends based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared via reactive blending performed in an internal mixer. The PCL and PLA content varied in a ratio of 70/30 and 55/45. Reactive modification of PCL/PLA via liquid organic peroxides (OP) including 0.5 wt.% of tert-butyl cumyl peroxide (BU), 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane (HX), and tert-butyl peroxybenzoate (PB) is reported. The materials were characterized by rotational rheometer, atomic force microscopy (AFM), thermogravimetry (TGA), differential scanning calorimetry (DSC), tensile tests and biodegradability tests. It was found that the application of peroxides improves the miscibility between PCL and PLA resulted in enhanced mechanical properties and more uniform morphology. Moreover, it was observed that the biodegradation rate of PCL/PLA blends reactively compatibilized was lower comparing to unmodified samples and strongly dependent on the blend ratio and peroxide structure. The presented results confirmed that reactive blending supported by organic peroxide is a promising approach for tailoring novel biodegradable polymeric systems with controllable biodegradation rates.This research work was funded by the National Science Centre (NCN Poland) grant number PRELUDIUM 15 project 2018/29/N/ST8/02042

Processing, mechanical and morphological properties of GTR modified by SBS copolymers

In this work, ground tire rubber (GTR) was thermo-mechanically treated in the presence of styrene-butadiene-styrene (SBS) copolymers. During preliminary investigation, the effects of different SBS copolymer grades, the variable content of SBS copolymer on the Mooney viscosity, and the thermal and mechanical properties of modified GTR were determined. Subsequently, GTR modified by SBS copolymer and cross-linking agents (sulfur-based system and dicumyl peroxide) was characterized by assessment of rheological, physico-mechanical, and morphological properties. Rheological investigations showed that linear SBS copolymer, with the highest melt flow rate among studied SBS grades, was the most promising modifier of GTR, considering processing behavior. It was also observed that an SBS improves the thermal stability of the modified GTR. However, it was found that higher content of SBS copolymer (above 30 wt%) does not bring any effective changes and, for economic reasons, is inefficient. The results showed that samples based on GTR modified by SBS and dicumyl peroxide have better processability and slightly higher mechanical properties compared to samples cross-linked by a sulfur-based system. This is due to the affinity of dicumyl peroxide to the co-cross-linking of GTR and SBS phasesThe authors are grateful for the research foundation of project WPC 2/SUSDEV4REC/2021, supported by the National Centre for Research and Development (Poland), and project 2021YFE0105200, supported by the Ministry of Science and Technology (China)Postprint (published version

Reclaimed rubber/poly(e-caprolactone) blends: structure, mechanical, and thermal properties

The amount of elastomeric waste, especially from tires is constantly increasing on a globalscale. The recycling of these residua should be considered a priority. Compounding the waste rubberswith other polymers can be an excellent alternative to reuse waste materials. This procedure requiressolving the issue of the lack of compatibility between the waste rubber particles and other polymers.Simultaneously, there is a claim for introducing biodegradable plastics materials to reduce theirenvironmental impact. In this work, reclaimed rubber/poly(e-caprolactone) (RR/PCL) blends areproposed to enhance the recycling and upcycling possibilities of waste rubbers. The results showthat the addition of PCL to the RR allows obtaining blends with improved mechanical properties,good thermal stability, and enhanced interfacial compatibility between the used components. Structureand properties of the proposed RR/PCL have been studied by means of static and dynamic mechanicaltesting, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA)-FTIR analysisPostprint (published version

Influencia de las condiciones de tratamiento con microondas de caucho triturado de neumático sobre las propiedades físico-mecánicas y estructurales de composites NBR / NR / GTR

The increasing amount of tires used in the industry induces the researchers to find alternatives to the recycling of the end-of-life tires. Several alternatives in order to application of ground tire rubber GTR include their incorporation as a filler in composites. The main issue in this approach is the lack of compatibility between GTR and polymer matrix. In order to solve this problem the devulcanization by microwaves has been proposed as an interesting approach in order to improve the subsequent crosslinking when the GTR is incorporated to an elastomeric matrix and subsequently co-vulcanizated. In this article a blend formed by natural rubber NR and nitrile butadiene rubber NBR has been proposed as a suitable matrix for composites including GTR. In order to improve the compatibility, the GTR was treated by microwaves prior to its application as semi-reinforcement in rubber matrix. The results indicate that the pretreatment of GTR by microwaves improves the cross-linking and co-vulcanization of used elastomers, what have a positive influence on the mechanical behaviour and microstructure of the NR/NBR/GTR composites evaluated by tensile tests, equilibrium swelling, Thermo Gravimetric Analysis (TGA), Infrared Spectroscopy (FTIR) and Scanning Electronic Microscopy (SEM)Postprint (published version