The influence of nano-silica on the hydration of ordinary Portland cement

Nucleation seeding is a new approach to control the kinetics of cement hydration. It is known that nano-silica has an accelerating effect on cement hydration. It is assumed that the surface of these particles act as a nucleation site for C–S–H-seeds which then accelerate the cement hydration. In this case the acceleration should depend on the particles surface area. To verify this, nano-silica particles of different sizes and specific surface areas were synthesised. The acceleration of cement hydration clearly correlates with the total surface size of the added particles, which was varied by either using smaller particles or higher concentration of particles in the cement lime. Additional in situ-XRD experiments show that the consumption of C₃S and the formation of portlandite are accelerated by the addition of nano-silica. In both cases the surface size is the major factor for the hydration kinetics.     

Effects of colloidal nanoSiO2 on fly ash hydration

The influences of colloidal nanoSiO₂ (CNS) addition on fly ash hydration and microstructure development of cement–fly ash pastes were investigated. The results revealed that fly ash hydration is accelerated by CNS at early age thus enhancing the early age strength of the materials. However, the pozzolanic reaction of fly ash at later age is significantly hindered due to the reduced CH content resulting from CNS hydration and the hindered cement hydration, as well as due to a layer of dense, low Ca/Si hydrate coating around fly ash particles. The results and discussions explain why the cementitious materials containing nanoSiO₂ had a lower strength gain at later ages. Methods of mitigating the adverse effect of nanoSiO₂ on cement/FA hydration at later ages were proposed.     

Effects of colloidal nanoSiO2 on fly ash hydration

The influences of colloidal nanoSiO₂ (CNS) addition on fly ash hydration and microstructure development of cement–fly ash pastes were investigated. The results revealed that fly ash hydration is accelerated by CNS at early age thus enhancing the early age strength of the materials. However, the pozzolanic reaction of fly ash at later age is significantly hindered due to the reduced CH content resulting from CNS hydration and the hindered cement hydration, as well as due to a layer of dense, low Ca/Si hydrate coating around fly ash particles. The results and discussions explain why the cementitious materials containing nanoSiO₂ had a lower strength gain at later ages. Methods of mitigating the adverse effect of nanoSiO₂ on cement/FA hydration at later ages were proposed.     

Mixtures of silicon and aluminum oxides to optimize the performance of nanoporous thin films in concrete

This study explored the effect of two combinations of silicon and aluminum oxides, nanosilica–nanoboehmite and nanosilica–gibbsite, on the hydration reaction of cement and the porosity of the interfacial transition zone (ITZ). The influence of sols on the cement hydration reaction was investigated using isothermal calorimetry while their effect on the porosity of the aggregate–paste interface was validated using scanning electron microscopy. The nanosilica–nanoboehmite mixtures were found to accelerate the hydration reaction to a higher degree than the individual components, nanosilica and nanoboehmite. Further, the effect was also found to be dependent on the stoichiometry of the mixture of nanoparticles. The nanosilica–gibbsite combinations not only accelerated the reaction but also increased the cumulative heat of hydration. In this case, the enhancement is attributed to the seeding effect of the gibbsite particles, being more prominent at the smaller particle sizes. Lastly, when these materials were applied as nanoporous thin films on the aggregates, all sol mixtures not only helped to decrease the overall porosity but also contributed to refinement of the porosity in the cement paste adjacent to the aggregate. These effects were observed up to 250 μm away from the surface of the aggregate thus not restricted to the typical length of the interfacial transition zone in concrete (40–50 μm).     

