1. Introduction
Today, polymers are one of the widest available types of materials with a wide range of properties. Unlike metals, polymers are highly elastic, which makes them suitable for a variety of applications. Polymers are composed of long-chain molecules made up of repeating units known as monomers. By altering the basic monomer units and incorporating different additives, a wide range of properties can be achieved. Polymers can achieve better properties by adding different fillers, which is called polymer compounding [
1]. For instance, advanced polymers are used in the process of water purification, tires, bulletproof vests, biological applications, automobile structures, plastic utensils, etc. [
2]. In this paper, the emphasis is placed on recycled rubber tiles obtained from waste tires, which represent a valuable raw material. Recycled rubber tiles are used to cover children’s playgrounds and sports fields, and with this research, we will try to improve their properties by adding fillers. The tiles are composed of rubber granulate and polyurethane, so attention should be paid to the interaction of the filler in the polyurethane mixture and with the rubber material.
Inorganic fillers in composites based on natural or synthetic rubber have increasing technological importance [
3], as well as with polyurethane composites [
4,
5,
6,
7,
8]. Over the last few years, several fillers were proposed to advance processability, physical properties modifying the composites, and cost reduction, such as titanium dioxide, zinc oxide, magnesium hydroxide, silanes, carbon black, carbon nanotubes, silver nanoparticles, etc. [
3,
8]. The performance of the composites is determined by filler dispersion and filler–rubber and filler-polyurethane interaction. At the same time, the other factors are the filler particles’ size, shape, structure, surface area, and surface reactivity [
3]. Fillers in the mixture have three types of effects on composite microstructures. Firstly, more obstacles are formed to impede micro-crack propagation in the matrix. Secondly, the stress level of neighboring particles gets better, and spacing between particles decreases, and lastly, there is an increase in aggregates which leads to easier separation from the matrix [
9]. One of the most important discoveries in material science is the reinforcement of rubber by rigid particles, such as titanium dioxide, silica, carbon black, calcium carbonate, clays, etc. [
10]. Titanium dioxide is widely used as a photocatalyst because of its high chemical stability, nontoxicity, inexpensiveness, commercial availability, and optical electronic properties [
11,
12]. Since it has photocatalytic and bactericidal effects [
3] and is safe for humans and animals [
3], it is generally used as a photocatalyst for environmental applications such as air and water purification, hazardous waste remediation, and water disinfection [
12].
TiO
2 is an interesting nanofiller for many reasons: it has the ability to photocatalytically decompose organic substances [
13,
14,
15], which positively affects the self-cleaning of surfaces [
16,
17,
18], achieves an antibacterial effect [
19,
20,
21], helps reduce photoaging through the absorption of ultraviolet light [
22,
23] and improves the mechanical properties of the material [
21]. On the other hand, one of the disadvantages of TiO
2 is its high bandgap, which is active only in a small fraction of the solar spectrum, so it can absorb only the UV part of the spectrum (<380 nm), which consists of 6.6% [
11]. The advantage of this kind of self-cleaning surface is that TiO
2 under ultraviolet (UV) illumination can decompose organic contaminants and/or kill bacteria adhering to the surface [
24], i.e., decompose a wide variety of organic compounds to water, carbon dioxide, and mineral acids or their salts [
25]. Nowadays, TiO
2 is already used in polymer materials, including rubber materials and polyurethanes, to improve the resistance to wear, chemical corrosion, rigidity, and oil, as a UV stabilizer and as a protective and antibacterial agent, for the achievement of photocatalytic properties, etc. [
3,
4,
6,
7]. Since rubber substrates are exposed to UV radiation throughout their lifetime, our primary goal is to reduce photoaging and enable a longer lifetime of the substrates while preserving and even improving the initial mechanical properties. Regarding the improvement of mechanical and physical properties, TiO
2 significantly impacts polymer composite reinforcement and thermal stability, making the final polymer product more economical. For these reasons, TiO
2 as a filler can be the most important additive, followed by the base polymer in rubber and polyurethane compounding [
6,
10]. Furthermore, because of the small size of particles and relatively high elastic modulus, TiO
2, compared with other fillers, achieves better interaction with polymer composites such as rubber and polyurethane [
3]. A literature review found that TiO
2 particles have free surface hydroxyl groups, which leads to good dispersion in polymer composites and causes a low tendency for aggregation [
3].
As stated earlier, this work aims to achieve a stable mixture with the addition of TiO2 as a filler to produce tiles from recycled tires. In relation to the literature review that is closely related to this topic, this work represents a great innovation for several reasons. Primarily, these tiles are of great environmental importance because they are made from recycled waste tires, i.e., the secondary raw material is used as the main raw material to produce the final product. Then, the modification is carried out using the non-toxic, easily available, and economically acceptable filler TiO2, which many available literatures have confirmed to have excellent compatibility in both rubber and polymer compounds. Finally, for the first time, an experimental investigation of the effect of TiO2 as a filler in a mixture containing both rubber and polyurethane was carried out. The goal of the work is based on the reduction of aging caused by UV radiation and, therefore, the extension of the service life of the substrate while preserving the necessary mechanical properties such as resistance to wear, hardness, and elasticity. In the future, this work will represent the basis for testing and achieving photocatalysis.
