1. Introduction
Carbon nanotubes (CNTs) have extraordinary mechanical properties. Compared to steel, these tiny particles’ ductility is 60 times higher, their tensile strength is 100 times higher, and their modulus of elasticity is five times larger [
1]. When incorporated into the concrete mixture, it creates a layer (measuring 1 to 5 µm in thickness) that covers the cement and filler particles, making them more tightly interlocked and thus preventing the formation and propagation of cracks at the microscale [
1]. Without CNT reinforcement, the presence of calcium hydro-silicate crystals at the interface between the cement particles and aggregates weakens the overall structure [
2]. Ferro et al. [
3] indicated that the addition of 0.5% weight of multiwall carbon nanotubes (MWCNTs) to the mortar as reinforcement caused an approximately 50% increase in the dissipated energy density, at any point during the curing process. This increased the internal damage before failure. CNTs impede the formation and spread of cracks at the nanoscale, rather than just at the microscale. Adhikary et al. [
4] examined the influence of different methods for producing CNTs on mechanical and microstructural properties. The authors’ conclusion was that CNTs integrated with cement-based composites exhibit a superior mechanical performance owing to an enhanced crack bridging and adhesion to concrete. The microstructure of the composite exhibited an increased production of calcium silicate hydrate (CSH) gel, which enhances the mechanical strength of the concrete. Additionally, the results demonstrated excellent compatibility between cementitious materials and CNTs. Du et al. [
5] investigated the durability and mechanical behaviors of a cement-based composite with CNTs. The durability test involved both impermeability and frost resistance. It showed an improvement in the diffusion coefficient of the CNT composite compared to the control sample.
Hunashyal et al. [
6] revealed that beam toughness and flexural capacity can be greatly enhanced by addition of 0.25 wt.% (by the mass of cement) of MWCNTs. Similar results were obtained by Cerro-Prada et al. [
7], who found that the compressive strength increased by 25% and the flexural strength by 20% upon the addition of 0.02 wt.% MWCNT. Yakovlev et al. [
2] focused on producing pre-stressed poles for high-voltage power lines. The authors stated that the flexural strength of cement concrete increased by as much as 46% when reinforced with MWCNTs, indicating a similar pattern of behavior. Ferro et al. [
3] examined the flexural capacity of plain mortar versus CNT-reinforced mortar at various curing times, finding that the greatest impact of the CNT reinforcement occurs within the first day of curing. However, given that the standard curing period is typically 28 days, a 30% boost in flexural capacity can be deemed the most significant outcome of the experiment. Mohsen et al. [
8] used a permeability test to demonstrate that the inclusion of 0.15 and 0.25 wt.% CNTs in concrete led to a boost of over 100% in the flexural strength compared to CNT-free concrete. Additionally, the use of CNTs resulted in an approximately 150% increase in concrete ductility. Lee et al. [
9] used multi-walled carbon nanotubes to study the bond between the composites and a reinforcing bar. They showed that there was a 46.42 MPa increase in the compressive strength when they used 0.5 wt.% of the fibers, whereas when the percentage increased over 1%, the compressive strength test results of the cementitious composites showed that there was an insufficient increase in the compressive strength of the specimen. Ramezani et al. [
10] studied the effects of the experimental variables of CNTs on the concrete flexural strength. They showed that a higher CNT aspect ratio (AR) from 400 to 800 and a concentration (κ) of 0.08–0.18 wt.% resulted in the highest improvement in the flexural strength.
Sasmal et al. [
11] noted that CNTs will one day help civil engineers to make “crack-free” concrete, but one of the problems associated with the addition of CNTs in cement paste is the lack of proper dispersion. Several studies have been conducted to increase the dispersion and effect of CNTs in concrete mixes by incorporating silica fumes (SFs), also known as microsilica. In a study conducted by Kim et al. [
12], the researchers attempted to incorporate CNTs into the concrete mix, with and without SFs. The researchers concluded that incorporating CNTs into the concrete mix without any silica fumes (or any other dispersion techniques) leads to negligible effects of CNTs on the behavior of concrete. On the other hand, adding silica fumes to the mix incorporating CNTs provided significant enhancements to the mechanical performance of concrete. Several techniques, such as the addition of dispersant materials (e.g., superplasticizers [
13,
14] and surfactants [
15,
16]) and defoaming agents [
17], the use of different mixing techniques (e.g., magnetic stirring [
18] and ultrasonication [
19]), or the application of experimental design to ascertain the materials’ factors [
20], have been employed to optimize and increase the dispersibility of CNTs, with varying results.
