Exploring the Impact of Bio-Based Plasticizers on the Curing Behavior and Material Properties of a Simplified Tire-Tread Compound.

The tire industry needs to become more sustainable to reduce pollution and fight climate change. Replacing fossil ingredients in a tire-tread compound with bio-based alternatives is an approach to create a more sustainable product. For instance, the plasticizer can be replaced, which is a petroleum-based ingredient used in relatively high amounts in the rubber. This approach was followed in the current study. Three plant-based plasticizers were selected as potential substitutes for treated distillate aromatic extract (TDAE) in a simplified tire-tread compound formulation, namely, sunflower oil, coconut oil, and cardanol. Additionally, squalane was used as a TDAE replacement to further investigate the possible interactions between plasticizers and other compound ingredients. Squalane (C30H62) is a fully saturated substance, containing six methyl groups but no additional chemical functional groups. Therefore, it was expected that squalane would result in limited interactions within the studied system. All alternatives to TDAE showed an increased cure rate and decreased scorch time, except squalane. This indicates that the three bio-based plasticizers might interact with the vulcanization system. For example, they could function as an additional coactivator of the curing system and/or shield the silica surface. A severe decrease in maximum torque and an increase in elongation at break were obtained for cardanol and sunflower oil. Both plasticizers also resulted in lower crosslink densities compared to the other compounds. A model study with the bio-plasticizers and sulfur verified that the unsaturation in the cardanol and sunflower oil reacted with the crosslinking agent. This leads to less sulfur available for the curing reaction, explaining the low maximum torque. The tan δ curves showed that all replacements resulted in a decrease in the glass transition temperature of the compound. Although all oil alternatives displayed promising results, none of them are suitable as a direct substitute for TDAE in a tire-tread compound due to its ability to interact additionally with other rubber ingredients and contribute in this form to the reinforcement of the compound.

Pilot analysis of tire tread characteristics and associated tire-wear particles in vehicles produced across distinct time periods.

Owing to stringent vehicle emission regulations and the shifting automotive landscape towards clean-energy vehicles, the emission of non-exhaust tire-wear particles and its implications for microplastic contamination have garnered substantial attention, emerging as a focal point of research interest. Unlike traditional source apportionment methods involving direct environmental sampling, this study focuses on the physical and chemical attributes of tire treads, the tread temperature changes, and the tire-wear particle emissions of three light-duty vehicles manufactured between 2011 and 2021. This study advances the understanding of the effects of tire properties on particle emissions, which provides preliminary information on low-wear tires. The results show that tire-wear particle emissions, mainly composed of ultrafine particles in terms of number, heavily depend on the elevated tread temperatures. The change in tread temperature is influenced not only by the initial tread temperature but also by tread pyrolysis characteristics. Ca, Mg, and Zn are abundantly contained in the tire tread and tire-wear particles.

The Influence of Styrene Content in Solution Styrene Butadiene Rubber on Silica-Filled Tire Tread Compounds.

In tire tread applications, achieving enhanced abrasion resistance, wet grip, and rolling resistance is crucial for optimizing overall performance. To realize improvements in these attributes for silica-filled tire tread compounds, it becomes imperative to improve the dispersity of silica filler by investigating the effect of each component in the tire tread compound. In this work, we study the effect of styrene content within solution styrene butadiene rubber (SSBR) on the properties of tire tread compounds. A higher styrene segment within SSBR contributes to increased silica dispersion and crosslink density. Thus, tire tread compounds featuring SSBR with increased styrene content not only improve physical and mechanical properties, but also enhance major characteristics tailored for tire tread applications. These findings provide valuable insights into advancing the reinforced performance of tire tread compounds through the strategic utilization of SSBR enriched in styrene content.

Micron-size tire tread particles leach organic compounds at higher rates than centimeter-size particles: Compound identification and profile comparison.