Water absorption control of ternary blended concrete with nano-SiO2 in presence of rice husk ash

In the current study, the effects of SiO₂ nanoparticles as additive with two different sizes of 15 and 80?nm on water absorption of rice husk ash (RHA) blended concrete have been investigated. Concrete samples were prepared by replacing 10, 15 and 20?wt% of cement with RHA and 0.5, 1.0, 1.5 and 2.0% of cement with SiO₂ nanoparticles followed by curing in lime solution for 7, 28 and 90?days. The results indicated that the resistance to water absorption of Portland cement?Cnano SiO₂?Crice husk ash (PC?CNS?CRHA) ternary blended concrete was considerably improved with respect to the control concrete. This improvement was observed at all curing ages and replacement levels but the optimal point was reached for 20% of RHA incorporating 2% of 80?nm SiO₂ particles at 90?days of curing. Fast formation of C?CS?CH gel in the presence of ultra high active nano-sized SiO₂ and micron level RHA particles together with their high filler effect may result in a continuous cement paste with the lowest weak zones. It has been concluded that the use of novel ternary blended concrete (PC?CNS?CRHA) provides significant reduction in the water absorption of concrete.     

Carboxylates and sulfates of polysaccharides for controlled internal water release during cement hydration

Calcium and aluminium carboxylates and sulfates of polysaccharides form hydrogels. Four Al- and three Ca-salt hydrogels of such polysaccharides, which were found to be stable enough to be mixed into fresh Portland cement pastes of low initial water-to-cement ratio of 0.275, were compared with respect to their water retardation potential using non-destructively operating low-field ¹H NMR relaxometry. All of the investigated hydrogels release their water to the cement mainly during the accelerated period of cement hydration. At a degree of hydration of about 0.7 the water in the hydrogels is consumed completely by the hydration reactions. Based on Powers’ hydration model the development of the volumetric phase distribution of the investigated hydrating cement with internal curing by the hydrogels was quantified. Within the hardening cement the Ca-salt hydrogels are more stable than the Al-hydrogels which is concluded from the changes of the T₂ relaxation times during the cement hydration.     

Influence of 15 and 80 nano-SiO2 particles addition on mechanical and physical properties of ternary blended concrete incorporating rice husk ash

This study demonstrates the effects of SiO₂ nanoparticles as additives with two different sizes of 15 and 80?nm on compressive strength and porosity of rice husk ash (RHA) blended concrete. Up to 20% of ordinary Portland cement (OPC) was replaced by RHA with average particle size of 5 micron. Also, SiO₂ nanoparticles were added to the above mixture at four different weight percentages of 0.5, 1.0, 1.5 and 2.0 and cured in lime solution. The results indicated that compressive strength of Portland cement–nano SiO₂–rice husk ash (PC–NS–RHA) ternary blended concrete was considerably increased. Moreover, the total amount of porosity decreased to a minimum with respect to the control concrete. This improvement was observed at all the curing ages and replacement levels, but there was a gain in the optimal point with 20% of RHA plus 2% of 80?nm SiO₂ particles at 90 days of curing.     

Hydration and properties of nano-TiO2 blended cement composites

Two types of nano-TiO₂ particles were blended into cement pastes and mortars. Their effects on the hydration and properties of the hydrated cement pastes were investigated. The addition of nano-TiO₂ powders significantly accelerated the hydration rate and promoted the hydration degree of the cementitious materials at early ages. It was demonstrated that TiO₂ was inert and stable during the cement hydration process. The total porosity of the cement pastes decreased and the pore size distribution were also altered. The acceleration of hydration rate and the change of microstructure also affected the physical and mechanical properties of the cement-based materials. The initial and final setting time was shortened and more water was required to maintain a standard consistence due to the addition of the nano-TiO₂. The compressive strength of the mortar was enhanced, practically at early ages. It is concluded that the nano-TiO₂ acted as a catalyst in the cement hydration reactions.     

Influence des fumées de silice sur l’évolution de l’hydratation des pâtes de chaux ou de Ciment Portland

The silica fume (SF) is used in civil engineering, in particular for the manufacture of high performance concrete.In order to better understand the gain in strength of the concretes containing SF, the microstructural aspect has been examined.Mixtures of SF–Lime pastes present a hydraulic setting which is due to the formation of a C–S–H phase (calcium silicate hydrate). The latter is semi-crystallized. It is characterized by the lines of X-ray diffraction, hk0 such as: 3,06 Å (220), 2,80 Å (400) and 1,83 Å (040).The mix design SF–Lime paste is thus a simplified approach of that of the mixtures SF–OPC in which the main reaction is the fixation, by the SF, of lime coming from the hydration of C₃S in the form of C–S–H.Tests have been carried out on two varieties of SF resulting from the same furnace with the presence of lime or Portland cement. The results show that the presence of certain impurities, by their actions on the solubility of silica plays a significant role on the evolution of the hydration of the principal components of Portland cements and the kinetics of lime fixation by the SF.Among the impurities contained in the SF, carbon delays considerably the hydration of the principal components of Portland cement (C₃S and C₃A) as well as the pozzolanic reactivity of the silica fume without removing it.     

