1. Introduction
Natural rubber (NR) stands as an exceptionally sustainable material, distinguishing itself as the sole agricultural product within the spectrum of rubber varieties. NR exhibits a myriad of distinctive physical properties, encompassing remarkable attributes like high elasticity, minimal heat generation, exceptional resistance to fatigue crack propagation, and more. These inherent properties render its applicability across a diverse array of engineering domains, including but not limited to its utilization in the construction of tires and shock absorbers [
1,
2,
3]. NR can be effectively compounded with synthetic rubbers to enhance its mechanical characteristics, including tensile strength, resilience, tear strength, fatigue resistance, and fracture toughness. It has been documented that the incorporation of NR into styrene butadiene rubber (SBR) blends can lead to enhancements in oxidative stability [
4]. Rubber blends find their most significant application within the tire manufacturing industry. SBR exhibits superior attributes in terms of crack resistance, wet traction, and resistance to adverse weather conditions when compared to natural rubber. Conversely, NR surpasses SBR in terms of strength, heat dissipation, and low-temperature performance. Therefore, the synergistic qualities of NR and SBR have led to their extensive use in the production of tires [
5]. It is worth noting that tire compositions typically incorporate substantial quantities of carbon black (CB) to enhance reinforcement and provide desirable properties related to fatigue resistance and abrasion [
6]. Nevertheless, the utilization of these fillers poses certain challenges. Their relatively high density contributes to an increase in the specific gravity of rubber compounds. Furthermore, their efficacy in reinforcing rubber materials is most pronounced when employed at substantial loadings [
7,
8,
9]. It is essential to note that, in the context of NR vulcanizates, an increase in CB ratios is accompanied by considerable heat build-up, which, in turn, adversely affects various performance attributes of vehicle tires. Enhancing the performance of vehicle tires entails addressing issues such as the mitigation of heat accumulation, the augmentation of wet handling characteristics, and the reduction in rolling resistance [
10,
11]. In pursuit of these objectives, researchers have explored the application of hybrid nanofillers, encompassing the use of CB or combinations of two or three distinct fillers. This approach has garnered attention for its potential in the development of advanced, high-performance rubber composites [
6,
12,
13,
14]. Researchers have undertaken investigations into the partial substitution of CB with carbon nanotubes (CNTs). Their studies have unveiled a synergistic interaction between CNT and CB, resulting in a significant enhancement in crack propagation resistance within NR composites. Moreover, this concurrent usage of CNT and CB has demonstrated notable efficiency in mitigating heat build-up in NR vulcanizates [
2,
15].
CNTs are cylindrical molecular structures composed of carbon, characterized by nanometer-scale diameters and micrometer-scale lengths. Their extraordinary mechanical properties, such as a remarkably high aspect ratio, expansive surface areas, exceptional tensile strength of 150–180 GPa, moduli ranging from 640 GPa to 1 TPa, and remarkable elasticity, endow them with substantial reinforcing capabilities [
7,
9,
16,
17,
18]. The enhancement of properties in polymer/CNT composites primarily hinges on factors including the uniform dispersion of CNTs, interactions between the filler and the matrix, and the inherent attributes of the CNTs themselves. Due to relatively weak intermolecular forces such as van der Waals and π-π interactions that govern the assembly of CNTs, these nanotubes exhibit a propensity to intertwine, forming sizeable aggregations referred to as “bundles” [
19,
20,
21]. The attainment of high-performance NR nanocomposites characterized by homogeneous dispersion of nanofillers necessitates the resolution of two prominent challenges: aggregation and inadequate matrix–filler interactions. The establishment of robust interactions between NR and nanofillers, along with the effective alleviation of filler–filler agglomerations, is of paramount importance in realizing property enhancements within NR-based nanocomposites. Several well-regarded processing techniques for the fabrication of NR nanocomposites include methods such as melt/mechanical mixing, solution mixing, and latex casting [
22].