Tire tread particles (TTP) are environmentally prevalent microplastics and generate toxic aqueous leachate. We determined the total carbon and nitrogen leachate concentrations and chemical profiles from micron (∼32 µm) and centimeter (∼1 cm) TTP leachate over 12 days. Dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) were used to measure the concentration of leached compounds. Nontargeted chemical analysis by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS) was used to compare the chemical profiles of leachates. After leaching for 12 days, DOC was 4.0 times higher in the micron TTP leachate than in the centimeter TTP leachate, and TDN was 2.6 times higher. The total GC×GC/TOF-MS chromatographic feature peak area was 2.9 times greater in the micron TTP leachate than the centimeter TTP leachate, and similarly, the total relative abundance of 54 tentatively identified compounds was 3.3 times greater. We identified frequently measured tire-related chemicals, such as 6PPD, N-cyclohexyl-N'-phenylurea (CPU), and hexa(methoxymethyl)melamine (HMMM), but nearly 50% of detected chemicals were not previously reported in tire literature or lacked toxicity information. Overall, the results demonstrate that smaller TTP have a greater potential to leach chemicals into aquatic systems, but a significant portion of these chemicals are not well-studied and require further risk assessment.

Optimized End Functionality of Silane-Terminated Liquid Butadiene Rubber for Silica-Filled Rubber Compounds.

As the world is shifting from internal combustion engine vehicles to electric vehicles in response to environmental pollution, the tire industry has been conducting research on tire performance to meet the requirements of electric vehicles. In this experiment, functionalized liquid butadiene rubber (F-LqBR) with triethoxysilyl groups at both ends was introduced into a silica-filled rubber compound as a substitute for treated distillate aromatic extract (TDAE) oil, and comparative evaluation was conducted according to the number of triethoxysilyl groups. The results showed that F-LqBRs improved silica dispersion in the rubber matrix through the formation of chemical bonds between silanol groups and the base rubber, and reduced rolling resistance by limiting chain end mobility and improving filler-rubber interaction. However, when the number of triethoxysilyl groups in F-LqBR was increased from two to four, self-condensation increased, the reactivity of the silanol groups decreased, and the improvement of properties was reduced. As a result, the optimized end functionality of triethoxysilyl groups for F-LqBR in silica-filled rubber compound was two. The 2-Azo-LqBR with the optimized functionality showed an improvement of 10% in rolling resistance, 16% in snow traction, and 17% in abrasion resistance when 10 phr of TDAE oil was substituted.

Urban runoff mortality syndrome in zooplankton caused by tire wear particles.

Stormwater runoff from roadways is a global threat to water quality, aquatic organisms, and ecosystems. Tire tread wear particles (TWP) from roadway runoff may lead to urban runoff mortality syndrome (URMS) in some aquatic organisms. We tested the hypothesis that urban runoff from roadways can kill zooplankton. Both roadway runoff and TWP leachate were acutely lethal to a model species, the water flea Daphnia pulex. Life table experiments further revealed the lowered survival rates, intrinsic rate of increase, average life span, and net productive rate of D. pulex when exposed to roadway runoff and TWP leachate. The tire rubber antioxidant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) mainly contributed to the TWP toxicity. The toxicity of TWP and 6PPD extracted varied with time in nature. Cladocerans and rotifers were more sensitive to TWP and 6PPD than copepods. These results demonstrate the presence of URMS in zooplankton, which may cascade through food webs and affect aquatic ecosystems.

Transformation Products of Tire Rubber Antioxidant 6PPD in Heterogeneous Gas-Phase Ozonation: Identification and Environmental Occurrence.