2. Experimental Part
2.1. Materials
Recycled rubber tiles were obtained from Gumiimpex GRP d.o.o., a company that collects waste tires of all types, which are then divided and separated into passenger, cargo (dumper and truck), semi-truck, tractor, and forklift. The collected tires are crushed by mechanical processing into a granulate, which is the main ingredient of our rubber tiles. A commercial formulation for the production of reference rubber tiles measuring (1000 × 1000 × 10) mm is obtained by mixing 9 kg of recycled rubber granulate (0.5–2.0 mm), 380 g of binder (polyurethane STOBICOLL 352.00) and 5 g of catalyst (DABCO K 2097). The commercial mixture of ingredients is pressed for 4 min at 120 °C and then cooled down.
2.2. Preparation of Novel Rubber Tile Mixture
The filler and photocatalyst titanium dioxide, TiO
2 (Evonik, Aeroxid
®, TiO
2 P25, 30 nm, 56 m
2/g, 75:25 anatase to rutile mass ratio) is added to a commercial formulation for the production of a reference rubber tile (hereafter RRT).
Table 1 shows the total masses of all necessary ingredients for producing an RRT and new tiles with the addition of TiO
2, and each tile is approximately (1000 × 1000 × 10) mm.
The added mass of TiO2 was calculated in percentages of 2, 4, and 10% of the total mass of polyurethane and catalyst (380 g + 5 g). Also, the addition of TiO2 was performed in different time periods for samples with 2% and 4%.
By adding fillers at different times, we want to investigate whether the mixing time affects the final properties and prove whether there are differences in the later results. The assumption is that it is not only the amount of added filler that is important but attention should also be paid to the time in which the filler will be added to the mixture.
Immediately after placing the mixture in the press mold, T/TiO2 (2% end) and T/TiO2 (4% end), we noticed that TiO2 particles were not evenly distributed within the mixture, and we concluded that adding TiO2 at the beginning was better due to achieving more uniform properties within the entire tile. Uneven distribution of TiO2 can lead to deterioration of the properties and result in tile cracking. Since the TiO2 particles in T/TiO2 (2% end) and T/TiO2 (4% end) were not evenly distributed, the analysis of these tiles will not be relevant. We conclude on the spot that the assumption about the time of adding the filler to the mixture was correct and that the time of addition also affects the final properties.
Due to the previous conclusion, the next tile was made only with the addition of TiO2 at the beginning of mixing. In the sample T/TiO2 (10% beginning), 38.5 g of TiO2 was added at the beginning of mixing the mixture. After the tile was removed from the press mold, it was immediately noticed that the tile began to crumble. Consequently, we conclude that it is necessary to add more binders to make the final product more resistant to crumbling. For this reason, we decided to increase the mass of polyurethane to 700 g. As a result of the above, we obtain a modified rubber tile (hereafter MRT), which consists of 9 kg of rubber granulate with a particle size of 0.5–2.0 mm, 700 g of polyurethane, 7 g of catalyst and 38.5 g of TiO2. By increasing the binder, the structure of the tile is improved, and there is no more crumbling.
2.3. Characterization
The characterization of the newly obtained materials was analyzed before and after the accelerated aging test in the form of mechanical properties, SEM/EDS, FTIR, and leaching tests.
2.3.1. The Experimental Investigation of the Accelerated Aging Test
The mechanical properties, SEM/EDS, FTIR, and leaching test will be examined before and after exposure to the experimental investigation of the accelerated aging test.
The properties of polymeric materials vary based on the exposure conditions at the site of use. The most crucial exposure factors are incidental solar radiation and the temperature of the object [
26]. This research does not consider other environmental conditions, such as humidity, rain, or air pollution. The used device, the ISOSun, was manufactured by infinityPV ApS, Møllehaven 12A, DK-4040 Jyllinge, Denmark (CVR: 36420367) to comply with EU regulations on electrical equipment (CE regulation). The system measures 96 cm in height, 57 cm in depth, and 52 cm in width. The system operates from a 240 VAC power line and has a power rating of 1490 Watts AC. A metal halide lamp with a power of 1200 W is used as a UV source, which also heats the room. With the help of a fan, it is possible to control the temperature inside the case. Depending on the filter used, the ISOSun can provide an intensity in the range of 0.5–1.5 sun equivalents. The solar simulator generates strong white light approaching the solar spectrum and generates ozone and much heat. The spectral irradiance (standard filter) of the solar simulator (ISOSun) compared with the reference global horizontal irradiance spectrum (AM 1.5G) is shown in
Figure 1. AM 1.5G is commonly used in terrestrial solar cell research, in accordance with the American Society for Testing and Materials (ASTM) G-173 as well as with the International Electrotechnical Commission IEC60904.