Within the solution mixing method, the polymer solution is intricately combined with the nanofiller dispersion through means such as ultrasonication, stirring, or shear mixing. Subsequently, the resultant polymer–nanofiller dispersion is cast into a mold and allowed to undergo solvent evaporation. This approach offers the advantage of achieving a more refined nanofiller dispersion. Nevertheless, the removal of solvents upon completion of this procedure presents a notable challenge. Moreover, the method is afflicted by drawbacks such as elevated costs, substantial solvent consumption, and environmental concerns related to solvent disposal [
22,
23]. Fakhrúl-Razi et al. [
24] undertook the preparation of nanocomposites comprising NR and multi-walled carbon nanotubes (MWCNTs) through the solution casting method. Toluene was used as the solvent for dispersing the MWCNTs, and NR was similarly dispersed in toluene. The two solutions were subsequently amalgamated, resulting in a final solution containing a well-balanced blend of MWCNTs within the NR matrix, which underwent further processing. This methodology facilitated the attainment of a uniformly dispersed MWCNT structure within the NR, thereby yielding enhancements in mechanical, chemical, and physical properties. In another study, the fabrication of NR/MWCNT nanocomposites was executed through the incorporation of MWCNTs at various loading levels, employing two distinct methodologies: mechanical mixing and solution mixing by Hanafi Ismail et al. [
25] The process entailed the initial swelling of natural rubber in toluene under sustained agitation. Concurrently, multi-walled carbon nanotubes were dispersed in toluene and subjected to magnetic stirring for a duration of 20 min. Following this interval, the MWCNT dispersion was amalgamated with the rubber–toluene solution and agitated vigorously for a period of 2 h. Subsequently, the solvents within the resultant dispersions were subjected to evaporation within a fume chamber until the weight of the rubber-MWCNT composite sample reached a constant value. Once this criterion was met, the sample was removed from the chamber and prepared for further mixing with additional rubber additives, accomplished on a laboratory-scale two-roll mill, resulting in an improved MWCNT dispersion in the rubber matrix [
25]. In an effort to enhance the dispersion of MWCNTs within the NR matrix, a solution-mixing method was undertaken by Huang et al. [
26]. Initially, MWCNTs were exfoliated and dispersed in water through ultrasonication, with the aid of tannic acid (TA) serving as a dispersing agent. Subsequently, this MWCNT dispersion was combined with interspersed SiO
2 microspheres (m-SiO
2). It is noteworthy that a notable attribute of this process is the ability to uniformly disperse both m-SiO
2 and MWCNTs within the NR matrix through direct mixing of the dry hybrid filler and NR within a double roller mill. This method capitalizes on the distinctive and synergistic dispersing effects between m-SiO
2 and MWCNTs, in addition to the dispersing efficacy conferred by TA. The ultimate research findings underscore the excellent mechanical, electrical, and thermal properties [
26].
The latex mixing method involves the utilization of rubber in its latex form. The dispersion of nanofillers is integrated with the polymer latex and subsequently undergoes a casting and drying procedure. Alternatively, latex coagulation can be employed to foster substantial interactions between the nanofiller and the polymer matrix. In this particular context, the coagulation of the latex and the nanofiller dispersion is achieved through the addition of an acidic agent, followed by the incorporation of additional curatives into the polymer nanocomposite utilizing mechanical techniques. It is noteworthy that this method obviates the necessity for highly toxic and expensive organic solvents, thereby establishing itself as an ecologically sustainable alternative to solution mixing, as elucidated [
22,
27]. Nonetheless, the substantial volume of deionized water employed for the dispersion of CNT results in the dilution of the latex, inducing a propensity for CNTs to settle within the diluted latex medium and, consequently, giving rise to a secondary agglomeration phenomenon [
28,