Clinkers and cements obtained from raw mix containing ceramic waste as a raw material. Characterization,hydration and leaching studies

A clinker and a cement obtained from a raw mix containing ceramic waste as an alternative raw material were characterized in the present study. Their hydration, physical–chemical properties and leaching behaviour in different acid media were also explored. The findings showed that both the clinker and the cement met all the requirements set out in European standards EN 197-1 [1], although they had higher ZnO, ZrO₂, and B₂O₃ contents than an industrially produced reference product.According to the hydration studies, initial hydration was somewhat retarded in the new cement, which exhibited longer initial and final setting times and lower 2-day mechanical strength. The SEM/BSE/EDS microstructural study showed, however, that morphologically and compositionally, the hydration products formed were comparable to unadditioned Portland cement paste products. While low concentrations of Zn and B were observed to leach in acid media, the biotoxicity trials conducted confirmed that these concentrations were not toxic. Zr was retained in the cement pastes.     

Strength development of ternary blended cement with limestone filler and blast-furnace slag

The benefits of limestone filler (LF) and granulated blast-furnace slag (BFS) as partial replacement of portland cement are well established. However, both supplementary materials have certain shortfalls. LF addition to portland cement causes an increase of hydration at early ages inducing a high early strength, but it can reduce the later strength due to the dilution effect. On the other hand, BFS contributes to hydration after seven days improving the strength at medium and later ages.Mortar prisms in which portland cement was replaced by up to 20% LF and 35% BFS were tested at 1, 3, 7, 28 and 90 days. Results show that the contribution of LF to hydration degree of portland cement at 1 and 3 days increases the early strength of blended cements containing about 5–15% LF and 0–20% BFS. The later hydration of BFS is very effective in producing ternary blended cements with similar or higher compressive strength than portland cement at 28 and 90 days. Additionally, a statistical analysis is presented for the optimal strength estimation considering different proportions of LF and BFS at a given age. The use of ternary blended cements (PC–LF–BFS) provides economic and environmental advantages by reducing portland cement production and CO₂ emission, whilst also improving the early and the later compressive strength.     

Effect of PCs superplasticizers on the rheological properties and hydration process of slag-blended cement pastes

The effect of polycarboxylate (PC) superplasticizers with different structure on the rheological properties and hydration process of slag-blended cement pastes with a slag content between 0 and 75% has been studied. Fluidizing properties of PCs admixtures are significantly higher in slag-blended cement with respect to non-blended Portland cement. Also, it has been observed that the rise of the fluidity induced by the PCs on the cement pastes increases with the slag content. This effect is mainly attributed to a decrease in the amount of C₃A available to adsorb and consume admixture to form an organo-mineral phase. Consequently, the PC admixtures are absorbed onto the silicate phases of the clinker and onto the slag particles, inducing a repulsion and the concomitant reduction in yield stress despite a reduction in the zeta potential. The rheological results allow us to conclude that the highest increase of the fluidity is caused by the admixtures with highest molecular weight due to the higher steric repulsion induced. As a consequence of the adsorption of the PCs, a delay of the hydration process of the pastes has been observed.     