Since the 1960s, researchers have found that reinforcing concrete with fibers in discrete form is a considerably effective method. Well-dispersed fibers increase the homogeneity of concrete and unify its overall mechanical properties in all directions and planes. Under loading, as concrete starts to crack, the fibers inside the concrete start to inhibit the crack growth and propagation, leading to the increase in the strength and ductility of concrete [
21]. Fibers that can reinforce concrete come in different shapes and can be made from different materials, and thus their properties and effects on concrete do vary. For the application of concrete reinforcement, the most common fibers include steel fibers, glass fibers, natural organic and mineral fibers, polypropylene fibers, Kevlar, nylon, and polyester. Fibers are usually characterized by their “aspect ratio”, which is a measure of the fiber’s length compared to its equivalent diameter (L/D) [
21]. According to Wafa [
21], it is essential to achieve a high level of dispersion of the fibers in the concrete to observe their effect on improving the mechanical properties of concrete, as fibers naturally tend to aggregate during mixing, especially while adding them to the mix. Common factors that increase the fibers’ tendency to aggregate include a high aspect ratio, high percentages of fibers in the mix, and the dimensions and amounts of the aggregates. Karim and Shafei [
22] compared the performance of ultra-high-performance concrete (UHPC) reinforced with synthetic fibers, namely, nylon, polypropylene, polyvinyl alcohol, alkali-resistant glass, and carbon instead of steel. The results revealed that polyvinyl alcohol fibers provided the best workability and, at the same time, exhibited the highest first-crack strength, maximum strength under flexural load, as well as the highest toughness, posing them as potential candidates to replace steel fibers.
Said and Abdul Razak [
23] studied the effect of adding polyethylene fibers with different aspect ratios using other engineered cementitious composites (ECCs). The authors highlighted that the compressive strength of FRC was found to be inversely proportional (at a low rate) to the reinforcing index (R.I.) and this, most logically, would be due to the fibers not being well dispersed in the mix. Polyethylene is a hydrocarbon (composed of carbon and hydrogen) with the chemical formula of (C
2H
4)
n, and polyethylene fibers have been widely utilized in recent studies as micro-reinforcement due to their mechanical performance and availability.
Salemi and Behfarnia’s [
24] study revealed that adding reinforcement to fiber-reinforced concretes at the nano-level does improve the compressive strength of concrete. By substituting 3% of the cement weight with nano-alumina, the compressive strength of the concrete was increased by 8%. Up to a 30% increase in compressive strength was also witnessed when using 5% nano-silica. This is a positive sign, indicating the compatibility and harmony in functionality between reinforcement at the micro-level and reinforcement at the nano-level within the same concrete mix. Similar to Said and Abdul Razak’s [
23] study, in which concrete was reinforced with polyethylene fibers alone, Salemi and Behfarnia [
24] also faced the lowered workability of the concrete mix after adding the nano-material. This means that both, the micro- and the nano-, reinforcements of concrete mixes do lower the workability of concrete. Most importantly, it can be concluded, from Salemi and Behfarnia’s [
24] study, that adding nano-reinforcement to FRC improves the durability measures of the concrete significantly. It is also worth mentioning that the researchers concluded that the concrete mix that had both fibers and nano-material had the highest frost resistance among the tested specimens that either had fibers alone, nanomaterial alone, or no reinforcement at all. More specifically, according to Salemi and Behfarnia [
24], around an 87% increase in durability was obtained by incorporating 5% nano-silica in addition to 0.2% polyethylene fibers in the same mix.
In a similar attempt, Shah et al. [
25] studied the effect of reinforcing concrete with both micro- and nano-fibers, which they referred to as “ladder reinforcement”. In this study, the authors reinforced concrete with both carbon nano-fibers (CNFs) and polyvinyl alcohol (PVA) microfibers. Shah et al. [
25] applied ultrasonic energy to disperse carbon nano-fibers (CNFs) in a surfactant solution before adding them to the concrete mix to achieve the sufficient dispersion of the CNFs in the mix. The study showed that reinforcing the concrete mix with 0.048% (weight of cement) CNFs yielded improvements in flexural capacity, modulus of elasticity, and toughness by up to 40%, 75%, and 35%, respectively, compared to the plain mix. Similarly, reinforcing plain concrete with PVA microfibers led to improvements in the flexural capacity, modulus of elasticity, and toughness. Shah et al. [
25] stated that the flexural capacity and the modulus of elasticity increased by less than 10%, while the toughness increased by 10 times. When the concrete was reinforced with both nano-fibers and PVA microfibers, all the mechanical properties (flexural capacity, modulus of elasticity, and toughness) improved. The improvement, in this case, exceeded those in the other cases, i.e., incorporating CNFs alone or incorporating PVA microfibers alone, individually.
Potapov et al. [
26] investigated the impact resistance of concrete reinforced with silicon dioxide nanoparticles and 1.5 wt.% basalt microfiber. The compressive strength of the specimens examined was 1.5 higher than that without nanoparticles and microfibers, the flexural strength was increased by 3.4 times, and the specific energy of impact destruction was 22.2 times higher. This was attributed to the increased volume fraction of the denser CSH gel, due to nanogranules filling its volume and the interfacial transition zone, and the enhanced shear stress of the CSH gel. Recently, multiscale analysis has been used to explain the physical characteristics of cement pastes using CNTs [
27,
28]. Authors have suggested that numerical analysis can provide guidance for optimizing cement-based composites and therefore reduce the need to carry out extensive and expensive experiments. Kavvadias et al. [
29] studied the results obtained experimentally with those predicted by a multiscale computational investigation. The investigators found that the 0.1 wt% MWCNTs/CementPaste composite demonstrated the least number of errors between the numerical model and the experimental measurements.