29]. The preparation of nanocomposites based on NR has been accomplished through a latex stage mixing technique featuring the incorporation of single-walled carbon nanotubes (SWNTs) by Anoop Anand K. SWNTs were initially dispersed in water using ultrasonication and subsequently stabilized through the introduction of a surfactant. This stabilized aqueous dispersion of SWNTs was then blended with NR latex to investigate the impact of the nanofiller on the rheological properties of the NR latex. Subsequent to the compounding of the latex and the curing process, high-quality composite films were obtained, characterized by a pronounced improvement in their mechanical properties. Remarkably, the composite film, including 2 phr SWNTs, exhibited a substantial increase of 56% in tensile strength and a 63% increase in modulus in comparison to pure NR films [
30]. In another study, Laiyun Wei et al. stated that the utilization of the latex mixing method was pivotal in enhancing the dispersion of graphene oxide (GO)/CNT hybrid fillers and CB within the NR matrix. This enhanced dispersion mechanism contributed to the development of a more robust and efficient filler network, consequently leading to significant enhancements in the modulus and energy dissipation properties of NR composites. The introduction of GO/CNT hybrid fillers and CB into the NR matrix resulted in a substantial improvement in resistance to fatigue crack propagation and a reduction in heat generation, thereby enhancing the overall performance of NR composite materials [
2]. In another work, polyvinylpyrrolidone (PVP) was employed as a dispersant for MWCNTs, and the effectiveness of various dispersion techniques, including high-speed shear, water bath ultrasonication, and tip ultrasonication, was systematically compared to assess their exfoliation capabilities. Following this, the appropriateness of employing nonionic PVP for the purpose of achieving high-speed shear exfoliation and dispersion of MWCNTs was thoroughly investigated and fine-tuned, while classical anionic sodium dodecyl benzene sulphonate (SDBS) and cationic cetyltrimethylammonium bromide (CTAB) were utilized as control agents for comparative assessment. Ultimately, an aqueous dispersion of MWCNTs, which had been noncovalently modified by PVP, hereinafter denoted as PVP-m-MWCNTs, was amalgamated with natural latex to produce a composite material comprising NR and MWCNTs, designated as W-NMC. A comparative assessment, conducted in relation to the conventional dry-mixing procedure (D-NMNCs), elucidated that the wet mixing methodology implemented in this investigation yielded W-NMCs distinguished by their superior tensile properties, reduced compression temperature rise, enhanced resistance to DIN abrasion, increased electrical and thermal conductivity, augmented resilience against ice and wet-slip, and diminished rolling resistance. These improvements can be attributed to the enhanced dispersion of MWCNTs and the reinforcement of the interfacial interaction between NR-MWCNTs within the W-NMNCs, aligning with the research findings of Wei Xiao [
31]. An investigation conducted by Song et al. focused on the development of high-performance nanocomposites comprising MWCNTs and SBR through a latex mixing process, with the utilization of lower MWCNT quantities. To augment MWCNT dispersion in the aqueous phase for latex mixing, a diverse array of surfactants was systematically employed to modify the MWCNTs. In a targeted approach, a suspension of MWCNTs was incorporated into the SBR latex to optimize the dispersion of MWCNTs within the elastomeric matrix, consequently bolstering interfacial strength. The successful realization of uniformly dispersed MWCNTs throughout the SBR matrix yielded composite materials distinguished by their exceptional mechanical, thermal, and electrical properties, even at low MWCNT loadings [
32].
In the melt/mechanical mixing method, the production of nanocomposites is achieved through the utilization of equipment such as an internal mixer, two-roll mill, ball mill, or similar apparatus. This method finds substantial favor within industrial applications owing to its environmentally conscientious attributes, cost effectiveness, elevated efficiency, and expeditious production capabilities. Notably, the solvent-free characteristic represents a pivotal advantage, rendering it a highly regarded alternative to solution mixing [
22,
23]. Hanafi Ismail et al. prepared NR/MWCNT samples by using a laboratory-sized two-roll mill in accordance with ASTM D3184 guidelines [
33]. The authors found a more favorable dispersion of MWCNTs within the NR matrix when employing the solution mixing method, in contrast to the mechanical mixing method. In terms of mechanical properties, the tensile modulus exhibited a direct proportionality with the MWCNT loading, while conversely, the tensile strength and elongation at break displayed an inverse relationship. Importantly, NR/MWCNT nanocomposites prepared via the solution mixing method exhibited superior tensile characteristics in comparison to composites produced through mechanical mixing techniques [
25].