Synthesis of nanoparticles from slag and their enhancement effect on hydration properties of CaO/CaSO4-activated slag binder

Developing a low-cost and eco-friendly alternative to cement is of great significance for reducing the CO₂ emissions. CaO/CaSO₄-activated slag binder may only be served as a promising cementitious material when the severe defect in the early strength is overcame. In this study, gel-like nanoparticles with an average size of ～ 328 nm were prepared from the slag through dissolution at room temperature and reprecipitation at 50 °C. Subsequently, synthetic nanoparticles (SNPs) were added as a supplementary additive to enhance the strength of CaO/CaSO₄-activated slag binder. The effects of SNPs on the strength development, hydration kinetics, hydration products, and microstructure of the slag binders were investigated. The results indicated that the addition of moderate SNPs shortened the duration of induction period and improved the reaction rate in the acceleration period of the slag binders. As a result, large amounts of calcium aluminosilicate hydrate (C-A-S-H) gel was generated at early hydration ages. Meanwhile, SNPs increased the polymerization degree of this gel through the nucleation effect. Gel products’ well-filled the pore spaces between slag particles and yielded a compact microstructure, consequently enhancing the binder strength. The sample with adding 1.5 wt% SNPs exhibited the optimum strengths of 7.78 and 39.86 MPa after 1 and 28 days.     

Study of aluminum sulfate and anhydrite on cement hydration process

The influences of aluminum sulfate (AS) introduction and dosage on setting time, hydration heat evolution, hydration product type and pore structure of Portland cement were studied, and the influence of AS on concrete strength was investigated also. The results indicate that AS can effectively accelerate setting time of Portland cement and enhance concrete at early age (1 day) strength. AS can promote hydration process of calcium aluminate but inhibit that of calcium silicate. The effect of AS on hydration process becomes more significant along with the increased dosage; and the introduction of AS can promote the formation of AFt. The research results of this paper favor the opinion of the existence of AFt precursor; and the AFt precursor is amorphous AFm which could not be identified by XRD. With anhydrite as setting regulator, the amorphous AFm retention time is prolonged, and the endothermal peaks produced by amorphous AFm during DSC–MS measurement correspond to 80–160 and 830–910 °C, losing H₂O and SO₂ respectively.     

Effects of metakaolin on autogenous shrinkage of cement pastes

The effects of partial replacements (5%, 10%, 15% and 20%) of Portland cement by high-purity metakaolin (MK) on the autogenous shrinkage of pastes (water/binder ratios 0.3 and 0.5) were investigated. In order to distinguish the effect of heterogeneous nucleation and pozzolanic activity from the dilution effect, some mixes were prepared using a coarse powder (Q_ref) instead of MK (10% and 20% for both w/b ratios). The hydration of cement–MK pastes was followed qualitatively by differential thermal analysis (DTA). DTA showed that C–S–H and gehlenite (C₂ASH₈) were the main compounds produced by MK pozzolanic reaction. Results showed that the long-term autogenous shrinkage of cement–MK pastes, for both w/b ratios, decreased as the cement replacement level by MK increased. No expansion was observed at early ages, contrary to the findings of other authors. With the elimination of the dilution effect, it was shown, at early ages, that the increase of autogenous shrinkage of the cement–MK pastes relative to cement–Q_ref mixes was due to heterogeneous nucleation. At later ages, autogenous shrinkage became lower for cement–MK pastes than for cement–Q_ref pastes, surely because the pozzolanic activity of MK became predominant. This behavior i.e. reduction of autogenous shrinkage, is one more benefit confirming the interest of using MK in concrete.     

Influence of finely ground limestone on cement hydration

Some work has been carried out on the effect of calcium carbonate on cement paste, but there is no general agreement on the relative effects of different amounts of calcium carbonate on cement paste properties. The objective of the present work is to assess the effect of various amounts of calcium carbonate on the hydration of tricalcium silicate in order to explain the physico-chemical changes occurring during Portland cement hydration. It is shown that calcium carbonate has an accelerating effect on C₃S and cement hydration and leads to the precipitation of some calcium carbosilicate hydrate.     

Effect of barium hydrosilicates on the early hydration rate of Portland cement

We have studied the effect of a barium hydrosilicate-based modifier on the phase composition of Portland cement hydration products. The results demonstrate that the addition of a modifier containing barium hydrosilicates, silicic acid, and calcium carbonate makes it possible to reduce the nucleation rate of crystals of new phases during the induction period of the hydration process, increase alite (3СaO · SiO₂) hydration, and reduce the rate of aluminate phase (3CaO · Al₂O₃) hydration. The use of such a modifier increases the degree of cement hydration and the amount of calcium hydrosilicates and reduces the amount of forming portlandite and ettringite, thereby improving the mechanical properties and durability of the set cement.     

Microstructure and mechanical properties of accelerated sprayed concrete

Considering the different hydration processes of concrete without accelerator, sprayed concrete with low-alkali accelerator not only presents short setting times and high early-age mechanical properties but also yields different hydration products. This study presents an analysis of the mechanical properties of concrete with and without accelerator and sprayed concrete with three water–binder (w/b) ratios and four dosages of fly ash (FA) after different curing ages. It also examines the setting time, mineral composition, thermogravimetric–differential scanning calorimetry curves and microscopic images of cement pastes with different accelerator amounts. Furthermore, the setting time and microstructure of accelerated sprayed concrete with different w/b ratios and FA contents are examined. Results show that the retarded action of gypsum disappears in the accelerated cement–accelerator–water system. C₃A is quickly hydrated to form calcium aluminate hydrate (CAH) crystals, and a mesh structure is formed by ettringite, albite and CAH. A large amount of hydration heat improves the hydration rate of the cement clinker mineral and the resulting density, thereby improving mechanical properties at early curing ages. The setting times of the pastes increase with increasing w/b ratio and FA dosage. Thus, the hydration level, microstructure and morphology of the hydration products also change. Models of mechanical properties as functions of w/b, FA and curing age, as well as the relationship between compressive strength and splitting tensile strength, are established.     

Effect of nano clay particles on mechanical, thermal and physical behaviours of waste-glass cement mortars

Worldwide, around 2.6 billion tons of cement is produced annually. This huge size of production consumes large amounts of energy and is one of the largest contributors to carbon dioxide (CO₂) release. Accordingly, there is a pressing demand to minimise the quantity of cement used in the concrete industry. The main challenge to this is to get durable concrete with less cement and within reasonable cost. The economic, environmental and engineering benefits of reusing ground waste-glass powder (WGP) as a partial cement replacement has been established, but low glass reactivity and the possible alkali-silica reaction (ASR) are a drawback. Recent advances in nano-technology have revealed that nano-sized particles such as nano clay (NC) have a high surface area to volume ratio that provides the potential for tremendous chemical reactivity, accelerating pozzolanic activity and hindering ASR. This paper presents a laboratory study of the properties of NC/WGP cement composites. The microstructure, ASR, fracture energy, compressive and flexural properties of cement mortars containing WGP as a cement replacement with and without NC are investigated and compared with plain matrix. In addition, the hydration of cement compounds was followed by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and also X-ray diffraction (XRD). The results showed that incorporation of glass powder has a positive effect on the mechanical properties of cement mortars after 28 days of hydration. Also, the results revealed that the mechanical properties of the cement mortars with a hybrid combination of glass powder and NC were all higher than those of plain mortar and with glass powder after 28 days of hydration. In addition, the DTA/TGA results and XRD analysis showed a reduction in the calcium hydroxide (CH) content in mortars with glass powder and with a hybrid combination of glass powder and NC, which confirms the improvements of mechanical properties and occurrence of pozzolanic reaction after 28 days of hydration.     

Effect of further water curing on compressive strength and microstructure of CO2-cured concrete

This study aims to investigate the effects of further water curing on the compressive strength and microstructure of CO₂-cured concrete. The results showed that concrete with a residual w/c ratio of 0.25 showed the most rapid strength development rate upon further water curing due to hydration of uncarbonated cement particles. Thermogravimetric, IR-spectrophotometric and scanning electron microscope examinations indicated that further hydration of the cement particles could form C-S-H gel and ettringite crystals. The results showed that the calcite formed during the initial CO₂ curing was consumed during the further hydration of C₃A, and produced calcium monocarbonaluminate hydrate. Also, Ca(OH)₂ was not detected due to its reaction with the formed silica gel. Mercury intrusion porosimetry test results indicated that the porosity and pore size of the CO₂ cured mortar decreased further after water curing.