6PPD, a tire rubber antioxidant, poses substantial ecological risks because it can form a highly toxic quinone transformation product (TP), 6PPD-quinone (6PPDQ), during exposure to gas-phase ozone. Important data gaps exist regarding the structures, reaction mechanisms, and environmental occurrence of TPs from 6PPD ozonation. To address these data gaps, gas-phase ozonation of 6PPD was conducted over 24-168 h and ozonation TPs were characterized using high-resolution mass spectrometry. The probable structures were proposed for 23 TPs with 5 subsequently standard-verified. Consistent with prior findings, 6PPDQ (C18H22N2O2) was one of the major TPs in 6PPD ozonation (∼1 to 19% yield). Notably, 6PPDQ was not observed during ozonation of 6QDI (N-(1,3-dimethylbutyl)-N'-phenyl-p-quinonediimine), indicating that 6PPDQ formation does not proceed through 6QDI or associated 6QDI TPs. Other major 6PPD TPs included multiple C18H22N2O and C18H22N2O2 isomers, with presumptive N-oxide, N,N'-dioxide, and orthoquinone structures. Standard-verified TPs were quantified in roadway-impacted environmental samples, with total concentrations of 130 ± 3.2 µg/g in methanol extracts of tire tread wear particles (TWPs), 34 ± 4 µg/g-TWP in aqueous TWP leachates, 2700 ± 1500 ng/L in roadway runoff, and 1900 ± 1200 ng/L in roadway-impacted creeks. These data demonstrate that 6PPD TPs are likely an important and ubiquitous class of contaminants in roadway-impacted environments.

Refinement of a microfurnace pyrolysis-GC-MS method for quantification of tire and road wear particles (TRWP) in sediment and solid matrices.

Tire and road wear particles (TRWP) are produced by abrasion at the interface of the pavement and tread surface and contain tread rubber with road mineral encrustations. Quantitative thermoanalytical methods capable of estimating TRWP concentrations are needed to assess the prevalence and environmental fate of these particles. However, the presence of complex organic constituents in sediment and other environmental samples presents a challenge to the reliable determination of TRWP concentrations using current pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) methodologies. We are unaware of a published study evaluating pretreatment and other method refinements for microfurnace Py-GC-MS analysis of the elastomeric polymers in TRWP including polymer-specific deuterated internal standards as specified in ISO Technical Specification (ISO/TS) 20593:2017 and ISO/TS 21396:2017. Thus, potential method refinements were evaluated for microfurnace Py-GC-MS, including chromatography parameter modification, chemical pretreatment, and thermal desorption for cryogenically-milled tire tread (CMTT) samples in an artificial sediment matrix and a sediment field sample. The tire tread dimer markers used for quantification were 4-vinylcyclohexene (4-VCH), a marker for styrene-butadiene rubber (SBR) and butadiene rubber (BR), 4-phenylcyclohexene (4-PCH), a marker for SBR, and dipentene (DP), a marker for natural rubber (NR) or isoprene. The resultant modifications included optimization of GC temperature and mass analyzer settings, along with sample pretreatment with potassium hydroxide (KOH) and thermal desorption. Peak resolution was improved while minimizing matrix interferences with overall accuracy and precision consistent with those typically observed in environmental sample analysis. The initial method detection limit for an artificial sediment matrix was approximately 180 mg/kg for a 10 mg sediment sample. A sediment and a retained suspended solids sample were also analyzed to illustrate the applicability of microfurnace Py-GC-MS towards complex environmental sample analysis. These refinements should help encourage the adoption of pyrolysis techniques for mass-based measurements of TRWP in environmental samples both near and distant from roadways.

Analysis of Polymeric Components in Particulate Matter Using Pyrolysis-Gas Chromatography/Mass Spectrometry.

Particulate matters (PMs) such as PM10 and PM2.5 were collected at a bus stop and were analyzed using pyrolysis-gas chromatography/mass spectrometry to identify organic polymeric materials in them. The major pyrolysis products of the PM samples were isoprene, toluene, styrene, dipentene, and 1-alkenes. The pyrolysis products generated from the PM samples were identified using reference polymeric samples such as common rubbers (natural rubber, butadiene rubber, and styrene-butadiene rubber), common plastics (polyethylene, polypropylene, polystyrene, and poly(ethylene terephthalate)), plant-related components (bark, wood, and leaf), and bitumen. The major sources of the principal polymeric materials in the PM samples were found to be the abrasion of the tire tread and asphalt pavement, plant-related components, and lint from polyester fabric. The particles produced by the abrasion of the tire tread and asphalt pavement on the road were non-exhaustive sources, while the plant-related components and lint from polyester fabric were inflowed from the outside.

Effects of the Diamine Chain End Functionalized Liquid Butadiene Rubber as a Processing Aid on the Properties of Carbon-Black-Filled Rubber Compounds.

The implementation of vehicle electrification and autonomous driving technologies has recently emphasized the importance of abrasion resistance and fuel efficiency of truck bus radial (TBR) tire treads that undergo high loads and long driving times. In this study, a functionalized liquid butadiene rubber (F-LqBR) was introduced to replace the treated distillate aromatic extracted (TDAE) oil as a way to improve abrasion resistance and fuel efficiency in the TBR tire tread compound and to solve the oil migration. First, radical polymerization was used to synthesize nonfunctionalized LqBR (N-LqBR) and amino-LqBR with an amine group at the chain ends. The synthesized LqBRs were then substituted in place of TDAE oil to manufacture carbon-black-filled natural rubber (NR) compounds and to evaluate their physical properties. The results show that LqBRs improved the migration resistance and enhanced the abrasion resistance by lowering the glass transition temperature (Tg) of the compound. In particular, amino-LqBR improved carbon black dispersion in the rubber matrix through a chemical bond between the functional group of the carbon black surface and the base rubber. In conclusion, amino-LqBR successfully served as a processing aid in a carbon black-filled NR compound while simultaneously enhancing its fuel efficiency and abrasion resistance.

Synthesis and Application of Silica Supported Calix[4]arene Derivative as a New Processing Aid Agent for Reducing Hysteresis of Tread Rubber Compounds Used in Low Rolling Resistance Tires.

Rolling resistance is one of the most important properties of a tire which is highly dependent on the viscoelastic properties of its rubber compounds. There are a lot of ways to reduce this parameter both in construction improvement of the tire and changing in rubber compound formulation especially in tire tread formulation. Rubber scientists have been trying to introduce new processing aid agents beyond the traditional tire components for reducing the rolling resistance. In this study, a unique structure of silica-supported calix[4]arene (SS-CSC[4]A) has been synthesized and applied as a processing aid agent in tire tread formulation. Fourier-transform infrared spectroscopy (FTIR), Nuclear Magnetic Resonance (1HNMR and 13CNMR), 29Si CP/MAS spectroscopy, thermal gravimetric analysis (TGA), elemental analysis, and acid-base titration were used to characterize its structure. Scanning Electron Microscopy (SEM) use to investigate the effect of prepared material on qualification of filler dispersion in the rubber matrix. The viscoelastic properties of the prepared rubber compound were measured by Dynamic Mechanical Thermal Analysis (DMTA) which showed the great decrease in rolling resistance of rubber compound based on SS-CSC[4]A as a processing aid agent. The mechanical and rheological properties of obtained tread rubber compound measured by tensometer and MDR rheometer showed no sensible changes in these properties.

Aging of tire and road wear particles in terrestrial and freshwater environments - A review on processes, testing, analysis and impact.

The environmental fate of tire and road wear particles (TRWPs) receives increasing attention due to the per capita emission volumes of 0.2-5.5 kg/(cap year) and recent reports on the environmental hazard of TRWP constituents. It is expected that aging impacts TRWPs fate in the environment but detailed knowledge is quite limited, yet. Making use of information on tire aging, the available knowledge on environmental aging processes such as thermooxidation, photooxidation, ozonolysis, shear stress, biodegradation and leaching is reviewed here. Experimental techniques to simulate aging are addressed as are analytical techniques to determine aging induced changes of TRWPs, covering physical and chemical properties. The suitability of various tire wear test materials is discussed. Findings and methods from tire aging can be partially applied to study aging of TRWPs in the environment. There is a complex interplay between aging processes in the environment that needs to be considered in future aging studies. In addition to existing basic qualitative understanding of the aging processes, quantitative understanding of TRWP aging is largely lacking. Aging in the environment needs to consider the TRWPs as well as chemicals released. Next steps for filling the gaps in knowledge on aging of TRWPs in the environment are elaborated.

