1. Introduction
Waste tire accumulation has become a global environmental issue [
1,
2,
3]. According to estimates, approximately one billion tires are made worldwide each year [
4]. Crumb rubber (CR) made from waste tires is commonly used in asphalt modification. Studies have shown that the use of CR particles in the asphalt industry has a number of advantages, including increased service life, lower noise levels by up to 70%, improved thermal characteristics and skid resistance, and a safe technique for scrap tire recycling [
5,
6]. The production of crumb rubber modified asphalt (CRMA) has two technical routes. The first route is the “dry process”, in which crumb rubber modifier (CRM) is used to replace 1% to 3% of the aggregate weight in the asphalt mixture. In the dry process, CRM and asphalt have little interaction during mixing in the mix plant hence is not the most preferred. The second route is the “wet technique”, which was devised by McDonald in the late 1960s. In this route, CRM is added to the bitumen or base asphalt as a modifier at 160 °C and eventually heated at 180~190 °C [
7]. The absorption of aromatic oils from asphalt cement into CRM is the predominant interaction between CRM and asphalt in the wet technique. According to Heitzman [
8], interaction between CRM and asphalt is a physical reaction, not a chemical reaction. The “wet process” has a long record of use and has the potential to significantly improve results. However, due to a lack of storage stability, thorough quality control of CRMA is difficult [
9].
According to the existing literature, there are several approaches for enhancing the storage stability of CRMA produced using the “wet process”. One of the most effective methods is to use terminal blend (TB) asphalt [
10,
11]. In this approach, CRMA is made at a high temperature and cured for a long time (more than four hours) to ensure that the CRM degradation is significant. TB asphalt, as with all other polymer modified asphalts, is made at the refinery (or terminal). The reaction conditions of TB binder are considerably different from those of CRM binder, making it more suitable for factory production. In TB asphalt, crumb rubber, loses its high-temperature anti-rutting properties when it is completely degraded [
12]. Rutting is recognized and employed as the initial failure mechanism and one of the most critical factors in the design of flexible pavements. Permanent deformation of the wheel path in the horizontal direction emerges on the longitudinal surfaces, reducing the efficiency of the pavement and making vehicles rough and unsafe. Bitumen properties are important, to improve the rutting resistance of asphalt pavements. As a result of this, several researchers are now exploring the use of nanomaterials to improve the high-temperature properties and enhance the performance of TB binders [
13], but the performance improvement and modification mechanism is not clearly understood. Additionally, it is worth noting that composite modified asphalt is an important solution for addressing the performance imbalance of single polymer modified asphalt [
4]. Generally, TB binder has a higher storage stability than asphalt rubber (AR) since the asphalt completely digests the crumb rubber particles [
12,
14,
15,
16]. Recently, the Federal Highway Administration in collaboration with the University of California, Berkeley conducted accelerated pavement tests and found that TB asphalt outperformed AR in terms of fatigue resistance and is suitable for preparation of densely graded mixes [
17,
18]; however, the inferior rutting of TB binders is still a source of concern [
19]. Lin et al. observed that light components such as aliphatic are generated during the manufacturing process of TB asphalt due to the desulfurization and degradation of rubber powder, which boosts TB asphalt’s low-temperature characteristics [
20].
Besides the inferior high-temperature rutting properties of TB binders, it is a well-known fact that crumb rubber (CR) has the stereo-network structures established by cross-linking. Therefore, it is difficult to swell and distribute in asphalt matrix [
6]. In this light, the surface activation of CR, which attempts to change the chemical and/or physical properties of the CR surface, is one possible solution to this challenge. Surface activation boosts the surface activity of CR particles, resulting in a strong interfacial adhesive ability between crumb rubber and asphalt matrix, and hence improves the properties of CRMA binders. In this context, microwave irradiation has emerged to be one of the economical methods of surface activation of CR particles. Surface activation treatment promotes the interaction between bitumen and crumb rubber particles [
6]. In this research, CR particles were microwave irradiated to desulfurize and depolymerize the rubber before being added to base asphalt. The surface vulcanization network of CR particles broken by microwave irradiation enhances surface activity and, as a result improves bitumen compatibility [
19]. According to Aoudia et al., the microwave irradiation of CR particles can disrupt the C-S and S-S bonds while keeping the C-C bond intact [
21].
The purpose of this paper was to evaluate the high-temperature properties of terminal blend rubber/nano silica composite modified asphalt using microwave-activated rubber particles as well as elucidate its reaction mechanism. The effect of nano silica modifier on reducing high temperature rutting failure and its reaction mechanism of TB rubberized asphalt was evaluated and compared to the control sample using laboratory experiments. The research was beneficial from the standpoint of improving the inferior rutting performance of the TB rubberized asphalt as well as addressing the compatibility issues of CR particles and bitumen for sustainable paving solutions.
2. Materials and Experimental Procedures
2.1. Materials
In this study, the bitumen penetration grade 80–100 provided by Beijing Lusheng Asphalt Co., Ltd. was used as the base binder. The fundamental properties of bitumen are presented in
Table 1. The 40-mesh CR produced from waste tires in which metals and fibers were removed was supplied by ZhongNeng Rubber Co. Ltd. Chengdu, Sichuan, China. The fundamental properties of CR are provided in
Table 2. The fumed silica particles (Aerosil R202), herein referred to as nano silica, was obtained from Evonik Industries, China with the fundamental properties provided in
Table 3.
2.2. Microwave Treatment of Crumb Rubber Particles
Microwave irradiation has emerged to be one of the economical methods of surface activation of CR particles. In this study, a domestic microwave with a frequency of 2450 MHz was used. Exactly 60 g of CR sample was put in a microwave beaker and microwave irradiated for 4 min. Prior to microwave irradiation, CR was dried at 60 °C to reduce its moisture content. The resulting sample was known as the Microwave-activated crumb rubber (MCR).
After the activation of crumb rubber particles, the surface topography of MCR was examined in scanning electron microscope (SEM). The results revealed that MCR sample was porous and loose, whereas those of unactivated crumb rubber (CR) was smooth and dense, as shown in
Figure 1. The loose and porous surface increases the reaction area of CR with asphalt binders because it decreases the density of CR particles; hence, the reaction area is extensive. On the other hand, the unactivated crumb rubber is flat and certainly not good enough for dispersion [
22]. Therefore, MCR modifier which would give better stability when blended with asphalt was employed in this research.
2.3. Asphalt Binder Modification
The terminal blend (TB) rubber–nano silica modified composite asphalt was prepared using a technique suggested by Han et al. [
19]. Herein, base asphalt was heated to 160 °C and blended with 8% MCR (by weight of asphalt). After the addition of MCR into base asphalt, the temperature was increased to 180~190 °C to promote the mixing and swelling of the blend while stirring manually for 20~30 min. The MCR/asphalt blend was then sheared at 3000~5000 rpm for 40~50 min at 180~190 °C. This was followed by the addition of 0.5, 1.5 and 3.0% of nano silica by weight of asphalt to produce TB rubber/nano silica composite modified asphalt. The composite mix was sheared at 3000~5000 rpm for another 40~50 min at 180~190 °C. The modification procedure is schematically presented in
Figure 2, and the labels used in this research are presented in
Table 4.
Following the preparation of terminal blend (TB) rubber/nano silica composite asphalt binders, various laboratory experiments were conducted to study the influence of nano silica on properties of TB binders. The experimental flow chart employed herein is shown
Figure 3.
2.4. Aging Procedure
One of the most important elements affecting the lifespan of an asphalt pavement is the aging of bituminous binder. Aging causes chemical and/or physical property changes in bituminous materials, making them harder and more brittle, increasing the likelihood of pavement failure. Bitumen aging is often divided into two stages: short-term aging at high temperatures during asphalt mixing, storage, and laying, and long-term aging at ambient temperatures while in service.
To simulate the short-term aging of asphalt binders in the laboratory, thin-film oven test (TFOT) was performed following ASTM D1754 standard [
23]. According to this test, the samples were held at 163 °C in the Thin-Film Oven for the TFOT test. The samples were aged for 20 h using the PAV standard technique (300 psi, 100 °C). After the TFOT test, the asphalt samples were placed in a pressure aging vessel (PAV) at 100 °C and 2.1 MPa pressure for 20 h during the long-term aging tests.
2.5. Segregation Test
A laboratory approach for testing the likelihood of polymer to separate from polymer modified asphalt under static heated storage conditions is known as a segregation test. Testing on material prepared according to this approach can be used as a guideline for creating goods or establishing field handling guidelines. Large discrepancies in test findings between top and bottom specimens suggest that the polymer and the base asphalt are incompatible.
In this research, exactly 50 g of each TB asphalt binder was put into standard aluminum tubes 25 mm diameter by 125 mm to 140 mm length, as per the Standard Practice for Determining the Separation Tendency of Polymer from Polymer Modified Asphalt, ASTM D 7173 [
24]. Then, the samples were maintained in the vertical vessel of an oven for 48 h at 163 °C. Thereafter, the samples were cooled in the refrigerator for 4 h after which three equal portions or parts were cut from the tube. The bottom and top parts of the modified bitumen samples were then separated and subjected to MSCR testing to determine the degree of separation or segregation index (SI).
2.6. Fourier Transport Infrared (FTIR) Test
FTIR spectroscopy is a non-dispersive and non-destructive technique of infrared (IR) spectroscopy that is widely used to investigate chemical functional groups in materials. The FTIR approach was created to address the limitations of dispersive infrared spectrometers, which only measure the intensity of a spectrum across a restricted range of wavelengths at a time. The dispersive infrared spectrometer uses a prism or grating to isolate distinct frequencies of energy produced from an IR source.
The FTIR test was undertaken in order to identify additives in modified binders and determine the modification mechanism. The modified bitumen was heated to flow at 160 °C before being placed on glass slides for the sample processing. The FTIR spectra of control and nano silica modified bitumen samples were obtained using a Thermo Fisher Scientific NICOLET-iZ10 FTIR spectrometer (Thermo Fisher Scientific, Waltham, Massachusetts, USA). The FTIR test wavenumber ranged between 4000 and 400 cm−1.
2.7. Atomic Force Microscopy (AFM) Test
AFM is a popular surface investigation tool for micro/nanostructured coatings. It provides both qualitative and quantitative data on a variety of physical attributes, such as size, morphology, surface texture, and roughness, among others. In this research, the homogeneity of asphalt samples modified with or without nano silica was obtained using a Bruker Dimension ICON2-SYS AFM instrument (Bruker Corporation, Billerica, MA, USA). The asphalt samples were poured on glass slides and allowed to flow. Further details about the preparation of AFM samples are described elsewhere [
25].
2.8. X-ray Diffraction (XRD) Test
The materials science technique of X-ray diffraction analysis (XRD) is used to determine the crystallographic structure of a material. XRD is a method of irradiating a substance with incoming X-rays and then measuring the intensities and scattering angles of the X-rays that depart the substance. In this study, The XRD test was conducted using X’Pert PRO MPD (λ = 1.54 A, Kα Ratio = 0.5, voltage = 40 kV) from PANalytical Co. (Armsterdam, The Netherlands) with CuKα a radiation. The diffraction pattern was collected in 2 h with a step of 0.025 in the range of 10 to 80. Each sample was flattened into a tiny tablet with a thickness of about 2 mm, weighing exactly 3 g. The tests were conducted out at a room temperature of 25 degrees Celsius. The patterns were used to investigate the presence of nano silica in the asphalt matrix and its dispersion.
2.9. Frequency Sweep (FS) Test
A frequency sweep test is conducted to measure the dynamic modulus and phase angle of the binder by subjecting the sample to oscillation shear loading and varying the loading frequency. In this research work, the FS image test was performed, utilizing the state-of-the-art DHR-2 manufactured by T.A. Instruments (New Castle, DE, USA). Therein, a 25 mm diameter by 1 mm thick and 8 mm diameter by 2 mm thick formed parallel metal plate samples were used. The former was used for temperatures above 40 °C, whereas the latter was utilized on test samples below 40 °C. To this end, the frequencies of between 0.1 and 50 Hz and preselected angular deflected (or torque) amplitudes were utilized. The chosen amplitudes were within the linear behavior region with test temperature ranging from −10 to 50 °C.
