Management of ground tire rubber waste by incorporation into polyurethane-based composite foams.

Rapid economic growth implicated the developing multiple industry sectors, including the automotive branch, increasing waste generation since recycling and utilization methods have not been established simultaneously. A very severe threat is the generation of enormous amounts of post-consumer tires considered burdensome waste, e.g., due to the substantial emissions of volatile organic compounds (VOCs). Therefore, it is essential to develop novel, environmentally friendly methods for their utilization, which would hinder their environmental impacts. One of the most promising approaches is shredding, resulting in the generation of ground tire rubber (GTR), which can be introduced into polymeric materials as filler. The presented work is related to the thermomechanical treatment of GTR in a twin-screw extruder with zinc borate, whose incorporation is aimed to enhance shear forces within the extruder barrel. Modified GTR was introduced into flexible polyurethane (PU) foams, and the impact of modification parameters on the cellular structure, static and dynamic mechanical performance, thermal stability, as well as thermal insulation, and acoustic properties was investigated. Emissions of VOCs from applied fillers and prepared composites were monitored and evaluated. Depending on the treatment parameters, beneficial changes in foams' cellular structure were noted, which enhanced their thermal insulation performance, mechanical strength, and thermal stability. It was proven that the proposed method of GTR thermomechanical treatment assisted by zinc borate particles might benefit the performance of flexible PU foamed composites and hinder VOC emissions, which could broaden the application range of GTR and provide novel ways for its efficient utilization.

Cross-Linking, Morphology, and Physico-Mechanical Properties of GTR/SBS Blends: Dicumyl Peroxide vs. Sulfur System.

In this work, ground tire rubber and styrene-butadiene block copolymer (GTR/SBS) blends at the ratio of 50/50 wt%, with the application of four different SBS copolymer grades (linear and radial) and two types of cross-linking agent (a sulfur-based system and dicumyl peroxide), were prepared by melt compounding. The rheological and cross-linking behavior, physico-mechanical parameters (i.e., tensile properties, abrasion resistance, hardness, swelling degree, and density), thermal stability, and morphology of the prepared materials were characterized. The results showed that the selected SBS copolymers improved the processability of the GTR/SBS blends without any noticeable effects on their cross-linking behavior-which, in turn, was influenced by the type of cross-linking agent used. On the other hand, it was observed that the tensile strength, elongation at break, and abrasion resistance of the GTR/SBS blends cured with the sulfur system (6.1-8.4 MPa, 184-283%, and 235-303 mm3, respectively) were better than those cross-linked by dicumyl peroxide (4.0-7.8 MPa, 80-165%, and 351-414 mm3, respectively). Furthermore, it was found that the SBS copolymers improved the thermal stability of GTR, while the increasing viscosity of the used SBS copolymer also enhanced the interfacial adhesion between the GTR and SBS copolymers, as confirmed by microstructure evaluation.

Insights into Stoichiometry Adjustments Governing the Performance of Flexible Foamed Polyurethane/Ground Tire Rubber Composites.

Polyurethanes (PU) are widely applied in the industry due to their tunable performance adjusted by changes in the isocyanate index-stoichiometric balance between isocyanate and hydroxyl groups. This balance is affected by the incorporation of modifiers of fillers into the PU matrix and is especially crucial for PU foams due to the additional role of isocyanates-foaming of the material. Despite the awareness of the issue underlined in research works, the contribution of additives into formulations is often omitted, adversely impacting foams' performance. Herein, flexible foamed PU/ground tire rubber (GTR) composites containing 12 different types of modified GTR particles differing by hydroxyl value (LOH) (from 45.05 to 88.49 mg KOH/g) were prepared. The impact of GTR functionalities on the mechanical, thermomechanical, and thermal performance of composites prepared with and without considering the LOH of fillers was assessed. Formulation adjustments induced changes in tensile strength (92-218% of the initial value), elongation at break (78-100%), tensile toughness (100-185%), compressive strength (156-343%), and compressive toughness (166-310%) proportional to the shift of glass transition temperatures (3.4-12.3 °C) caused by the additional isocyanates' reactions yielding structure stiffening. On the other hand, formulation adjustments reduced composites' thermal degradation onset due to the inferior thermal stability of hard segments compared to soft segments. Generally, changes in the composites' performance resulting from formulation adjustments were proportional to the hydroxyl values of GTR, justifying the applied approach.

Ground tire rubber functionalization as a promising approach for the production of sustainable adsorbents of environmental pollutants.

Waste tires management and further utilization are currently one of the biggest concerns regarding the environment and human health protection. At present, shredding, grinding, or pulverization of waste tires are the most popular options for industrial recycling. Although many solutions for ground tire rubber (GTR) applications were checked and verified so far, their further implementation at an industrial scale is still very limited. In this brief review work, ground tire rubber functionalization strategies as a promising approach for the production of sustainable adsorbents of environmental pollutants were presented and discussed. Our findings indicate that suitable functionalization of GTR significantly improves adsorption capacity or selectivity of prepared GTR-based adsorbents. However, it should be mentioned that most of the performed research based on multi-step and time-consuming protocols of GTR functionalization is performed usually in the presence of solvents, which results in very low efficiency and as a consequence high-cost and limited applications. Current research trends showed that reactive extrusion can be considered as efficient, solvent-free, and pro-ecological alternative for commonly investigated periodic methods of GTR functionalization. This work shows that reactive extrusion is a promising method for further development of GTR-based adsorbents dedicated to environmental pollutants.

Ground Tire Rubber Modified by Elastomers via Low-Temperature Extrusion Process: Physico-Mechanical Properties and Volatile Organic Emission Assessment.

In this paper, low-temperature extrusion of ground tire rubber was performed as a pro-ecological waste tires recycling method. During this process, ground tire rubber was modified with constant content of dicumyl peroxide and a variable amount of elastomer (in the range: 2.5-15 phr). During the studies, three types of elastomers were used: styrene-butadiene rubber, styrene-ethylene/butylene-styrene grafted with maleic anhydride and ethylene-octene copolymer. Energy consumption measurements, curing characteristics, physico-mechanical properties and volatile organic compounds emitted from modified reclaimed GTR were determined. The VOCs emission profile was investigated using a passive sampling technique, miniature emission chambers system and static headspace analysis and subsequently quantitative or qualitative analysis by gas chromatography. The VOCs analysis showed that in the studied conditions the most emitted volatile compounds are dicumyl peroxide decomposition by-products, such as: α-methylstyrene, acetophenone, α-cumyl alcohol, methyl cumyl ether, while the detection level of benzothiazole (devulcanization "marker") was very low. Moreover, it was found that the mechanical properties of the obtained materials significantly improved with a higher content of styrene-butadiene rubber and styrene-ethylene/butylene-styrene grafted with maleic anhydride while the opposite trend was observed for ethylene-octene copolymer content.

GTR/Thermoplastics Blends: How Do Interfacial Interactions Govern Processing and Physico-Mechanical Properties?

In this work, GTR/thermoplastics blends (in ratio 50/50 and 75/25 wt.%) were prepared by melt-compounding in an internal mixer. During research, trans-polyoctenamer rubber (TOR), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (EOC), and linear low-density polyethylene (LLDPE), were used in their thermoplastic phase. Microstructure and processing-performance property interrelationships of the studied materials were investigated by: atomic force microscopy (AFM), scanning electron microscopy (SEM), rubber process analyzer (RPA), Mooney viscometer, plastometer, gas chromatography with mass spectrometry, differential scanning calorimetry (DSC), tensile tests and swelling behavior. In blends of thermoplastics with a high content of GTR (50 and 75 wt.%), the thermoplastic modifier type had a significant impact on the processing behavior and microstructure of blends. In terms of the physico-mechanical properties, the GTR/thermoplastics ratio affected elongation at break, hardness, and density, while its effect on tensile strength was negligible. DSC analysis showed that thermoplastics, as modifiers of GTR, should be considered as binders and not plasticizers, as reflected in the almost constant glass-transition temperature of the blends. RPA measurements indicated higher values of G* and η* for GTR-rich blends. SEM showed a rubber-like interfacial break, while AFM confirmed interfacial contact between GTR and thermoplastics.

Processing, Performance Properties, and Storage Stability of Ground Tire Rubber Modified by Dicumyl Peroxide and Ethylene-Vinyl Acetate Copolymers.

In this paper, ground tire rubber was modified with dicumyl peroxide and a variable content (in the range of 0-15 phr) of ethylene-vinyl acetate copolymers characterized by different vinyl acetate contents (in the range of 18-39 wt.%). Modification of ground tire rubber was performed via an auto-thermal extrusion process in which heat was generated during internal shearing of the material inside the extruder barrel. The processing, performance properties, and storage stability of modified reclaimed ground tire rubber were evaluated based on specific mechanical energy, infrared camera images, an oscillating disc rheometer, tensile tests, equilibrium swelling, gas chromatography combined with a flame ionization detector, and gas chromatography with mass spectrometry. It was found that the developed formulas of modified GTR allowed the preparation of materials characterized by tensile strengths in the range of 2.6-9.3 MPa and elongation at break in the range of 78-225%. Moreover, the prepared materials showed good storage stability for at least three months and satisfied processability with commercial rubbers (natural rubber, styrene-butadiene rubber).

GTR/NBR/Silica Composites Performance Properties as a Function of Curing System: Sulfur versus Peroxides.

In this work, conventional sulfur and two types of organic peroxides (dicumyl peroxide (DCP) and di-(2-tert-butyl-peroxyisopropyl)-benzene (BIB)) curing systems were used to investigate the possibility for tailoring of the performance properties of GTR/NBR blends reinforced with a variable content of highly dispersive silica (0-30 phr). The curing characteristics, static mechanical and acoustical properties, swelling behavior, thermal stability, and microstructure of the prepared composites were investigated. The results show that regardless of the curing system used, increasing the content of highly dispersive silica resulted in the improvement of the mechanical properties of the studied materials. It was observed that sulfur-based systems are the best choice in terms of cross-linking efficiency determined based on torque increment and cross-link density parameters. However, further analysis of the physico-mechanical properties indicated that the cross-linking efficiency does not match the performance of specimens, and the materials obtained using organic peroxides show higher tensile properties. This is due to the improved physical interactions between the GTR/NBR matrix and highly dispersive silica when using peroxide systems. It was confirmed using the analysis of the Wolff activity coefficient, indicating the enhanced synergy.

Ground Tire Rubber Filled Flexible Polyurethane Foam-Effect of Waste Rubber Treatment on Composite Performance.

The application range of flexible polyurethane (PU) foams is comprehensive because of their versatility and flexibility in adjusting structure and performance. In addition to the investigations associated with further broadening of their potential properties, researchers are looking for new raw materials, beneficially originated from renewable resources or recycling. A great example of such a material is ground tire rubber (GTR)-the product of the material recycling of post-consumer car tires. To fully exploit the benefits of this material, it should be modified to enhance the interfacial interactions between PU and GTR. In the presented work, GTR particles were thermo-mechanically modified with the addition of fresh and waste rapeseed oil in the reactive extrusion process. The introduction of modified GTR particles into a flexible PU matrix caused a beneficial 17-28% decrease in average cell diameters. Such an effect caused an even 5% drop in thermal conductivity coefficient values, enhancing thermal insulation performance. The application of waste oil resulted in the superior mechanical performance of composites compared to the fresh one and thermo-mechanical modification without oils. The compressive and tensile performance of composites filled with waste oil-modified GTR was almost the same as for the unfilled foam. Moreover, the introduction of ground tire rubber particles enhanced the thermal stability of neat polyurethane foam.

The Impact of Ground Tire Rubber Oxidation with H2O2 and KMnO4 on the Structure and Performance of Flexible Polyurethane/Ground Tire Rubber Composite Foams.

The use of waste tires is a very critical issue, considering their environmental and economic implications. One of the simplest and the least harmful methods is conversion of tires into ground tire rubber (GTR), which can be introduced into different polymer matrices as a filler. However, these applications often require proper modifications to provide compatibility with the polymer matrix. In this study, we examined the impact of GTR oxidation with hydrogen peroxide and potassium permanganate on the processing and properties of flexible polyurethane/GTR composite foams. Applied treatments caused oxidation and introduction of hydroxyl groups onto the surface of rubber particles, expressed by the broad range of their hydroxyl numbers. It resulted in noticeable differences in the processing of the polyurethane system and affected the structure of flexible composite foams. Treatment with H2O2 resulted in a 31% rise of apparent density, while the catalytic activity of potassium ions enhanced foaming of system decreased density by 25% and increased the open cell content. Better mechanical performance was noted for H2O2 modifications (even by 100% higher normalized compressive strength), because of the voids in cell walls and incompletely developed structure during polymerization, accelerated by KMnO4 treatment. This paper shows that modification of ground tire rubber is a very promising approach, and when properly performed may be applied to engineer the structure and performance of polyurethane composite foams.

Reactive Sintering of Ground Tire Rubber (GTR) Modified by a Trans-Polyoctenamer Rubber and Curing Additives.