There have been several attempts to reinforce concrete with fibers in order to inhibit crack growth at the micro-level, and new insights include using nano-materials to reinforce cement-based composites at the nano-level in order to inhibit crack initiation and growth at earlier stages. The main challenge associated with these ideas is dispersing the nano- or micromaterial thoroughly within the cementitious mix. In fact, the poor dispersion of these materials yields almost no considerable effects or even adverse ones, since the fibers act as voids in the concrete under compressive loading [
21].
The present study aims to provide a practical solution to efficiently control crack initiation and growth in cementitious materials in order to reduce their quasi-brittle behavior. The main concept is to reinforce concrete at the nano-level, micro-level, and both at the same time. The dispersion challenge is also addressed in this study by applying novel approaches to disperse each of the reinforcing materials in the cementitious mix. Furthermore, this work is oriented towards the mechanical performance of reinforced concrete rather than other performance criteria, such as electrical conductivity and frost resistance, which have already been addressed in the literature. This study aims to enrich and fill a gap in the literature, especially since nano-technology is still poorly employed in civil engineering applications and not enough research has been conducted to understand its potential benefits in the field.
4. Conclusions
The effects of incorporating CNTs, polyethylene fibers, or their combination as reinforcement on the mechanical performance and the durability of mortar were studied in this paper. The compressive strength of the mortar was not considerably affected by the addition of CNTs, PE fibers, or both. The modulus of elasticity of the mortar in compression (E
c) was considerably decreased after adding CNTs, PE fibers, or their combination. E
c was lowered by 11%, 16%, and 30% after adding CNTs, PE fibers, and both, respectively, compared to the control mix. On the other hand, ductility in compression (defined as the ratio of the maximum strain to the yield strain) was significantly increased by both types of reinforcement. It was enhanced by 50%, 34%, and 20% owing to CNTs, PE fibers, and their combination, respectively. The flexural strength was also significantly enhanced with the addition of both CNTs and PE fibers. The maximum enhancement was around 194% due to the incorporation of PE fibers. The second maximum enhancement was observed in Mix D (which incorporated both CNTs and PE fibers), and it reached around 169%. Incorporating CNTs alone did increase the flexural strength, with an approximately 66% increase. The maximum displacement at failure for the mortar prisms in the bending test was significantly improved. Improvements of 57%, 350%, and 398% were recorded for the mixes incorporating CNTs, PE fibers, and both at once, respectively. It is important to note that a key success factor during sample preparation is the proper dispersion of the constituents, and a large degree of variability can exist in the samples depending on the procedure adopted for the dispersion, leading to mixed results [
20]. Whenever CNTs or PE fibers are intended to be used as reinforcement for mortar, extensive care should be taken in proportioning, mixing, and casting the mortar. Dispersing CNTs and PE fibers in mortar is a highly sensitive activity that requires accuracy at all stages of execution. This includes taking into consideration the important factors that have a direct impact on the workability of the mix, namely, the % of silica fumes, % of CNTs, % of fibers, and the accurate measurement of the water absorption of the aggregates. In light of the significant decrease in the workability of Mixes C and D, future researchers are encouraged to investigate the effects of using superplasticizers with different dosages on the performance of these mixes.
Contrary to our expectations, the RCPT results reveal that the mixes that incorporated CNTs (Mixes B and D) had more than double the permeability for chloride ions compared to that of the control mix. The RCPT is a valid, quick, and easy test to measure the chloride permeability of normal mortar, but it is very important to note that this test fails to measure the real chloride permeability of mortars that incorporate conductive materials, such as CNTs. Alternative tests that rely on measuring the chloride concentration rather than the electric charge that passes through the specimen, such as AASHTO T259, ASTM C1543, and ASTM C1556, may be used to measure the chloride permeability of mortars that incorporate CNTs or any other conductive material.
The SEM images and EDX spectra obtained for the four different mortar types confirmed and matched with the experimental results related to the mechanical performance. Most notably, Mix D (which incorporated both CNTs and PE fibers) had the highest level of homogeneity, which was evident in both SEM images and EDX spectra. Additionally, the effect of CNTs, as well as PE fibers, was clear in reducing the microcracks and voids in the mortar matrix, which signals to the excellent interlocking of PE fibers and CNTs. The novel attempt in this study to combine both CNTs and PE fibers as reinforcement for mortar, based on the experimental results presented, is worth of further research. In several cases, especially for the strain gain property of mortar upon flexure, the combined effect of both CNTs and PE fibers exceeded the individual effect of any of the two, and this is a clear sign of the rationality and the promising future of this concept. This should also be a strong motive to investigate the combined effect of PE fibers and CNTs on large-scale beams and to work on standardizing and regulating this type of engineered construction material.