2.10. Multiple Stress Creep Recovery (MSCR) Test
Rutting is recognized and employed as the first failure mechanism in the majority of flexible pavement design scenarios. As one of the key elements used in asphalt mixtures, bitumen or asphalt binder can play a critical role, and altering its properties can considerably postpone or even prevent these failures in some cases. To better determine bitumen performance at high temperatures, the US Federal Highway Agency (FHWA) proposed a multi stress creep recovery (MSCR) test and an unrecoverable accepted parameter. In the present study, the asphalt sample’s elastic response under creep and recovery were determined at 0.1 kPa and 3.2 kPa stress levels at a temperature of 64 °C using the DHR-2 Rheometer. The asphalt sample was tested following ASTM D 7175 specification using a 25 mm parallel plate and a setting of 1 mm gap. Constant stress for 1 s was loaded on the specimen before 9 s recovery. The non-recoverable creep compliance (
Jnr) and the difference in
Jnr values from the MSCR test results were calculated using Equations (1)–(3).
where
Jnr is the non-recoverable creep compliance and
Jnr_diff is the difference between the 0.1 kPa and the 3.2 kPa stress level, respectively.
εp represents the peak strain, and
εu represents the unrecovered strain.
4. Conclusions
It has been primarily reported in the published literature that TB rubberized asphalt binders exhibit inferior high-temperature rutting performance. Rutting is identified and used as the first failure mechanism and most important design criteria of flexible pavement. The main cause of rutting in asphalt pavement has been recognized as “accumulated strain”, which is caused by traffic loading. Although, the addition of nanomaterials, particularly nano silica, has been reported to improve the durability and performance of crumb rubber modified asphalt essentially, the performance improvement and reaction mechanism studies have not been extended to TB binders. Moreover, the modification or reaction mechanism has not been clearly understood. Consequently, this research evaluated the high-temperatures properties and reaction mechanism of terminal blend (TB) rubber/nano silica composite modified asphalt using microwave-activated rubber. To this end, laboratory tests such as TFOT and PAV aging tests, segregation test, frequency sweep, MSCR, FTIR, FTIR and AFM were conducted using prepared samples. Based on these rigorous tests, the following conclusions were made:
The addition of nano silica significantly improved the rheological properties, storage stability and high-temperature rutting resistance of terminal blend rubberized asphalt. This is attributed to the reinforcing effect of nano silica on TB rubber asphalt and its interaction, which leads to the formation of polymeric network structures with PDMS chains intertwined with rubber particles, thereby reducing the movements around the particles and hence reducing phase separation. In addition, the polymeric network structure increases the binder stiffness and decreases nonrecoverable permanent strains, which is beneficial to reducing the permanent deformation of asphalt binders.
The rheological aging index (RAI) on PAV samples revealed that nano silica improves the aging of asphalt. This aging improvement of TB samples with nano silica is due to the interaction of polymer chains and nano silica particles which could delay the aging of polymers and raise the decomposition temperature. In addition, nanosilica migrates to the surface of composite materials and serve as a barrier to protect host polymers, resulting in improved anti-aging properties of the binders.
The incorporation of nano silica into TB rubberized binders improves material compatibility between SiO2 and TB binders, which is related to two factors: the manufacturer’s surface pretreatment of fumed silica, which inhibited particle–particle (SiO2-SiO2) interaction while increasing particle–polymer interaction and the microwave activation of CR resulting in a loose and porous surface, which increased the reaction area of CR with asphalt binders.
Based on XRD results, the TB-rubberized asphalt with different contents of nano silica had no sharp peaks in their pattens, which indicates that the materials were amorphous and did not have a crystalline structure.
AFM images showed bee-like structures which eventually disappeared after the addition of 3% Nano-SiO2, indicating that the light components of asphalt were absorbed by nano silica particles, which prevent aggregation.
The reaction mechanism between asphalt and rubber particles was physical, owing to the absence of new absorption peaks in the IR spectrum, whereas the interaction between TB binder and nano silica was chemical.
Despite the performance improvement of TB rubber/nano silica composite modified asphalt, this research did not examine the effect of activated and unactivated CR particles on TB rubberized/nano silica composite modified asphalt. Further research can examine the influence of microwave activation of rubber on the performance of TB rubber/nano silica composite modified asphalt.