Treading Water: Tire Wear Particle Leachate Recreates an Urban Runoff Mortality Syndrome in Coho but Not Chum Salmon.

Tire tread wear particles (TWP) are increasingly recognized as a global pollutant of surface waters, but their impact on biota in receiving waters is rarely addressed. In the developed U.S. Pacific Northwest, acute mortality of adult coho salmon (Oncorhynchus kisutch) follows rain events and is correlated with roadway density. Roadway runoff experimentally triggers behavioral symptoms and associated changes in blood indicative of cardiorespiratory distress prior to death. Closely related chum salmon (O. keta) lack an equivalent response. Acute mortality of juvenile coho was recently experimentally linked to a transformation product of a tire-derived chemical. We evaluated whether TWP leachate is sufficient to trigger the acute mortality syndrome in adult coho salmon. We characterized the acute response of adult coho and chum salmon to TWP leachate (survival, behavior, blood physiology) and compared it with that caused by roadway runoff. TWP leachate was acutely lethal to coho at concentrations similar to roadway runoff, with the same behaviors and blood parameters impacted. As with runoff, chum salmon appeared insensitive to TWP leachate at concentrations lethal to coho. Our results confirm that environmentally relevant TWP exposures cause acute mortalities of a keystone aquatic species.

Quantification of tire tread wear particles in microparticles produced on the road using oleamide as a novel marker.

In general, tire tread rubber compounds contain oleamide for improvement of manufacturing processibility, mold release characterization, and abrasion resistance. Tire tread wear particles (TWPs) are one of major contributors to microplastic emissions. In this study, a novel analytical method for quantification of TWP in microparticles produced on the road (road dust, MPRs) was developed by employing oleamide as a new marker. MPRs were collected at bus stops in autumn, winter, and summer seasons. MPRs of 38-63, 63-106, 106-212, and 212-500 µm obtained by size separation were employed for the analysis. Rubber components for bus and passenger car tire tread compounds were identified using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Oleamide was extracted from the MPRs with acetone and was identified using GC/MS. The oleamide concentration was analyzed using GC equipped with flame ionization detector (FID). The TWP contents of the MPRs were determined using the oleamide concentrations and the reference compound formulations. In order to reduce the sampling errors, each experiment was carried out five times and the results were averaged. The TWP contents of the MPRs were 1.4-4.7 wt% and were different according to the sampling seasons and places. The TWP contents were increased by increasing the traffic volume and the temperature.

New Insights into the Morphology of Silica and Carbon Black Based on Their Different Dispersion Behavior.

Precipitated silica in combination with bifunctional organosilanes almost fully replaces currently the commonly used carbon black fillers in modern passenger car tire tread compounds to improve tire properties such as wet traction (safety) and rolling resistance (fuel consumption). However, it is still challenging to reach a sufficient level of abrasion resistance (service life). An optimum macrodispersion quality of the silica is a fundamental precondition for an optimum abrasion resistance. This goal can be reached by the development of new tailor-made highly dispersible silica grades. In order to achieve this, it is essential to be aware of the analytical silica parameters, which affect the dispersion process. One of these parameters known from carbon black is the structure of the filler. To gain deeper insights into the in-rubber dispersibility of the silica, the structure was investigated by two different methods, the DOA measurement and the void volume measurement. The results were correlated to the in-rubber macrodispersion. In contrast to carbon black filled compounds, no sufficient correlation of the structure with the macrodispersion could be found for the silica-filled compounds. Therefore, it was concluded that the morphology of silica differs from that one that is claimed for carbon black. Additional investigations like TEM, FT-IR and X-ray diffraction measurements were carried out. Carbon black shows a more elastic structure, which can withstand the external forces during the mixing process in a better way. Silica contains a much higher void volume in the structure even after exposed to high forces. These new findings will help to understand the macrodispersion process in rubber in a better way.

The Effect of Silanization Temperature and Time on the Marching Modulus of Silica-Filled Tire Tread Compounds.