Laboratory-scale formulation development traditionally relies on small-scale internal mixers and two-roll mills, which are encumbered with several significant drawbacks. These conventional compounding methods entail labor-intensive procedures, requiring at least two personnel for the preparation of a single batch. Furthermore, these methods pose problems in terms of contamination, especially when dealing with different types of samples, necessitating separate Banbury machines for black and nonblack samples. Moreover, there is an extended turnaround time involved in the process. In addition to these operational challenges, safety concerns are associated with the open mixing area of two-roll mills. This process typically demands a substantial material volume, thus exacerbating the cost implications, especially when dealing with expensive additives. Moreover, the spatial requirements of both open mills and internal mixers are substantial, consuming approximately 6 square meters of laboratory space, particularly due to the dusting associated with carbon black additives. However, the adoption of high-torque laboratory twin-screw micro-compounders, which have served the plastic industry for over three decades, presents a more efficient alternative for the formulation of new rubber compounds. This method streamlines sample preparation, contributing to the overall cost effectiveness of research and development efforts. Micro-compounders offer the advantage of being operated by single personnel, characterized by ease of operation, reduced labor intensity, and a remarkably expedited compound preparation time, typically as short as 5 min. These devices require only minimal quantities of materials, which is particularly advantageous when working with costly additives. Additionally, micro-compounders enable the formulation of more precise compound compositions and occupy significantly less laboratory space compared to their conventional counterparts. Their ease of cleaning and enhanced safety features further underscore the advantages of this modern approach to rubber compounding at the laboratory scale.
Hence, the primary aim of this research is to investigate the influence of a hybrid microstructure developed within a tire tread compound composed of an NR/SBR blend and augmented by the inclusion of MWCNT and CB. This study seeks to elucidate the impact of this hybrid filler system on various properties, encompassing the mechanical, thermal, rheological, morphological, and electrical and thermal conductivity aspects of the composites. The distribution of these hybrid fillers within the NR/SBR matrix was accomplished through the use of a high-torque lab-scale twin-screw micro-compounder, a method until now unreported in the literature. Within this context, MWCNTs were introduced into the NR/SBR composite, in conjunction with the reinforcing CB, within the formulation of a tire tread composition. This approach aims to provide deeper insights into the intricate dynamics of this composite system, particularly with regard to the structure-property relationships arising from the distinctive synergism inherent in a macro-nano dual filler system.
4. Conclusions
The intrinsic low thermal conductivity inherent in tires contributes to the phenomenon of heat build-up and concurrent material degradation. In light of this, there is a recognized necessity to enhance the thermal conductivity of tires, a goal that can be effectively realized through the incorporation of conductive fillers. Accordingly, carbon-based fillers emerge as particularly auspicious additives for augmenting the thermal characteristics of polymer composites, owing to their exceptional thermal properties. Therefore, in this study, it was aimed to decrease the heat accumulation properties as well as to improve the mechanical, rheological, and morphological properties of NR/SBR-based tire tread compounds using thermally conductive carbon nanotube nanoparticles. For this purpose, different tire thread compound recipes, including different loading levels of MWCNT, were prepared. The improved distribution of MWCNT/CB hybrid fillers was achieved by using a laboratory-scale high-torque micro-compounder, serving as an economically viable and expeditious research facility, presenting opportunities for the manipulation of small quantities of materials.
The incorporation of MWCNT nanoparticles in the NR/SBR compounds significantly developed the thermal conductivity of the samples, resulting in heat removal from the tire tread compound, which can improve the service life of a tire. Moreover, the enhancement in MWCNT distribution within the NR/SBR compound had a discernible impact on mechanical, rheological, and stress relaxation characteristics. Specifically, with an increase in the distribution of MWCNT, several key vulcanization parameters, such as scorch time and cross-link density, were notably amended. Moreover, the homogeneous distribution of MWCNT created more interfacial interaction and interfacial area between the fillers and rubber matrix; therefore, mechanical properties such as tensile strength and Young modulus were substantially developed. In addition, the findings of the study revealed that the percolation threshold for the NR/SBR composite occurred at a loading level of 3 phr of MWCNTs. It was observed that CB aggregates were uniformly distributed throughout the tire tread compound, effectively establishing robust interconnections with the MWCNTs.