Published on Nov 30, 2023
Concrete, the most ubiquitous material in the world, is a nanostructured, multi-phase, composite material that ages over time. It is composed of an amorphous phase, nanometer to micrometer size crystals, and bound water. The amorphous phase, calcium-silicate-hydrate (C-S-H) is the ''glue" that holds concrete together and is itself a nanomaterial.
Viewed from the bottom-up, concrete at the nanoscale is a composite of molecular assemblages, surfaces (aggregates, fibres), and chemical bonds that interact through local chemical reactions, intermolecular forces, and intraphase diffusion. Properties characterizing this scale are molecular structure; surface functional groups; and bond length, strength (energy), and density. The structure of the amorphous and crystalline phases and of the interphase boundaries originates from this scale. The properties and processes at the nanoscale define the interactions that occur between particles and phases at the microscale and the effects of working loads and the surrounding environment at the macroscale. Processes occurring at the nanoscale ultimately affect the engineering properties and performance of the bulk material .
Nano-Fe 2 O 3 has been found to provide concrete with self-sensing capabilities as well as to improve its compressive and flexural strengths. Nano-Al 2 O 3 has been shown to significantly increase the modulus of elasticity (up to 143% at a dosage of 5%) but to have a limited effect on the compressive strength. Nanosized cement particles and nanobinders have been proposed as a way to improve cement performance while reducing carbon emissions. Cement pastes made with nanosized cement particles have shown faster setting times and an increase in early compressive strength compared to pastes prepared with common . The concept of a nanobinder involves mechano-chemical activation that is obtained by inter-grinding cement with dry mineral additives in a ball mill. Mechano-chemical modification of cement with high volumes of blast furnace slag has been shown to increase the compressive strength by up to 62%.
Nanoclay particles have shown promise in enhancing the mechanical performance, the resistance to chloride penetration, and the self-compacting properties of concrete and in reducing permeability and shrinkage. Natural clay particles are micron and sub-micron in size, and the base structure of clay is composed of crystalline layers of aluminum phyllosilicates with thicknesses on the order of 1 nm. Chemical binding of PVA (polyvinyl alcohol) to exfoliated clay particles recently has been proposed to create linked clay particle chains that, when incorporated in cement, were shown to improve the post-failure properties of the material
Carbon nanotubes/nanofibers (CNTs/CNFs) are potential candidates for use as nanoreinforcements in cement-based materials. CNTs/CNFs exhibit extraordinary strength with moduli of elasticity on the order of TPa and tensile strength in the range of GPa, and they have unique electronic and chemical properties.
CNTs/CNFs, thus, appear to be among the most promising nanomaterials for enhancing the mechanical properties of cement-based materials and their resistance to crack propagation while providing such novel properties as electromagnetic field shielding and self-sensing. Single-wall CNTs (SWCNTs), multi-wall CNTs (MWCNTs), and CNFs are highly structured graphene ring-based materials with very large aspect ratios (of 1000 or more) and very high surface areas. SWCNTs are single graphene cylinders and MWCNTs are multiple, concentric graphene cylinders coaxially arranged around a hollow core.
Unlike CNTs, CNFs present numerous exposed edge planes along the surface that constitute potential sites for advantageous chemical or physical interaction. Compared to CNTs, vapor grown CNFs have a lower production cost (about 100 times lower than SWCNTs ) and are suitable for mass production. While CNTs/CNFs have been extensively studied in polymeric composites, their use in cement has, to date, remained limited. Most research efforts have focused on CNTs compared to CNFs and have been performed on cement pastes.
Nanosized particles have a high surface area to volume ratio, providing the potential for tremendous chemical reactivity. Much of the work to date with nanoparticles has been with nano-silica (nano-SiO2) and nano-titanium oxide (nano-TiO2) .There are a few studies on incorporating nano-iron (nano-Fe2O3), nano-alumina (nano-Al2O3) , and nanoclay particles . Additionally, a limited number of investigations are dealing with the manufacture of nanosized cement particles and the development of nanobinders .
Nanoparticles can act as nuclei for cement phases, further promoting cement hydration due to their high reactivity, as nanoreinforcement, and as filler, densifying the microstructure and the ITZ, thereby, leading to a reduced porosity. The most significant issue for all nanoparticles is that of effective dispersion. Though it is particularly significant at high loadings, even low loadings experience problems with self-aggregation, which reduces the benefits of their small size and creates un-reacted pockets leading to a potential for concentration of stresses in the material.
Nano-SiO2 has been found to improve concrete workability and strength, to increase resistance to water penetration, and to help control the leaching of calcium, which is closely associated with various types of concrete degradation. Nano-SiO2, additionally, was shown to accelerate the hydration reactions of both C3S and an ash–cement mortar as a result of the large and highly reactive surface of the nanoparticles. Nano-SiO2 was found to be more efficient in enhancing strength than silica fume. Addition of 10% nano-SiO2 with dispersing agents was observed to increase the compressive strength of cement mortars at 28 days by as much as 26%, compared to only a 10% increase with the addition of 15% silica fume.
Even the addition of small amounts (0.25%) of nano-SiO2 was observed to increase the strength, improving the 28 day compressive strength by 10% and flexural strength by 25%. It was noted that the results obtained depended on the production route and conditions of synthesis of the nano-SiO2 (e.g., molar ratios of the reagents, type of reaction media, and duration of the reaction for the sol–gel method) and that dispersion of the nano-SiO2 in the paste plays an important role. Nano-SiO2 not only behaved as a filler to improve the microstructure but also as an activator to promote pozzolanic reactions .
Nano-TiO2 has proven very effective for the self-cleaning of concrete and provides the additional benefit of helping to clean the environment. Nano-TiO2 containing concrete acts by triggering a photocatalytic degradation of pollutants, such as NOx, carbon monoxide, VOCs, chlorophenols, and aldehydes from vehicle and industrial emissions. ‘‘Self-cleaning” and ‘‘de-polluting” concrete products are already being produced by several companies for use in the facades of buildings (e.g., the Jubilee Church in Rome, Italy). In addition to imparting self-cleaning properties, a few studies have shown that nano-TiO2 can accelerate the early-age hydration of Portland cement, improve compressive and flexural strengths, and enhance the abrasion resistance of concrete. However, it was also found that aging due to carbonation may result in loss in catalytic efficiency.
Nano-Fe2O3 has been found to provide concrete with self-sensing capabilities as well as to improve its compressive and flexural strengths. Nano-Al2O3 has been shown to significantly increase the modulus of elasticity (up to 143% at a dosage of 5%) but to have a limited effect on the compressive strength. Nanosized cement particles and nanobinders have been proposed as a way to improve cement performance while reducing carbon emissions. Cement pastes made with nanosized cement particles have shown faster setting times and an increase in early compressive strength compared to pastes prepared with common. The concept of a nanobinder involves mechano-chemical activation that is obtained by inter-grinding cement with dry mineral additives in a ball mill. Mechano-chemical modification of cement with high volumes of blast furnace slag has been shown to increase the compressive strength by up to 62%.
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