Marching modulus phenomena are often observed in silica-reinforced solution styrene-butadiene rubber/butadiene rubber (S-SBR/BR) tire tread compounds. When such a situation happens, it is difficult to determine the optimum curing time, and as a consequence the physical properties of the rubber vulcanizates may vary. Previous studies have demonstrated that the curing behavior of silica compounds is related to the degree of silanization. For the present work, the effect of silanization temperature and time on the marching modulus of silica-filled rubber was evaluated. The correlations between these mixing parameters and their effect on the factors that have a strong relation with marching modulus intensity (MMI) were investigated: the amount of bound rubber, the filler flocculation rate (FFR), and the filler-polymer coupling rate (CR). The MMI was monitored by measuring the vulcanization rheograms using a rubber process analyzer (RPA) at small (approximately 7%) and large (approximately 42%) strain in order to discriminate the effects of filler-filler and filler-polymer interactions on the marching modulus of silica-filled rubber compounds. The results were interpreted via the correlation between these factors and their effect on the MMI. A higher temperature and a longer silanization time led to a better degree of silanization, in order of decreasing influence.

The Investigation of the Silica-Reinforced Rubber Polymers with the Methoxy Type Silane Coupling Agents.

The methoxy-type silane coupling agents were synthesized via the modification of the hydrolyzable group and characterized to investigate the change in properties of silica/rubber composites based on the different silane coupling agent structures and the masterbatch fabrication methods. The prepared methoxy-type silane coupling agents exhibited higher reactivity towards hydrolysis compared to the conventional ethoxy-type one which led to the superior silanization to the silica filler surface modified for the reinforcement of styrene-butadiene rubber. The silica/rubber composites based on these methoxy-type silane coupling agents had the characteristics of more developed vulcanization and mechanical properties when fabricated as masterbatch products for tread materials of automobile tire surfaces. In particular, the dimethoxy-type silane coupling agent showed more enhanced rubber composite properties than the trimethoxy-type one, and the environmentally friendly wet masterbatch fabrication process was successfully optimized. The reactivity of the synthesized silane coupling agents toward hydrolysis was investigated by FITR spectroscopic analysis, and the mechanical properties of the prepared silica-reinforced rubber polymers were characterized using a moving die rheometer and a universal testing machine.

Glycidyl Methacrylate-Emulsion Styrene Butadiene Rubber (GMA-ESBR)/Silica Wet Masterbatch Compound.

In the tire industry, solution styrene butadiene rubber (SSBR), which can introduce a functional group with good reactivity to silica at chain ends, is used to increase rolling resistance performance by considering fuel economy. However, this is not environmentally friendly because SSBR uses an organic solvent for polymerization, and it is difficult to increase its molecular weight. Functionalized emulsion SBR (ESBR) can solve the problems of SSBR. The molecular weight of ESBR molecules can be easily increased in an eco-friendly solvent, i.e., water. A functionalized ESBR introduces a functional group with good reactivity to silica by introducing a third monomer during polymerization. In this field, glycidyl methacrylate (GMA) has been reported to show the best properties as a third monomer. However, for GMA-ESBR, the viscosity is high and processability is disadvantageous. Therefore, we polymerized GMA-ESBR and manufactured silica compounds to clarify the causes of these problems. In addition, wet masterbatch (WMB) technology, which is a new compound manufacturing method, was applied to manufacture the silica compound, and the physical properties are compared with those of a dry masterbatch. The results clarified the problem of GMA-ESBR, which could be solved by using WMB technology.

Skin blister formation together with patterned intradermal hematoma: a special type of tire mark injury in victims run over by a wheel.

A traffic accident victim run over by a vehicle may show a patterned skin hematoma reflecting the grooves of the tire's profile. Apart from this well-known type of imprint mark, the affected skin can also be blistered provided that the wheel exerts high pressure on the body for a prolonged period of time. The macro- and micromorphological findings as well as the protein composition of the blister fluid were investigated on the basis of a relevant autopsy case. Analogous to blisters associated with hanging marks, the transudation of serous fluid with consecutive detachment of the epidermis is interpreted as a pressure-related effect which cannot be regarded as a sign of vitality.