The proposed method of ground tire rubber (GTR) utilization involves the application of trans-polyoctenamer rubber (TOR), a commercially available waste rubber modifier. The idea was to investigate the influence of various curing additives (sulfur, N-cyclohexyl-2-benzothiazole sulfenamide (CBS), dibenzothiazole disulfide (MBTS) and di-(2-ethyl)hexylphosphorylpolysulfide (SDT)) on curing characteristics, physico-mechanical, thermal, acoustic properties as well as the morphology of modified GTR, in order to evaluate the possibility of reclaiming GTR and the co-cross-linking between applied components. The results showed that the presence of the modifier without the addition of curing additives hinders the physico-mechanical properties of revulcanized GTR. The addition of SDT, CBS, MBTS and sulfur change the melting kinetics of TOR, indicating partial degradation and/or co-cross-linking between components. In the studied conditions, the best mechanical properties were obtained by the samples cured with sulfur. The morphology analysis, combined with the physico-mechanical results, indicated that when the surface of the GTR is more developed, obtained by the addition of TOR, the properties of the GTR improve.

Ground Tire Rubber Modified by Ethylene-Vinyl Acetate Copolymer: Processing, Physico-Mechanical Properties, Volatile Organic Compounds Emission and Recycling Possibility.

Ground tire rubber (GTR) was reclaimed and modified with 10 phr of ethylene-vinyl acetate copolymer via low-temperature extrusion process. Processing, physico-mechanical properties, volatile organic compounds emission, and recycling possibility were investigated. In order to better understand the impact of used modifiers, their efficiency was compared with trans-polyoctenamer, which is an additive that is commercially dedicated to waste rubber recycling. The results showed that a relatively small amount of ethylene-vinyl acetate copolymer improves the mechanical properties of modified reclaimed GTR and also allows further recycling by multiple processing without the deterioration of performance after three cycles.

Reclaimed Rubber/Poly(ε-caprolactone) Blends: Structure, Mechanical, and Thermal Properties.

The amount of elastomeric waste, especially from tires is constantly increasing on a global scale. The recycling of these residua should be considered a priority. Compounding the waste rubbers with other polymers can be an excellent alternative to reuse waste materials. This procedure requires solving 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 their environmental impact. In this work, reclaimed rubber/poly(ε-caprolactone) (RR/PCL) blends are proposed to enhance the recycling and upcycling possibilities of waste rubbers. The results show that 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. Structure and properties of the proposed RR/PCL have been studied by means of static and dynamic mechanical testing, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA)-FTIR analysis.

Waste tire rubber as low-cost and environmentally-friendly modifier in thermoset polymers - A review.

Nowadays, waste tire rubber (WTR) management is a growing and serious problem. Therefore, research works focused on the development of cost-effective and environmentally-friendly methods of WTR recycling are fully justified. Incorporation of WTR into polymer matrices and composite materials attracts much attention, because this approach allows sustainable development of industrially applicable waste tires recycling technologies. Generally, utilization of WTR as a filler for polymer composites noticeably reduces materials costs, while suitable modification/functionalization of WTR may significantly enhance the performance of plastics and rubbers. This work aims to summarize the literature reports related to the thermoset/WTR composites based on various matrices such as: polyurethanes, epoxy and other resins. It particularly focuses on compatibilization strategies in thermosets/WTR systems and their impact on the chemistry and physical interfacial interactions between thermoset matrix and WTR filler phase, what significantly affecting performance properties of prepared materials. Moreover, future trends and limitation related to thermoset/WTR composites development are discussed.

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 fillers.

Preliminary Investigation on Auto-Thermal Extrusion of Ground Tire Rubber.

Ground tire rubber (GTR) was processed using an auto-thermal extrusion as a prerequisite to green reclaiming of waste rubbers. 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 conditions (with/without external barrel heating) on the reclaiming process of GTR. Moreover, samples were cured to assess the impact of reclaiming heating conditions on curing characteristics and physico-mechanical properties. Detailed analysis of the results indicated that the application of auto-thermal extrusion is a promising approach for the sustainable development of reclaiming technologies.

Synergistic Effects of Bitumen Plasticization and Microwave Treatment on Short-Term Devulcanization of Ground Tire Rubber.

Ground tire rubber (GTR) was mechano-chemically modified with road bitumen 160/220 and subsequently treated using a microwave radiation. The combined impact of bitumen 160/220 content and microwave treatment on short-term devulcanization of GTR was studied by thermal camera, wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), static headspace, and gas chromatography-mass spectrometry (SHS-GC-MS), thermogravimetric analysis combined with Fourier transform infrared spectroscopy (TGA-FTIR), oscillating disc rheometer and static mechanical properties measurements. The obtained results showed that bitumen plasticizer prevents oxidation of GTR during microwave treatment and simultaneously improves processing and thermal stability of obtained reclaimed rubber.