The exposed area of the sample was approximately (11 × 15) cm. Due to unavoidable thermal edge effects, only a (9 × 13) cm area (2 cm smaller than the whole area) was used for the analyses. The samples were placed in the chamber and subjected to UV light for periods of 28, 42, and 56 days, which correspond to 4, 6, and 8 weeks. The relationship between the accelerated aging time and the actual time for the material (rubber tiles) is determined using the following equation [
27,
28]:
The target real-time (RT) is established at 180 months, equivalent to 15 years. The accelerated aging temperature (T
AA) was set at 85 °C, while the ambient temperature (T
RT) was 19 °C. The aging factor (Q
10) for ambient temperature (T
RT) generally ranges from 1.8 to 2.5, with 2.0 being the most used value. Under these conditions, to replicate 15 years of aging, the material (rubber tiles) must undergo accelerated aging for 56.5 days [
27,
28]. Consequently, the accelerated aging experiment spanned 8 weeks (56 days), with some samples aged for only 4 and 6 weeks to observe changes throughout the process.
2.3.2. Mechanical Properties Testing
Abrasion Testing
The rubber wear test was conducted using a Gibitre Abrasiometre A (Gibitre Instruments, Bergamo, Italy), which estimates the sample’s abrasion resistance according to the DIN 53516.11 standard [
29]. The test involves pressing the sample against a rotating drum covered with standardized sandpaper, applying a defined force, and measuring abrasion over a rotating length of 40 m. Each sample was tested three times, with the results expressed as the average of the three measurements.
Tensile Strength Test
Mechanical properties were determined using a tensile tester (Tensor Check Profile, Gibitre Instruments, Bergamo, Italy) according to the DIN 53504.8 standard [
30], measuring maximum stress (TS), stress at break (TSb), and elongation at break (ε). Each sample was tested three times, with the results averaged. During the measurement, knives were used to cut samples according to a certain standard (DIN 53504) (length and width are standard, defined by the size of the knife), and the thickness was measured on the device during the measurement itself.
Hardness Test
A hardness test was conducted using a Shore hardness tester (Shore hardness tester micro, Gibitre Instruments, Bergamo, Italy) to measure the material’s resistance when the device’s needle is pressed into the sample. The test follows the DIN 53505.9 standard [
31], using the Shore A scale (ShA) for measurement. Each sample was tested five times, and the results were averaged.
2.3.3. Scanning Electron Microscopy (SEM) and Energy Dispersion Spectroscopy (EDS)
Characterization was conducted using a FEG SEM Quanta 250 FEI (FEI Company, Hilsboro, OR, USA equipped with OXFORD PENTAFET EDS detector, Oxford Instruments, Abingdon, Oxfordshire, UK) scanning electron microscope, operating at 20 kV with a working distance of 20 mm, under low vacuum conditions (“as is”) without evaporation.
2.3.4. Fourier Transform Infrared Spectroscopy (FTIR)
The infrared spectra of the materials were recorded using a Fourier transform infrared (FTIR) spectrometer (Bruker Vertex 70, Billerica, MA, USA) equipped with an attenuated total reflection (ATR) accessory featuring a diamond crystal. For each measurement, 32 scans were collected across the spectral range of 375–4000 cm⁻¹ with a resolution of 2 cm⁻¹.
2.3.5. Leaching Test
The analysis of Total Dissolved Solids (TDS) was conducted using a Hach Lange Sension 156 multimeter (Hach Company, Ames, IA, USA), while Dissolved Organic Carbon (DOC) was measured with a Shimadzu TOC/TN analyzer (Shimadzu, Kyoto, Japan). Chlorides, fluorides, and sulfates were analyzed using a Hach Lange DR 5000 spectrophotometer (Hach Company, Ames, IA, USA), and metals were examined with a PerkinElmer AAnalyst 800 spectrometer (PerkinElmer, Waltham, MA, USA). Three techniques were employed for the metal analysis: flame atomic absorption spectroscopy (FAAS) for zinc (Zn), chromium (Cr) and copper (Cu); graphite furnace atomic absorption spectroscopy (GFAAS) for arsenic (As), barium (Ba), cadmium (Cd), molybdenum (Mo), nickel (Ni), lead (Pb), selenium (Se), silicon (Si) and titanium (Ti); and flow injection atomic spectroscopy (FIAS) for mercury (Hg).
For the study, samples were cut and rinsed in deionized water for 24 h, with a liquid-to-sample ratio (L/S) of 1/10. The water used for leaching the rubber samples was then filtered through a 0.45 μm filter. The leaching test results of the rubber tiles, both before and after the addition of TiO
2, were compared with the limit values for waste disposal as outlined in the Ordinance on methods and conditions for landfill waste, specifically for the stabilized waste fraction following mechanical-biological treatment [
32]. The results were also compared to the Toxicity Characteristic Leaching Procedure (TCLP) protocol [
33], which is used by the U.S. Environmental Protection Agency (EPA) to assess how much toxic content from products would leach under normal conditions. Products that do not exceed regulatory limits for toxic material leaching are considered TCLP compliant [
33].
For easier comparison, due to differences in units, the measured leaching concentrations were converted using a specific conversion formula (Equation (2)) [
34]: